JP2006258901A - Non-magnetic one-component electrostatic charge image developing toner and image forming method using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-magnetic one-component electrostatic charge image developing toner which suppresses filming of a release agent to a photoreceptor and a developing member in a modified polyester-containing toner and is excellent in the release property from a roller and to provide an image forming method which prevents the staining of members in a process of oilless fixing and by which excellent image stability can be obtained. <P>SOLUTION: The non-magnetic one-component electrostatic charge image developing toner used in the image forming apparatus including a cleaning means for cleaning the toner remaining on the photoreceptor surface with a cleaning blade and an oilless fixing unit is the modified polyester-containing toner of 0.1 to 0.4 in the ratio of the peak derived from the release agent by an ATR method and the peak derived from the resin as the value to regulate the amount of the release agent existing at a depth from the toner surface down to 0.3 μm is 0.1 to 0.4. At least one external additive is an inorganic oxide and/or inorganic acid salt and the Mohs hardness of the external additive is 7 to 13. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention has a nonmagnetic one-component electrostatic charge developing toner, particularly an oilless fixing device in which a fixing member such as a heating member or a pressure member does not require fixing oil, and further has means for cleaning the image carrier. The present invention relates to a toner suitable for an image forming apparatus and an image forming method.
Furthermore, the present invention relates to an electrostatic charge developing toner composition using the toner and used in an electrophotographic technology copying machine, printer, and the like, and an image forming method using the toner composition. The present invention relates to an electrostatic charge developing toner composition and an image forming method capable of obtaining high image stability.

Conventionally, in electrophotography, an electrostatic latent image formed by charging and exposing a photoreceptor surface is developed with a colored toner to form a toner image, and the toner image is transferred to a transfer medium such as transfer paper. This is fixed with a heat roll or the like to form an image. Since untransferred toner generally remains on the surface of the photoreceptor after the toner image has been transferred, it is necessary to remove this residual toner by some cleaning means prior to the next image forming process. Further, generally, other foreign matters adhering to the surface of the photosensitive member are removed together with the residual toner by a cleaning means.
Various cleaning means such as a fur brush, a magnetic brush, a rubber blade, and the like can be used as a cleaning means for removing the residual toner and adhered matter after the transfer. A means for scraping off the toner by rubbing the body is generally used.
Further, dry development methods employed in electrophotography, electrostatic recording, and the like include a method using a two-component developer composed of a toner and a carrier, and a method using a one-component developer not containing a carrier. The former method provides a relatively stable and good image, but it is difficult to obtain a constant quality image over a long period of time because carrier deterioration and a change in the mixing ratio of toner and carrier are likely to occur. In addition, there are difficulties in maintaining and managing the apparatus and making it compact. In view of this, a method using the latter one-component developer which does not have such drawbacks has been attracting attention.

  By the way, in this system, means for visualizing the electrostatic latent image formed on the latent image carrier by the toner (developer) usually conveyed by at least one toner conveying member and the conveyed toner. In this case, the layer thickness of the toner transported on the surface of the toner transport member must be made as thin as possible. In particular, when a one-component developer is used and a toner having a high electrical resistance is used, the toner needs to be charged by a developing device, so that the toner layer thickness must be significantly reduced. This is because if the toner layer is thick, only the surface of the toner layer is charged, and the entire toner layer is difficult to be uniformly charged.

  In view of this demand, various methods have been proposed as means for regulating the toner layer thickness on the toner conveying member (toner layer thickness regulating means). As a typical example, a regulating blade is used, and this blade is used as the toner conveying member. Thus, the toner conveyed on the surface of the toner conveying member is pressed by a pressing member (regulating blade) to control the toner layer thickness. There is also a type that obtains the same effect by contacting a roller instead of a blade.

In recent years, oilless fixing devices have been attracting attention from the viewpoint of writing properties and the like. Of these, the heat roller method is the cheapest and most compact. A heat roller type fixing device has a heat source such as a halogen lamp inside, and has a rotation roller pair of a fixing roller that is adjusted to a predetermined temperature and a pressure roller that is in pressure contact with the fixing roller. A recording material is introduced into a contact portion of the rotating roller pair, that is, a fixing nip portion, and conveyed, and an unfixed toner image is melted and fixed by heat and pressure from the fixing roller and the pressure roller.
However, in order to realize so-called oil-less fixing that does not use oil in the fixing portion, the presence of a release agent near the surface of the toner is more advantageous for releasability, but one component that does not contain a carrier. Due to the structure of the developer, process member contamination is likely to occur.

In the case of the wet polymerization toner of Patent Document 1 in which the development and the cleaning member are less contaminated with the release agent, when the release agent is contained, it is difficult to finely disperse the release agent in the toner, and the release of a large particle size is difficult. The agent was often in the center of the toner. For this reason, even if heat and pressure are applied by the fixing device, it is difficult for the toner to ooze from the toner center to the toner surface, and the effect of preventing hot offset to the roller cannot be exhibited.
On the other hand, when a large amount of the release agent is exposed on the toner surface as proposed in Patent Document 2, it acts advantageously in the fixing process to prevent hot offset, but the release agent is generally softened. Since the dots and the like are low and the hardness is low, fusion occurs during rubbing with a regulating blade or rubbing with a cleaning blade in the development process, causing image defects.
In addition, when a toner having a release agent on its surface is used, such as in Patent Document 3 and Patent Document 4, the same problems as in the case where there are many release agents may occur.

JP 2001-34016 A JP-A-8-101526 JP 2003-131416 A JP 2003-207925 A

The present invention has been made for the purpose of solving the above-mentioned problems in the prior art.
An object of the present invention is to use a modified polyester-containing toner, to suppress filming of a release agent on a photosensitive member and a developing member, and to provide excellent non-magnetic property and excellent releasability from a roller in an oilless fixing system. The object is to provide a toner for developing an electrostatic component. Another object of the present invention is to provide an image forming method capable of preventing process member contamination in an oilless fixing toner and obtaining excellent image stability.

According to a first aspect of the present invention, there is provided a nonmagnetic one-component electrostatic charge developing toner used in an image forming apparatus equipped with a cleaning means for cleaning toner remaining on the surface of a photoreceptor with a cleaning blade and an oilless fixing device. As a value that defines the amount of the release agent existing at a depth of up to 0.3 μm, the ratio of the release agent-derived peak (2850 cm ⁻¹ ) to the resin-derived peak (828 cm ⁻¹ ) by the ATR method is 0.1 to 0.1 A modified polyester-containing toner of 0.4, wherein at least one external additive is an inorganic oxide and / or an inorganic acid salt, and the external additive has a Mohs hardness of 7 to 13. The present invention relates to a non-magnetic one-component electrostatic charge developing toner.
In the second aspect of the present invention, the toner particles are formed by dissolving or dispersing a composition containing a toner binder component, a colorant, and a release agent composed of a modified polyester resin capable of reacting at least with active hydrogen in an organic solvent. The solution or dispersion is reacted with a crosslinking agent and / or an extender in an aqueous medium containing a dispersant, and after removing the solvent from the resulting polymer dispersion, the resin fine particles adhering to the toner surface are washed. The toner according to claim 1, wherein the toner is obtained by desorption.
A third aspect of the present invention relates to the nonmagnetic one-component electrostatic charge developing toner according to claim 1, wherein the content A (mass%) of the release agent in the toner particles is 4 ≦ A ≦ 10.
The fourth aspect of the present invention is the nonmagnetic one-component electrostatic charge development according to any one of claims 1 to 3, wherein the release agent is a fatty acid ester wax composed of carnauba wax and / or a divalent to hexavalent polyhydric alcohol. Relates to toner.
The fifth aspect of the present invention is that the external additive is a compound selected from the group consisting of titanium oxide, aluminum oxide, strontium titanate, calcium titanate and magnesium titanate. The present invention relates to a one-component electrostatic charge developing toner.
A sixth aspect of the present invention relates to the nonmagnetic one-component electrostatic charge developing toner according to any one of claims 1 to 5, wherein the number average diameter of the external additive is 30 to 800 nm.
According to a seventh aspect of the present invention, in the image forming method using the nonmagnetic one-component electrostatic charge developing toner according to any one of claims 1 to 6, the cleaning blade has a JIS-A hardness of 60 ° to 80 ° and a photosensitive member. The present invention relates to an image forming method characterized by being used at a linear pressure of 25 to 45 N / m.
An eighth aspect of the present invention is the image forming method using the nonmagnetic one-component electrostatic charge developing toner according to any one of claims 1 to 6, wherein the oilless fixing device is composed of a two-roller composed of a heating roller and a pressure roller. The present invention relates to an image forming method using a fixing system.
According to a ninth aspect of the present invention, when developing a latent image on an image carrier in a development process using the nonmagnetic one-component electrostatic charge developing toner according to any one of claims 1 to 6, a non-contact alternating electric field is developed. Is applied to the image forming method.

In the present invention, a peak derived from the releasing agent by ATR method as a value that defines the release agent amount present on the depth from the toner surface to 0.3 [mu] m (2850 cm ^-1) and the resin derived from the peak (828 cm ^-1 ) Is 0.1 to 0.4, preferably 0.11 to 0.3, and more preferably 0.11 to 0.25. By setting the amount within this range, the release agent is efficiently eluted between the roller surface of the fixing device and the toner at the time of fixing, and an excellent fixing separation performance can be obtained even in an oilless fixing system. If it is less than 0.1, the effect of the release agent cannot be fully exhibited, and high temperature offset occurs. When it is larger than 0.4, a problem occurs in heat-resistant storage stability.

  Further, the Mohs hardness of the external additive is 7 to 13, and preferably 7 to 12, so that the adhering matter to the surface of the photoconductor is not damaged when the cleaning blade and the photoconductor are rubbed without damaging the surface of the photoconductor. In addition, it is possible to remove deposits on the surface of the regulating blade when the regulating blade and the developing roller are rubbed. If it is smaller than 7, a sufficient polishing effect cannot be obtained, deposits are accumulated on the regulating blade, a conveyance failure occurs in a line shape, and an image defect occurs in a white line shape. Further, medaka is generated on the photosensitive member, and an image defect due to black spots occurs on the image. If it is larger than 13, the surface of the photoreceptor is scraped and the life is shortened.

  As the toner binder component, it is preferable to use a toner binder component composed of a modified polyester resin in which toner particles can react with at least active hydrogen in an organic solvent. The reason is that, in the case of using an oilless fixing device in the non-magnetic one-component electrostatic charge development method, if the amount of the release agent is large, the fixing characteristics are improved, but process member contamination occurs. For the above reason, when it is impossible to use a large amount of a release agent, the mold release is performed by adjusting the viscoelasticity with a modified polyester in order to ensure the release property while preventing the contamination of the parts of the process. Can be secured.

  In the present invention, the content A (% by mass) of the release agent in the toner particles is preferably in the range of 4 ≦ A ≦ 10. When the content is less than 4% by mass, the effect of improving the offset resistance and the oil-less fixing separation performance are insufficient, and when the content is more than 10% by mass, the heat resistant storage stability is lowered.

  In the present invention, the release agent is a fatty acid ester wax composed of carnauba wax and / or a divalent to hexavalent multi-valued alcohol, whereby a toner having good dispersion in the polyester toner can be obtained.

  The toner suitably used in the present invention includes at least a modified polyester having a functional group containing a nitrogen atom (hereinafter sometimes referred to as a polyester prepolymer), an unmodified polyester (hereinafter sometimes simply referred to as a polyester), A toner obtained by crosslinking and / or extending a toner material solution in which a colorant and a release agent are dispersed in an organic solvent in an aqueous solvent. Hereinafter, the constituent material and the manufacturing method of the toner will be described.

(Unmodified polyester)
Unmodified polyester (hereinafter sometimes simply referred to as polyester) is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.

Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable.
Examples of the dihydric alcohol (DIO) 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, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, 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.
The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred.
Divalent carboxylic acids (DIC) 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) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
The polycondensation reaction between a polyhydric alcohol (PO) and a polycarboxylic acid (PC) is carried out in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and heated to 150 to 280 ° C. while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group.

  The hydroxyl value of the polyester is preferably 5 or more, and the acid value of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and furthermore, when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.

  The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

(Modified polyester)
In addition to the unmodified polyester obtained by the above polycondensation reaction, the binder resin used in the present invention is modified to have a urethane or / and urea group in order to adjust viscoelasticity for the purpose of preventing offset and the like. A polyester resin is preferably contained. The content of the modified polyester resin having a urethane or / and urea group 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, the terminal carboxyl group and hydroxyl group of the polyester and a polyvalent isocyanate compound (PIC) ), A modified polyester resin having an isocyanate group (hereinafter sometimes referred to as a polyester prepolymer) and an amine that reacts with the binder resin are mixed in a binder resin, and a chain is formed during or after granulation. It is preferable that the modified polyester resin having the urethane or / and urea group is obtained by elongation or / and crosslinking reaction. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity in the core portion.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; phenol derivatives, oximes, polyisocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

  The amount of the polyvalent isocyanate compound (PIC) used is usually 5/1 to 1/1, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group, preferably Is 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

The ratio of the amines (B) used is the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the polyester prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance may be deteriorated.

  The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance may be deteriorated.

  The urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester.

  When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).

  In addition, in the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000-15000, preferably 2000-10000, more preferably 2000-8000. If it exceeds 15000, the low-temperature fixability and the glossiness when used in a full-color device may deteriorate.

By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the glossiness when used in a full-color image forming apparatus are improved. Therefore, it is preferable to use the urea-modified polyester alone. The unmodified polyester may include a polyester modified with a chemical bond other than a urea bond.
The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition and / or chemical structure.

  The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance is deteriorated, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient.

  In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded together with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

(Release agent)
As the release agent, a low melting point wax having a melting point of 60 to 100 ° C., preferably 70 to 90 ° C., is more effectively used as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. This works against high temperature offset without applying a release agent such as oil to the fixing roller. Examples of such a wax component include the following. The waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline and petrolatum. And petroleum wax. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. . In the present invention, carnauba wax and fatty acid ester wax which is a synthetic wax of ester are preferably used.
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.
Moreover, the addition amount of the mold release agent of this invention is the mass% in a resin component.

(External additive)
As the external additive used in the present invention, at least one external additive is an inorganic oxide and / or an inorganic acid salt, and the external additive has a Mohs hardness of 7 to 13. Here, the Mohs hardness is a 15-step modified Mohs hardness. Specific examples include titanium oxide (Mohs hardness 7), aluminum oxide (Mohs hardness 12), strontium titanate (Mohs hardness 8), calcium titanate (Mohs hardness 7), magnesium titanate (Mohs hardness 7), and the like. Can do. The number average diameter of the external additive is preferably 30 to 800 nm, more preferably 40 to 700 nm. If it is smaller than 30 nm, it is difficult to obtain a polishing effect, and the effect is not sufficient. If it is larger than 800 nm, the photoreceptor may be scratched or the life of the photoreceptor may be shortened.

In addition to the external additives used in the present invention, the following external additives may be used in combination.
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 0.5 μm. 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 wt% of the toner, and particularly preferably 0.01 to 3.0 wt%.
Specific examples of the inorganic fine particles include, for example, silica, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, sulfuric acid. Examples thereof include barium, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Next, a toner manufacturing method will be described. Here, the preferred production methods (1) to (5) are shown in the following configuration order, but are not limited thereto.

(Toner production method)
(1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

(2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Moreover, as the cationic surfactant, aliphatic quaternary ammonium such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt which has a right fluoroalkyl group is used. Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

  The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao Corporation), SGP (manufactured by Soken Co., Ltd.), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).

  In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Of lauric acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or vinyl alcohol ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Nitrogen-containing compounds such as ethyleneimine, or homopolymers or copolymers such as those having heterocycles thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, a high-speed shearing type is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

(3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

(4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

(5) Toner is obtained by externally adding inorganic fine particles to the toner base particles obtained above.
The external addition of the inorganic fine particles is performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

  The toner preferably has a volume average particle size in the range of 3 to 10 μm. The smaller the particle size, the higher the reproducibility of fine lines and the higher quality image can be obtained. If the thickness is less than 3 μm, it is difficult to form droplets. The particle size distribution is preferably such that the ratio (Dv / Dn) of the volume average particle size (Dv) to the number average particle size (Dn) is 1.05 to 1.40. By sharpening the particle size distribution, the charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and the transfer rate can be increased. If Dv / Dn is less than 1.05, it is difficult to produce, and if it exceeds 1.40, the charge amount distribution is widened, so that it is difficult to obtain a high-quality image.

  In addition, the sphericity of the toner can be made relatively high. Here, when the circularity of the image projected with the sphericity is SR, the average circularity is preferably 0.93 or more. Definition: SR = (peripheral length of circle having the same area as the projected particle area / perimeter length of projected particle image) × 100%, and the closer the toner is to a true sphere, the closer the value is to 100%.

  Various cleaning means such as a fur brush, a magnetic brush, a rubber blade, and the like can be used as a cleaning means for removing residual toner and adhered matter after the transfer. The cleaning blade is made of an elastic material. A means for scraping off the toner by rubbing the body is generally used. The cleaning blade is preferably used at a JIS-A hardness of 60 ° to 80 ° and a linear pressure on the photoreceptor of 25 to 45 N / m. When the JIS-A hardness is less than 60 °, the cleaning blade is abruptly worn and lacks durability. If it is larger than 80 °, the photoreceptor is abraded so that the durability is insufficient.

  Examples of the fixing device include those using a belt and those using a roller. Among them, the heat roller type is the cheapest and most compact. The heat roller method is a two-roll fixing method composed of a heat roller and a pressure roller. In this case, the pressure roller and the heating roller may have a rubber surface layer or may not have a rubber surface layer. When color toner is used, it is most preferable that both rollers have a rubber surface layer in consideration of the paper discharge direction and fixing time.

  Examples of non-magnetic one-component development methods include contact and non-contact development. In consideration of the life of the photoreceptor, non-contact development is preferable, and it is desirable to apply an alternating electric field in order to obtain a good image.

[Surface release agent amount]
The amount of the release agent in the vicinity of the toner particle surface can be obtained by ATR (total reflection absorption infrared spectroscopy). From the measurement principle, the analysis depth is about 0.3 μm, and by this analysis, the relative release agent amount in the depth region of 0.3 μm from the surface of the toner particles can be obtained. The measuring method is as follows.
First, as a sample, 3 g of toner was pressed with an automatic pellet molding machine (Type M No. 50 BRP-E; manufactured by MAEKAWA TESTING MACHINE CO.) For 1 minute at a load of 6 t to produce a 40 mmφ (about 2 mm thick) pellet. . The toner pellet surface was measured by the ATR method. The microscopic FTIR apparatus used was one in which a MultiScope FTIR unit was installed in Spectrum One manufactured by PERKIN ELMER, and measurement was performed with a micro ATR of a germanium (Ge) crystal having a diameter of 100 μm. The measurement was performed at an infrared incident angle of 41.5 °, a resolution of 4 cm −1 and a total of 20 times.
The intensity ratio (P2850 / peak of the obtained release agent-derived peak (2850 cm ⁻¹ : peak derived from —CH of methylene group) and the peak derived from binder resin (828 cm ⁻¹ : peak derived from aromatic —CH) P828) was defined as a relative release agent amount in the vicinity of the toner particle surface. The average value after measuring four times by changing the measurement location was used.

[External additive particle size (SEM)]
A method for measuring the particle diameter of the external additive will be described.
The particle diameter of 1000 particles was measured by SEM, and the number average diameter was calculated.
[Toner particle size (Coulter)]
Next, a method for measuring the particle size distribution of toner particles will be described.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing an about 1% NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of the measurement sample is further added as a solid content.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

[Average circularity]
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle.
This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(1) With the configuration of claim 1, it is possible to efficiently release the roller and prevent filming and obtain a good image.
(2) According to the constitution of claim 2, a toner having an appropriate elastic component can be produced, and a toner having excellent thermal storage stability and capable of fixing with low sound can be obtained.
(3) According to the configuration of claim 3, it is possible to obtain a toner having both heat storage stability and good fixing releasability.
(4) According to the configuration of claim 4, a toner having good dispersion in the polyester toner can be obtained.
(5) With the configuration of claim 5, good cleaning characteristics can be obtained.
(6) With the constructions of claims 6 to 7, it was possible to obtain good cleaning characteristics while maintaining the life of the photoreceptor.
(7) With the configuration of the eighth aspect, an inexpensive and good fixing characteristic can be obtained.
(8) With the configuration of the ninth aspect, a good image can be obtained while maintaining the life of the photoreceptor.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Parts” means all parts by mass.

[Toner base 1]
(Synthesis of low molecular weight polyester)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel, and leave for 2 hours at 180 ° C. under normal pressure. The reaction yielded [low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

[Synthesis of modified polyester (prepolymer)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

[Synthesis of master batch]
Carbon black (Cabot Co., Ltd. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

[Preparation of pigment / WAX dispersion (oil phase)]
378 parts of [Low molecular weight polyester 1], 200 parts of carnauba wax, and 947 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. [Pigment / WAX Dispersion 1] was prepared with ethyl acetate so that the solid concentration (130 ° C., 30 minutes) was 50%.

(Preparation of aqueous phase)
953 parts of water, 88 parts of a 25 wt% aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), 48.48% of sodium dodecyl diphenyl ether disulfonate. 90 parts of 5% aqueous solution (Eleminol MON-7: Sanyo Chemical Industries) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

[Emulsification process: Mixing amines and sulfonating agent in oil phase]
[Pigment / WAX Dispersion 1] 976 parts and 6.0 parts of isophoronediamine as amines were put in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika). After adding 137 parts and mixing with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, add 1200 parts of [aqueous phase 1] and using TK homomixer at 13,000 rpm for 20 minutes. By mixing, [Emulsified slurry 1] was obtained.

[Desolvent]
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

[Washing → Drying]
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. The volume average particle diameter (Dv) was 5.6 μm, the number average particle diameter (Dp) was 5.0 μm, Dv / Dp was 1.12 and the average circularity was 0.97.

[Toner base 2]
[Toner Base 2] was obtained in the same manner as the toner base except that 265 parts of carnauba wax were used when the pigment / WAX dispersion (oil phase) was prepared. The volume average particle diameter (Dv) was 5.6 μm, the number average particle diameter (Dp) was 5.0 μm, Dv / Dp was 1.12 and the average circularity was 0.96.

[Toner base 3]
[Toner Base 3] was obtained in the same manner as the toner base except that 95 parts of carnauba wax was used when the pigment / WAX dispersion (oil phase) was prepared. The volume average particle diameter (Dv) was 5.5 μm, the number average particle diameter (Dp) was 4.9 μm, Dv / Dp was 1.12 and the average circularity was 0.96.

[Toner base 4]
[Toner Base 4] was obtained in the same manner as the toner base except that 70 parts of carnauba wax was used when the pigment / WAX dispersion (oil phase) was prepared. The volume average particle diameter (Dv) was 5.6 μm, the number average particle diameter (Dp) was 4.9 μm, Dv / Dp was 1.14, and the average circularity was 0.96.

[Toner base 5]
[Toner base 5] was obtained in the same manner as the toner base except that 300 parts of carnauba wax was used when preparing the pigment / WAX dispersion (oil phase). The volume average particle diameter (Dv) was 5.4 μm, the number average particle diameter (Dp) was 4.9 μm, Dv / Dp was 1.10, and the average circularity was 0.97.

[Toner base 6]
[Toner base 6] was obtained in the same manner as toner base 1 except that 200 parts of fatty acid ester wax (WEP-5: manufactured by Nippon Oil & Fats Co., Ltd.) was used when the pigment / WAX dispersion (oil phase) was prepared.
The volume average particle diameter (Dv) was 5.5 μm, the number average particle diameter (Dp) was 4.9 μm, Dv / Dp was 1.12 and the average circularity was 0.96.

[Toner base 7]
Toner base 7 was prepared in the same manner as toner base 1 except that 100 parts of carnauba wax and 100 parts of fatty acid ester wax (WEP-5: manufactured by Nippon Oil & Fats Co., Ltd.) were used when the pigment / WAX dispersion (oil phase) was prepared. ] Was obtained.
The volume average particle diameter (Dv) was 5.4 μm, the number average particle diameter (Dp) was 4.9 μm, Dv / Dp was 1.12 and the average circularity was 0.96.

Example 1
[Toner Base 1] 100 parts of hydrophobic silica TG811F (manufactured by Cabot), 1.0 part of RX50 (manufactured by Nippon Aerosil Co., Ltd.), strontium titanate (number average) as an external additive used in the present invention Toner 1 of the present invention was obtained by mixing 0.8 parts of 400 nm in diameter with a Henschel mixer.
In Examples 2 to 6 and Comparative Examples 1 to 4, toners 2 to 10 were obtained by combining the toner base of Table 1 and the external additive used in the present invention.

[Evaluation]
Evaluation was carried out by the following evaluation methods, and the results were as shown in Table 1.
(Fixed separation evaluation)
Using a non-magnetic one-component development type full-color printer LP-1500C (manufactured by Epson Corporation), a solid band image (adhesion amount 9 g / m ² ) having a width of 36 mm is printed on the tip 3 mm with test pattern A4 longitudinal paper. Created an image. This unfixed image was fixed at various fixing temperatures using the following fixing device, and a separable temperature range was obtained. The paper used and the direction of paper passing were 45 g / m ² paper of Y-th vertical paper that is unfavorable for separability. The peripheral speed of the fixing device was 120 mm / sec.
The fixing device used was a soft roller type with a fluorine surface layer composition. Specifically, the heating roller has an outer diameter of 40 mm, an aluminum core metal having a thickness of 1.5 mm made of silicone rubber, and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer. It has a heater inside the aluminum core. The pressure roller has an outer diameter of 35 mm, and has an elastic body layer made of silicone rubber and a thickness of 3 mm and a PFA surface layer on an aluminum cored bar. A nip (nip width 7 mm) is formed at the pressing portion between the heating roller and the pressure roller. The experiment was conducted without using fixing oil.
A: Separable temperature range was 50 ° C. or higher B: Separable temperature range was 30 ° C. or higher and lower than 50 ° C. ×: Separable / non-offset temperature range was lower than 30 ° C. (medaka)
A predetermined print pattern with a B / W ratio of 6% was continuously printed in an N / N environment (23 ° C., 45%) using a full-color printer LP-1500C (manufactured by Epson, non-contact development method). The cleaning blade had a JIS-A hardness of 75 ° and was used at a linear pressure of 38 N / m on the photoreceptor. After continuous printing of 2000 sheets in an N / N environment (after durability), the surface of the photoreceptor was visually observed and evaluated. Judgment criteria are as follows.
◎: No filming or medaka on the photoconductor, no problem. ○: Filming or medaka on the photoconductor, but not visible on the copied image. ×: Filming and medaka are generated on the photoconductor, and can be confirmed on the image.
There was a problem in practical use.
(Regulator blade adhering)
In the same manner as the evaluation method for cleaning property, continuous copying was performed, and after the continuous copying of 2000 sheets in an N / N environment (after endurance), the state of the developing roller of the developing device and the copy image were visually observed and evaluated. Judgment criteria are as follows.
◎: No streaks or unevenness occurred on the developing roller ○: Although some streaks or unevenness occurred on the developing roller, there were no vertical streaks on the copied image, and there was no problem in practical use ×: On the developing roller There are many streaks or unevenness in
Vertical streaky omissions occurred on the copied image, causing a problem in practical use.
(Photoconductor lifetime)
In the same manner as the evaluation method for cleaning property, continuous copying was performed, and after 2,000 continuous copying in an N / N environment (after endurance), the state on the photoreceptor and the copy image were visually observed and evaluated. Judgment criteria are as follows.
◎: No streaking due to scraping on the photoconductor ○: Although slight streaking was generated on the photoconductor, there were no vertical streaks on the copied image, and there was no practical problem ×: Sleeve There were many streaks on the top, and vertical streaky image unevenness occurred on the copied image, causing problems in practical use.
(Thermal storage stability)
The toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. The residual ratio on the wire mesh was used as an index for heat resistant storage stability. The heat resistant storage stability was evaluated in the following four stages.
×: 30% or more △: 20-30%
○: 10 to 20%
A: Less than 10%

Claims (9)

In a non-magnetic one-component electrostatic charge developing toner used in an image forming apparatus equipped with a cleaning means for cleaning toner remaining on the surface of a photoreceptor with a cleaning blade and an oilless fixing device, a depth of 0.3 μm from the toner surface. modified polyester ratio of the peak derived from the releasing agent by ATR method as a value for defining the release agent amount present (2850 cm ^-1) and the resin derived from the peak (828 cm ^-1) is 0.1 to 0.4 in A non-magnetic one-component electrostatic charge comprising a toner containing at least one external additive is an inorganic oxide and / or an inorganic acid salt, and the external additive has a Mohs hardness of 7 to 13. Developing toner.   A solution or dispersion formed by dissolving or dispersing a composition containing a toner binder component, a colorant, and a release agent composed of a modified polyester resin in which toner particles can react with at least active hydrogen in an organic solvent, It is obtained by reacting with a crosslinking agent and / or an extender in an aqueous medium containing a dispersant, removing the solvent from the resulting polymer dispersion, and then washing and desorbing the resin fine particles adhering to the toner surface. The non-magnetic one-component electrostatic charge developing toner according to claim 1.   The toner for non-magnetic one-component electrostatic charge development according to claim 1, wherein the content A (mass%) of the release agent in the toner particles is 4 ≦ A ≦ 10.   The toner for non-magnetic one-component electrostatic charge development according to any one of claims 1 to 3, wherein the release agent is a fatty acid ester wax composed of carnauba wax and / or a divalent to hexavalent polyhydric alcohol.   The nonmagnetic one-component electrostatic charge developing toner according to any one of claims 1 to 4, wherein the external additive is a compound selected from the group consisting of titanium oxide, aluminum oxide, strontium titanate, calcium titanate and magnesium titanate. .   The toner for non-magnetic one-component electrostatic charge development according to any one of claims 1 to 5, wherein the number average diameter of the external additive is 30 to 800 nm.   7. The image forming method using the non-magnetic one-component electrostatic charge developing toner according to claim 1, wherein the cleaning blade has a JIS-A hardness of 60 ° to 80 ° and a linear pressure on the photosensitive member of 25 to 45 N / m. And an image forming method.   The image forming method using the non-magnetic one-component electrostatic charge developing toner according to any one of claims 1 to 6, wherein the oil-less fixing device is a two-roll fixing type constituted by a heating roller and a pressure roller. An image forming method. A development process using the non-magnetic one-component electrostatic charge developing toner according to claim 1, wherein an alternating electric field is applied in a non-contact manner when developing a latent image on the image carrier. Image forming method.