JP5347398B2 - Developer and image forming apparatus - Google Patents

Description

The present invention relates to a current image agents and image forming apparatus.

  In general, electrophotographic image formation is performed by developing a latent image formed on the surface of a photoreceptor with toner using a developing roller, and then transferring and fixing the toner image onto a sheet. Among these, from the viewpoints of high speed printing, high image quality, colorization, simple apparatus configuration, etc., a non-magnetic one-component developing system using a non-magnetic one-component developer (non-magnetic toner) is frequently used. In the non-magnetic one-component developing system, an elastic developing roller having at least a surface of a semiconductive elastic material such as urethane rubber is used as the developing roller. Further, a blade is used as a member for charging the nonmagnetic one-component developer while regulating the thickness of the nonmagnetic one-component developer formed on the developing roller.

  A non-magnetic one-component developer is a pulverization method in which a composition obtained by kneading a material containing a binder resin, a colorant and a release agent is pulverized and then classified, or the binder resin and color in an aqueous medium. Particles by spraying a fluid containing a polymerization method (for example, suspension polymerization method, emulsion polymerization aggregation method, dissolution suspension method) to form particles containing an agent and a release agent, a binder resin, a colorant and a release agent It is manufactured by using a spray granulation method or the like for forming.

  On the other hand, with the colorization of printed matter, various binder resins having excellent color developability, transparency when printed on OHP paper, and low-temperature fixability have been studied. Among them, polyester is frequently used because it has excellent durability even when the molecular weight is lowered in order to satisfy transparency, and also has good pigment dispersibility.

Patent Document 1 discloses an electrostatic image development containing resins (A) and (B) having a glass transition point of 58 ° C. or higher and lower than 75 ° C. and a resin (C) having a glass transition point of 45 ° C. or higher and lower than 58 ° C. Toner is disclosed. However, when such a toner having a low glass transition point of the resin (C) is used as a non-magnetic one-component developer, there is a problem that the toner is fixed because the pressing force of the blade against the developing roller is large.
Japanese Patent No. 3219230

The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a non-magnetic one-component developer excellent in low-temperature fixability and anti-sticking property and an image forming apparatus using the developer.

The invention according to claim 1 is a developer comprising a non-magnetic toner having base particles containing a binder resin, a colorant and a release agent , wherein the binder resin is a polyester, Obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid, the polyhydric alcohol is an aromatic compound, and was produced in the same manner as the non-magnetic toner except that the release agent was not added. The particles have only a glass transition point of 60 ° C. or more and less than 70 ° C. and a glass transition point of 70 ° C. or more and less than 78 ° C., and the maximum value of the glass transition point of 60 ° C. or more and less than 70 ° C. The difference from the maximum value of the glass transition point of less than 0 ° C. is 3 ° C. or more.

  The invention according to claim 2 is the developer according to claim 1, wherein the endothermic curve of the base particle has a maximum endothermic peak of 30 ° C. or more and 200 ° C. or less at 65 ° C. or more and 85 ° C. or less. And

A third aspect of the present invention is the developer according to the first or second aspect , wherein the nonmagnetic toner further includes inorganic particles.

According to a fourth aspect of the invention, in the developer according to the third aspect , the inorganic particles are silica particles .

The invention according to claim 5 is the developer according to claim 3 or 4 , wherein the non-magnetic toner has a content of the inorganic particles of 1.5% by mass or more and 5% by mass. .

A sixth aspect of the present invention is the developer according to any one of the first to fifth aspects, wherein the base particles have a volume average particle diameter of 5 μm to 12 μm.

The invention according to claim 7 is the developer according to any one of claims 1 to 6 , wherein the base particles have an average circularity of 0.89 to 0.95. .

The invention according to claim 8, in the image forming apparatus, the photosensitive member, means for forming an electrostatic latent image on the photosensitive member, an electrostatic latent image formed on the photosensitive body, according to claim 1 to 7 A means for developing with the developer according to any one of the above, a means for forming a toner image, a means for transferring the toner image formed on the photoconductor to the transfer target, and a toner transferred to the transfer target It has a means for fixing an image .

According to the present invention, it is possible to provide a non-magnetic one-component developer excellent in low-temperature fixability and anti-sticking property and an image forming apparatus using the developer.

  Next, the best mode for carrying out the present invention will be described.

  The developer of the present invention comprises a non-magnetic toner having base particles containing a binder resin, a colorant and a release agent, and the binder resin has a glass transition point of 60 ° C. or higher and lower than 70 ° C. and a temperature of 70 ° C. or higher and 78 ° C. And the difference between the maximum value of the glass transition point of 60 ° C. or more and less than 70 ° C. and the maximum value of the glass transition point of 70 ° C. or more and less than 78 ° C. is 3 ° C. or more. This suppresses physical toner destruction and suppresses fusion caused by heat generated between the member that regulates the thickness of the developer supplied to the developer carrying member and the developer carrying member. Therefore, the developer of the present invention is excellent in sticking resistance. Furthermore, the developer of the present invention is excellent in low-temperature fixability.

  The non-magnetic toner includes a first resin having a glass transition point of 60 ° C. or higher and lower than 70 ° C., a second resin having a glass transition point of 70 ° C. or higher and lower than 78 ° C., a colorant, and a release agent. However, the glass transition point of the binder resin is the same as that of the nonmagnetic toner except that a material having a glass transition point other than the first resin and the second resin is not added. Means the glass transition point of the particles. The glass transition point can be measured using a differential scanning calorimeter (DSC).

  When the binder resin has a glass transition point of less than 60 ° C., the developer sticks between the member that regulates the thickness of the developer supplied to the developer carrying member and the developer carrying member. Further, when the binder resin has a glass transition point of 78 ° C. or higher, the low-temperature fixability of the developer is lowered.

  When the binder resin has only a glass transition point of 60 ° C. or more and less than 70 ° C., the fixing of the developer between the member that regulates the thickness of the developer supplied to the developer carrying member and the developer carrying member Will occur. Further, when the binder resin has only a glass transition point of 70 ° C. or higher and lower than 78 ° C., the low-temperature fixability of the developer is lowered.

  Furthermore, a component having a relatively high glass transition point when the difference between the maximum value of the glass transition point of 60 ° C. or more and less than 70 ° C. and the maximum value of the glass transition point of 70 ° C. or more and less than 78 ° C. is less than 3 ° C. Increases, and the low-temperature fixability of the developer decreases.

  In the present invention, when the first resin and the second resin are compatible, the glass transition point of the binder resin becomes a single temperature between the glass transition points of the first resin and the second resin, and the low temperature Fixability and anti-sticking property cannot be fully expressed.

  In the present invention, the endothermic curve of the base particles preferably has a maximum endothermic peak of 30 to 200 ° C. at 65 to 85 ° C., more preferably 70 to 85 ° C. When this maximum endothermic peak is present at less than 65 ° C., the developer may be stuck between the member that regulates the thickness of the developer supplied to the developer carrying member and the developer carrying member. If it exceeds 85 ° C., the low-temperature fixability of the developer may deteriorate. In addition, the endothermic curve of the base particles can be measured using a differential scanning calorimeter (DSC).

  Although it does not specifically limit as 1st resin and / or 2nd resin, Polycondensation type resin, (meth) acrylic resin, styrene- (meth) acrylic resin, epoxy resin, cyclic olefin copolymer (For example, TOPAS ( Two or more types may be used in combination, among them, from the viewpoint of oilless fixing, polycondensation resin is preferable, and polyester is particularly preferable.

  The polyester is obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. Examples of the polyhydric alcohol include dihydric alcohols, trihydric alcohols and the like, and two or more kinds may be used in combination. Examples of the divalent alcohol include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3,3) -2,2-bis (4-hydroxyphenyl). ) Bisphenol A alkylene oxides such as propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane Adduct, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol 1,6-hexanediol, 1,4-cyclohexane Methanol, dipropylene glycol, polyethylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like. Examples of the trivalent or higher alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Moreover, as polyvalent carboxylic acid, bivalent carboxylic acid, trivalent or more carboxylic acid, etc. are mentioned, You may use 2 or more types together. Examples of the divalent carboxylic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, Examples include malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, isooctyl succinic acid and the like. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2, 4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexane Examples thereof include tricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, and empole trimer acid. In place of the polyvalent carboxylic acid, an anhydride or a lower alkyl ester of the polyvalent carboxylic acid may be used.

  As another example of a condensation polymerization resin, a polyester raw material monomer, a vinyl resin raw material monomer, and a monomer that reacts with both raw material monomers are mixed, and then a condensation polymerization reaction to obtain a polyester and a vinyl resin are obtained. Examples thereof include vinyl-based polyester resins obtained by performing radical polymerization reactions in parallel.

  Monomers that react with both raw material monomers include, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and unsaturated alcohols such as 2-propen-1-ol. Is mentioned.

  Examples of the polyester raw material monomer include the above-described polyhydric alcohols and polyhydric carboxylic acids (excluding monomers that react with both raw material monomers).

  Examples of the raw material monomer for the vinyl resin include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-tert- Styrene or styrene derivatives such as butylstyrene and p-chlorostyrene; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; methyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate , 3-methylbutyl (meth) acrylate, (meth) a Unsaturated carboxylic acid esters such as hexyl rillate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate; acrylonitrile; vinyl chloride A vinyl carboxylate such as vinyl acetate and vinyl benzoate; a vinyl alkyl ketone such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; and a vinyl alkyl ether such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.

  Examples of the polymerization initiator for radical polymerization of the monomer include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis ( Azo or diazo polymerization initiators such as cyclohexane-1-carbonitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide And peroxide polymerization initiators such as isopropyl peroxycarbonate and lauroyl peroxide.

  The mass ratio of the first resin to the first resin and the second resin is preferably 50 to 95%, and more preferably 60 to 85%. When this mass ratio is less than 50%, the low-temperature fixability may be lowered, and when it exceeds 95%, the sticking resistance may be lowered.

  In the present invention, the colorant is not particularly limited, but is 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 Rake, 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, Faise Red, Parachloro Ortho Nitroaniline , Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, Tolujing 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, Polyazole Chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, 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, Phthalocyanine And anthraquinone green, titanium oxide, zinc white, lithobon and the like.

  The content of the colorant in the base particles is usually 1 to 15% by mass, and preferably 3 to 10% by mass.

  The colorant can also be added as a master batch combined with the first resin and / or the second resin.

  In the present invention, the release agent is not particularly limited, and examples thereof include hydrocarbon paraffin. Examples of hydrocarbon paraffin include low molecular weight polyalkene obtained by polymerizing alkenes under high pressure using radical polymerization or low pressure using Ziegler catalyst; polyalkene obtained by thermally decomposing high molecular weight polyalkene; carbon monoxide and hydrogen And hydrocarbons obtained by synthesizing a synthesis gas using the age method, and hydrocarbons obtained by hydrogenation. By using such a release agent, the release agent sufficiently oozes out from the developer during fixing, and excellent fixing characteristics can be exhibited.

  Further, the release agent may be added when the base particles are produced, but may be added when the first resin and / or the second resin is synthesized. When the polyester is synthesized as the first resin and / or the second resin, the polycondensation reaction may be performed in a state where a hydrocarbon-based paraffin is added to a polyhydric alcohol and a polycarboxylic acid. Moreover, when synthesizing a vinyl-based polyester resin as the first resin and / or the second resin, while adding a hydrocarbon-based paraffin to the polyester raw material monomer, stirring and heating, A raw material monomer may be dropped to perform a condensation polymerization reaction and a radical polymerization reaction in parallel.

  In the present invention, the base particles may contain a dispersant for dispersing the release agent. Although it does not specifically limit as a dispersing agent, The block copolymer and graft copolymer which have a segment with high compatibility with a mold release agent, and a segment with high compatibility with 1st resin and / or 2nd resin ( Specifically, unsaturated hydrocarbons such as ethylene, propylene, butene, styrene, and α-styrene, and acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and the like can be used. Examples include α, β-unsaturated carboxylic acids, copolymers thereof or anhydrides thereof, vinyl polyester resins, and the like.

  Examples of the highly compatible segment for the release agent include a long-chain alkyl group having 12 or more carbon atoms, polyethylene, polypropylene, polybutene, polybutadiene, or a copolymer thereof, and the first resin and / or the second resin. Examples of the segment having high compatibility with the resin include polyester and vinyl resin.

  In the present invention, the base particle may further contain a charge control agent for controlling the charge amount. The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salts), alkylamides, phosphorus or phosphorus compounds, tungsten or tungsten compounds, fluorine-based surfactants, salicylic acid metal salts, metal salts of salicylic acid derivatives, and the like, and two or more of them may be used in combination. Commercially available products include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex E-. 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (made of 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) ), Copper phthalocyanine, perylene, quinacridone And azo pigments. Examples of other charge control agents include polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium bases. Among these, those that control the base particles to negative polarity are preferable.

  The addition amount of the charge control agent is not uniquely limited, but is usually 0.1 to 10% by mass and preferably 0.2 to 5% by mass with respect to the binder resin. If the amount added is less than 0.1% by mass, the effect of controlling the amount of charge may be insufficient. If the amount added exceeds 10% by mass, the chargeability of the toner will be too high, so The attraction force may increase, and the fluidity of the developer may decrease or the image density may decrease.

  In the present invention, the non-magnetic toner preferably further includes inorganic particles as an external additive for assisting fluidity, chargeability / developability / transferability.

  As inorganic particles, although not particularly limited, silica, zinc oxide, tin oxide, silica sand, titanium oxide, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, Aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like may be mentioned, and two or more kinds may be used in combination. Among these, silica is preferable in consideration of fluidity imparting ability and chargeability assisting ability.

The inorganic particles preferably have a specific surface area of 30 to 300 m ² / g by the BET method.

  The inorganic particles preferably have a primary particle size of 10 to 50 nm. If the primary particle size is less than 10 nm, the inorganic particles are less likely to be embedded in the base particles, and the deterioration of the image quality may increase at the endurance. If it exceeds 50 nm, the inorganic particles are detached from the non-magnetic toner, Filming may occur on the photoreceptor.

  The content of inorganic particles in the nonmagnetic toner is preferably 1.5 to 5% by mass, and more preferably 2.0 to 4.0% by mass. If the content of the inorganic particles is less than 1.5% by mass, the effect of adding the inorganic particles may not be obtained. If the content exceeds 5% by mass, the chargeability may be too high, It may become contaminated.

  In the present invention, the base particles preferably have a volume average particle size of 5 to 12 μm, and more preferably 6 to 10 μm. If the volume average particle size is less than 5 μm, the adhesion force of the toner increases, filming on the developing roller may occur, and control of the toner image by electrostatic force may be difficult. If it exceeds, the image quality may deteriorate. In addition, the volume average particle diameter of the base particles can be measured using Multisizer III (manufactured by Coulter).

  The base particles preferably have an average circularity of 0.89 to 0.95, more preferably 0.90 to 0.94. When the average circularity is less than 0.89, transferability becomes insufficient, and a high-quality image without dust may not be formed. When the average circularity exceeds 0.95, a system that employs blade cleaning or the like As a result, poor cleaning of the photoconductor, transfer belt, etc. may occur. The circularity is obtained by using an optical detection band method in which a suspension containing base particles is passed through an imaging unit detection band on a flat plate, and an image is optically detected and analyzed using a CCD camera. This is a value obtained by dividing the circumference of a circle equal to the projected area obtained by the circumference of a real particle. The average circularity can be measured using a flow type particle image analyzer.

  In the present invention, the production method of the non-magnetic toner is not particularly limited, and examples thereof include a pulverization method, a polymerization method (for example, suspension polymerization method, emulsion polymerization aggregation method, dissolution suspension method), spray granulation method and the like. .

  In the present invention, a toner image is obtained by developing an electrostatic latent image formed on a photoreceptor with the developer of the present invention using a known non-magnetic one-component developing image forming apparatus, An image can be formed by transferring this to a transfer medium and fixing it. At this time, the developer is supplied to the developing roller, the thickness of the developer is regulated by the blade, and the electrostatic latent image formed on the photoreceptor is developed with the developer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, a part means a mass part.

[Example 1]
A 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube was charged with 2210 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and terephthalic acid. 850 g, 120 g of 1,2,4-benzenetricarboxylic anhydride and 0.5 g of dibutyltin oxide (catalyst) were added, and the temperature was raised to 230 ° C. using a mantle heater in a nitrogen atmosphere to perform a condensation polymerization reaction. At this time, the degree of polymerization was tracked by measuring the softening point using a constant load extrusion capillary rheometer, and the reaction was terminated when the softening point corresponded to 115 ° C. to obtain the first resin A1.

  In addition, after heating up 1st resin A1 to 200 degreeC using the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.), it heated up the sample cooled to 0 degreeC with the temperature-fall rate of 10 degree-C / min. When the temperature was raised at a rate of 10 ° C./min, the glass transition point was 64.6 ° C. In addition, 1.5 g of the first resin A1 was weighed using a flow tester CFT-500 (manufactured by Shimadzu Corporation), and the temperature rising rate was 3. using a die having a height of 1.0 mm and a diameter of 1.0 mm. Under the conditions of 0 ° C./min, preheating time 180 seconds, load 30 kg, measurement temperature range 80 to 160 ° C., the temperature at which 1/2 of the sample flowed out was measured as the softening point, and the softening point was 115.5 ° C. It was.

  A 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube was charged with 1230 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 290 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 250 g of isododecenyl succinic anhydride, 310 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst) In a nitrogen atmosphere, the temperature was raised to 230 ° C. using a mantle heater to perform a condensation polymerization reaction. At this time, in the same manner as the first resin A1, the degree of polymerization was traced, and when the softening point was 138 ° C., the reaction was terminated to obtain the first resin B1. The first resin B1 had a glass transition point of 68.0 ° C. and a softening point of 137.8 ° C. measured in the same manner as the first resin A1.

  Into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen introducing tube, 1370 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 150 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 120 g of isododecenyl succinic anhydride, 440 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst) In a nitrogen atmosphere, the temperature was raised to 230 ° C. using a mantle heater to perform a condensation polymerization reaction. At this time, the degree of polymerization was tracked in the same manner as the first resin A1, and when the softening point was 142 ° C., the reaction was terminated to obtain the second resin 1. The second resin 1 had a glass transition point of 72.0 ° C. and a softening point of 142.3 ° C. measured in the same manner as the first resin A1.

  Next, 50 parts of C.I. I. Pigment Red 57-1 and 50 parts of the first resin A1 were mixed using a mixer and then melt-kneaded using a two-roll mill. The obtained kneaded product was rolled and cooled and then coarsely pulverized using a pulverizer to prepare a master batch.

  8 parts of the master batch obtained (equivalent to 4 parts of CI Pigment Red 57-1), 36 parts of the first resin A1, 45 parts of the first resin B1, 15 parts of the second resin 1 and release Four parts of the mold WEP-5 (manufactured by NOF Corporation) were sufficiently mixed using a Henschel mixer to obtain a toner material.

  The obtained toner material was melt-kneaded using a twin-screw extrusion kneader PCM (Ikegai Kogyo Co., Ltd.). At this time, the supply rate is 95 kg / hour, the screw rotational speed is 85 rpm, the temperature of the supply part (F) is 10 ° C., the temperature of the barrel part is 140 ° C., the temperature of the vent part (V) is 100 ° C., and the temperature of the die part (D) is 100 ° C. Set to.

  The obtained kneaded material was rolled to a thickness of 2 mm using a cooling press roller, cooled with a cooling belt, and then coarsely pulverized using a feather mill. Next, after pulverizing using a mechanical pulverizer KTM (manufactured by Kawasaki Heavy Industries, Ltd.) until the volume average particle size becomes 10-12 μm, using a jet pulverizer IDS (manufactured by Nippon Pneumatic Industrial Co., Ltd.), The powder was pulverized while being classified. Furthermore, fine powder was classified using a Teplex type classifier type 100ATP (manufactured by Hosokawa Micron Corporation), a rotor type classifier, to obtain base particles having a volume average particle diameter of 9.0 μm and an average circularity of 0.910. . Moreover, when the endothermic curve of the base particles was measured by a method similar to the method for measuring the glass transition point of the first resin A1 using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), the maximum endothermic peak was found. It was at 81.8 ° C.

  100 parts of base particles and 2.5 parts of silica particles TS530 (manufactured by Cabozil) were mixed using a Henschel mixer to obtain a magenta toner.

  Next, when the toner material was prepared, particles were prepared in the same manner as the magenta toner except that the release agent was not added. The binder resin was a glass measured in the same manner as the first resin A1. The transition points were 3 points of 64.2 ° C, 67.6 ° C and 71.5 ° C.

  In addition, the volume average particle diameter of the base particles was measured using Multisizer III (manufactured by Coulter). Specifically, first, 0.1 to 0.3 ml of a surfactant dry well (manufactured by Fuji Photo Film) and 2 to 20 mg of base particles are added to 100 to 150 ml of an electrolytic solution ISOTON-II (manufactured by Coulter). It was. Next, after dispersing for about 1 to 3 minutes using an ultrasonic disperser, Dv and Dn of the base particles were measured using a 100 μm aperture.

  As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm were used, and particles having a particle diameter of 2.00 to 40.30 μm were measured.

Further, the average circularity of the base particles was measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation). Specifically, first, 0.1 to 0.5 ml of a surfactant alkylbenzene sulfonate and 0.01 to 0.10 g of base particles are added to 100 to 150 ml of water from which impure solids have been removed in advance. It was. Next, the average degree of circularity of the base particles is measured by dispersing for 1 to 3 minutes using a desktop ultrasonic cleaner MODEL: VS-150 and setting the concentration of the dispersion to 3000 to 1.0 × 10 ⁴ particles / μl. did. Note that particles having a circularity of 0.40 to 1.00 were measured.

[Example 2]
Into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen introducing tube, 1370 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Put 150 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 560 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst). Using a mantle heater, the temperature was raised to 230 ° C. to conduct a condensation polymerization reaction. At this time, in the same manner as in Example 1, the degree of polymerization was traced, and when the softening point was 143 ° C., the reaction was terminated to obtain a second resin. The second resin 2 had a glass transition point of 78.0 ° C. and a softening point of 143.1 ° C.

  A magenta toner was obtained in the same manner as in Example 1 except that the second resin 2 was used instead of the second resin 1. At this time, the base particles had a volume average particle size of 9.1 μm and an average circularity of 0.912. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 64.0 ° C., 67.3 ° C., and 77.7 ° C.

[Example 3]
A magenta toner was obtained in the same manner as in Example 1 except that the addition amounts of the first resin B1 and the second resin 1 when preparing the toner material were 20 parts and 40 parts, respectively. At this time, the base particles had a volume average particle size of 8.9 μm and an average circularity of 0.913. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.1 ° C. Further, the binder resin had three glass transition points of 64.3 ° C., 67.0 ° C. and 71.4 ° C.

[Example 4]
A magenta toner was obtained in the same manner as in Example 2 except that the addition amounts of the first resin B1 and the second resin 2 when preparing the toner material were 20 parts and 40 parts, respectively. At this time, the base particles had a volume average particle size of 8.8 μm and an average circularity of 0.915. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 81.9 ° C. Further, the binder resin had three glass transition points of 64.1 ° C., 67.8 ° C. and 77.2 ° C.

[Example 5]
A magenta toner was obtained in the same manner as in Example 1 except that the addition amounts of the first resin A1 and the first resin B1 when producing the toner material were 66 parts and 15 parts, respectively. At this time, the base particles had a volume average particle size of 9.0 μm and an average circularity of 0.913. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 64.0 ° C, 67.6 ° C and 71.2 ° C.

[Example 6]
A magenta toner was obtained in the same manner as in Example 2 except that the addition amounts of the first resin A1 and the first resin B1 in preparing the toner material were 66 parts and 15 parts, respectively. At this time, the base particles had a volume average particle size of 9.1 μm and an average circularity of 0.912. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.2 ° C. Further, the binder resin had three glass transition points of 63.8 ° C., 67.2 ° C. and 77.5 ° C.

[Example 7]
The same procedure as in Example 1 was conducted except that the addition amounts of the first resin A1, the first resin B1, and the second resin 1 were 66 parts, 10 parts, and 20 parts, respectively, when preparing the toner material. A magenta toner was obtained. At this time, the base particles had a volume average particle size of 8.9 μm and an average circularity of 0.916. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 81.7 ° C. Further, the binder resin had three glass transition points of 64.1 ° C, 67.6 ° C and 70.9 ° C.

[Example 8]
Except that the addition amounts of the first resin A1, the first resin B1, and the second resin 2 when preparing the toner material were 66 parts, 10 parts, and 20 parts, respectively, in the same manner as in Example 2. A magenta toner was obtained. At this time, the base particles had a volume average particle size of 8.7 μm and an average circularity of 0.920. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.2 ° C. Further, the binder resin had three glass transition points of 64.4 ° C., 67.3 ° C. and 77.0 ° C.

[Example 9]
A magenta toner was obtained in the same manner as in Example 1 except that the addition amounts of the first resin B1 and the second resin 1 in preparing the toner material were 50 parts and 10 parts, respectively. At this time, the base particles had a volume average particle size of 9.0 μm and an average circularity of 0.914. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 64.0 ° C., 67.6 ° C. and 71.5 ° C.

[Example 10]
A magenta toner was obtained in the same manner as in Example 2 except that the addition amounts of the first resin B1 and the second resin 2 in preparing the toner material were 50 parts and 10 parts, respectively. At this time, the base particles had a volume average particle size of 9.2 μm and an average circularity of 0.912. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 81.9 ° C. Further, the binder resin had three glass transition points of 64.1 ° C., 67.3 ° C., and 77.7 ° C.

[Example 11]
A magenta toner was obtained in the same manner as in Example 1 except that the addition amounts of the first resin B1 and the second resin 1 in preparing the toner material were 10 parts and 50 parts, respectively. At this time, the base particles had a volume average particle size of 9.2 μm and an average circularity of 0.918. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.2 ° C. Further, the binder resin had three glass transition points of 64.2 ° C., 67.0 ° C. and 71.4 ° C.

[Example 12]
A magenta toner was obtained in the same manner as in Example 2 except that the addition amounts of the first resin B1 and the second resin 2 in preparing the toner material were 10 parts and 50 parts, respectively. At this time, the base particles had a volume average particle size of 9.4 μm and an average circularity of 0.920. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 64.0 ° C., 67.8 ° C. and 77.2 ° C.

[Comparative Example 1]
A 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube was charged with 1930 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 280 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 850 g of terephthalic acid, 120 g of 1,2,4-benzenetricarboxylic anhydride and 0.5 g of dibutyltin oxide (catalyst) were added, and a nitrogen atmosphere The polycondensation reaction was performed by raising the temperature to 230 ° C. using a mantle heater. At this time, in the same manner as in Example 1, the degree of polymerization was traced, and when the softening point was 113 ° C., the reaction was terminated to obtain the first resin A2. The first resin A2 had a glass transition point of 57.7 ° C. and a softening point of 112.9 ° C.
Met.

  A magenta toner was obtained in the same manner as in Example 1 except that the first resin A2 was used instead of the first resin A1. At this time, the base particles had a volume average particle size of 9.1 μm and an average circularity of 0.913. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 81.9 ° C. Further, the binder resin had three glass transition points of 57.8 ° C., 67.5 ° C., and 71.5 ° C.

[Comparative Example 2]
Into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen introduction tube, 760 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 760 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 250 g of isododecenyl succinic anhydride, 310 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst) In a nitrogen atmosphere, the temperature was raised to 230 ° C. using a mantle heater to perform a condensation polymerization reaction. At this time, the degree of polymerization was tracked in the same manner as in Example 1, and the reaction was terminated when the softening point corresponded to 140 ° C. to obtain the first resin B2. The first resin B2 had a glass transition point of 57.0 ° C. and a softening point of 140.5 ° C.

  A magenta toner was obtained in the same manner as in Example 1 except that the first resin B2 was used instead of the first resin B1. At this time, the base particles had a volume average particle size of 8.8 μm and an average circularity of 0.910. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.1 ° C. Further, the binder resin had three glass transition points of 57.6 ° C., 64.0 ° C. and 71.4 ° C.

[Comparative Example 3]
A 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube was charged with 1320 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 200 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 250 g of isododecenyl succinic anhydride, 310 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst) In a nitrogen atmosphere, the temperature was raised to 230 ° C. using a mantle heater to perform a condensation polymerization reaction. At this time, in the same manner as in Example 1, the degree of polymerization was traced, and when the softening point was 142 ° C., the reaction was terminated to obtain the second resin 3. The second resin 3 had a glass transition point of 69.0 ° C. and a softening point of 142.4 ° C.

  A magenta toner was obtained in the same manner as in Example 1 except that the second resin 3 was used instead of the second resin 1. At this time, the base particles had a volume average particle size of 9.1 μm and an average circularity of 0.916. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 63.9 ° C., 67.6 ° C. and 69.1 ° C.

[Comparative Example 4]
Into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen introduction tube, 1420 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 100 g of ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 540 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride and 7 g of dibutyltin oxide (catalyst) were put under a nitrogen atmosphere. Using a mantle heater, the temperature was raised to 230 ° C. to conduct a condensation polymerization reaction. At this time, in the same manner as in Example 1, the degree of polymerization was traced, and when the softening point corresponded to 147 ° C., the reaction was terminated, and the second resin 4 was obtained. The second resin 4 had a glass transition point of 80.0 ° C. and a softening point of 147.5 ° C.

  A magenta toner was obtained in the same manner as in Example 1 except that the second resin 4 was used instead of the second resin 1. At this time, the base particles had a volume average particle size of 9.2 μm and an average circularity of 0.918. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 81.9 ° C. Furthermore, the glass transition point of the binder resin was 3 points of 64.0 ° C, 67.7 ° C and 79.8 ° C.

[Comparative Example 5]
A magenta toner was obtained in the same manner as in Example 1 except that the second resin 3 was used instead of the first resin B1. At this time, the base particles had a volume average particle size of 9.1 μm and an average circularity of 0.913. Further, when the endothermic curve of the base particles was measured, the maximum endothermic peak was present at 82.0 ° C. Further, the binder resin had three glass transition points of 63.9 ° C., 69.0 ° C. and 71.3 ° C.

  The properties of the first resins A and B and the second resin are shown in Table 1.

［評価方法及び評価結果］
実施例及び比較例のマゼンタトナーを非磁性一成分現像剤として用いて、低温定着性及び耐固着性を評価した結果を表２に示す。

[Evaluation method and evaluation results]
Table 2 shows the results of evaluating low-temperature fixability and anti-sticking property using magenta toners of Examples and Comparative Examples as non-magnetic one-component developers.

表２より、実施例のマゼンタトナーは、低温定着性及び耐固着性に優れることがわかる。このとき、実施例９、１０では、第一の樹脂に対する第二の樹脂の質量比が小さいため、耐固着性が若干低下している。また、実施例１１、１２では、第二の樹脂に対する第一の樹脂の質量比が小さいため、低温定着性が若干低下している。一方、比較例１、２では、結着樹脂が６０℃未満のガラス転移点を有するため、耐固着性が不十分となっている。また、比較例３では、結着樹脂が７０℃以上７８℃未満のガラス転移点を有さないため、耐固着性が不十分となっている。さらに、比較例４では、結着樹脂が７８℃以上のガラス転移点を有するため、低温定着性が不十分である。また、比較例５では、結着樹脂中のガラス転移点が高い成分の含有量が多いため、低温定着性が不十分である。

From Table 2, it can be seen that the magenta toners of the examples are excellent in low-temperature fixability and anti-sticking property. At this time, in Examples 9 and 10, since the mass ratio of the second resin to the first resin is small, the sticking resistance is slightly lowered. In Examples 11 and 12, since the mass ratio of the first resin to the second resin is small, the low-temperature fixability is slightly lowered. On the other hand, in Comparative Examples 1 and 2, since the binder resin has a glass transition point of less than 60 ° C., the adhesion resistance is insufficient. In Comparative Example 3, since the binder resin does not have a glass transition point of 70 ° C. or higher and lower than 78 ° C., the anti-sticking property is insufficient. Further, in Comparative Example 4, since the binder resin has a glass transition point of 78 ° C. or higher, the low-temperature fixability is insufficient. In Comparative Example 5, since the content of the component having a high glass transition point in the binder resin is large, the low-temperature fixability is insufficient.

  In addition, the evaluation method of each characteristic is shown below.

(Low temperature fixability)
An unfixed image was formed using Ipsio CX3000 (manufactured by Ricoh Co., Ltd.) using a non-magnetic one-component developing system so that the adhesion amount was 1.0 ± 0.1 mg / cm ² . Next, only the fixing part of Ipsio CX2500 (manufactured by Ricoh) is taken out, and the fixing temperature is 130 to 200 ° C. using a fixing test apparatus modified so that the temperature of the fixing belt and the belt linear velocity become desired values. The unfixed image was fixed. The obtained fixed image was evaluated by conducting a smear test. At this time, the case where the temperature satisfying the smear property was less than 155 ° C. was evaluated as “◯”, the case where it was 155 ° C. or more and less than 165 ° C. was evaluated as Δ, and the case where it was 165 ° C. or more was evaluated as “X”.

(Sticking resistance)
Using an Ipsio CX3000 (manufactured by Ricoh Co., Ltd.), a predetermined print pattern with a printing rate of 6% was continuously copied in an N / N environment (23 ° C., 45% RH) for 2000 sheets, and then the developing roller of the developing unit The condition and the copied image were visually observed and evaluated. At this time, the sleeve has no streak or unevenness, and the sleeve has 1 or 2 streaks or unevenness, but if the image has no defect, Δ, 3 or more streaks or unevenness occurs. Judgment was made as x.

Claims (8)

A developer comprising a non-magnetic toner having base particles containing a binder resin, a colorant and a release agent,
The binder resin is polyester,
The polyester is obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid,
The polyhydric alcohol is an aromatic compound;
The particles produced in the same manner as the non-magnetic toner, except that the release agent is not added , have only a glass transition point of 60 ° C. or more and less than 70 ° C. and a glass transition point of 70 ° C. or more and less than 78 ° C.,
A developer, wherein a difference between the maximum value of the glass transition point of 60 ° C. or more and less than 70 ° C. and the maximum value of the glass transition point of 70 ° C. or more and less than 78 ° C. is 3 ° C. or more.   2. The developer according to claim 1, wherein the endothermic curve of the base particle has a maximum endothermic peak of 30 ° C. or more and 200 ° C. or less at 65 ° C. or more and 85 ° C. or less. The non-magnetic toner, a developing agent according to claim 1 or 2, characterized in that it further comprises inorganic particles. The developer according to claim 3 , wherein the inorganic particles are silica particles . The non-magnetic toner, a developing agent according to claim 3 or 4, wherein the content of the inorganic particles is 5 wt% or more and 1.5 mass%. The base particles, the developer according to any one of claims 1 to 5, wherein the volume average particle diameter is 5μm or more 12μm or less. The base particles, the developer according to any one of claims 1 to 6, wherein an average circularity is 0.89 to 0.95. A photoreceptor,
It means for forming an electrostatic latent image on the photosensitive body,
It means for forming a toner image photoreceptor electrostatic latent image formed on, and developed with a developer according to any one of claims 1 to 7,
Means for transferring a toner image formed on the photosensitive member to a transfer target;
An image forming apparatus comprising means for fixing the toner image transferred to the transfer target.