JP5365190B2 - Method for producing developer - Google Patents

Description

The present invention relates to how to produce a developer comprising non-magnetic toner having a base particles.

  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. However, since the pressing force of the blade against the developing roller is large, there is a problem that the toner is easily fixed to the blade.

  The non-magnetic one-component developer is a pulverization method in which a kneaded product obtained by kneading a material containing a binder resin, a colorant and a release agent is cooled and then pulverized, or a binder resin in an aqueous medium. , A polymerization method for forming particles containing a colorant and a release agent (for example, suspension polymerization method, emulsion polymerization aggregation method, dissolution suspension method), spraying a fluid containing a binder resin, a colorant and a release agent. Thus, it is manufactured by using a spray granulation method for forming particles.

Patent Document 1 discloses a composition containing a binder resin, a colorant, and a wax, wherein the content of the wax is 3 to 20% by weight with respect to the binder resin. Disclosed is a method for producing a toner having a step of performing melt kneading using a kneader under conditions where the temperature of the kneaded product at the time of melt kneading is Tm-20 ° C to Tm + 20 ° C (Tm: melting temperature of the binder resin). Yes. However, when such a toner is used as a one-component developer, since the temperature of the kneaded product at the time of melt kneading is high, there is a problem that the shear stress is not sufficiently applied and the low-temperature fixability becomes insufficient.
JP 2000-75548 A

In view of the problem of the prior art has for its object to provide a manufacturing how the low-temperature fixability and the non-magnetic one-component developer which is excellent in sticking resistance.

The invention according to claim 1 is a method for producing a developer comprising a non-magnetic toner having base particles, and a toner containing polyester , a colorant and a release agent using a continuous open roll kneader. A step of obtaining a kneaded product by melt-kneading the material, a step of cooling the obtained kneaded product, a step of pulverizing the cooled kneaded product, and classifying the crushed kneaded product. A process of obtaining base particles, wherein the polyester is obtained by polycondensation of an alkylene oxide adduct of bisphenol A, terephthalic acid and 1,2,4-benzenetricarboxylic acid anhydride, and is a component that does not dissolve in THF . content is 30 wt% or less than 15 wt%, the developer, the content of the component which is insoluble in THF is not more than 1 mass% or more 0 wt%, the Poriesu The temperature at which the melt viscosity becomes 2.0 × 10 ³ Pa · sec when shear stress of 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6.13 × 10 ⁵ Pa is applied to the tellurium, T _r-1 [° C.], T _r-2 [° C.] and T _r-3 [° C.], 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6.13 × 10 ^{5 for the} developer. The temperatures at which the melt viscosity becomes 2.0 × 10 ³ Pa · sec when a shear stress of Pa is applied are T _t-1 [° C.], T _t-2 [° C.], and T _t-3 [° C.], respectively. Then, the formula 130 ≦ T _r−2 ≦ 145
10 ≦ T _r−1 −T _r−2 ≦ 30
| T _r−3 −T _r−2 | ≦ 3
115 ≦ T _t−2 ≦ 130
| T _t-1 −T _t-2 | ≦ 5
| T _t−3 −T _t−2 | ≦ 3
15 ≦ T _r−1 −T _t−1
10 ≦ T _r−2 −T _t−2
10 ≦ T _r−3 −T _t−3
Meets, said temperature of the kneaded material at the time of the toner material to melt-kneading is 20 ° C. temperature lower than the softening point of 50 ° C. lower temperature than the binder resin than the softening point of the binder resin It is characterized by.

Invention according to claim 2, in the method for manufacturing a developing agent according to claim 1, wherein the developer, in the endothermic curve obtained by differential thermal analysis measurement, the following maximum endothermic peak 200 ° C. 30 ° C. or higher Is present at 65 ° C. or higher and 85 ° C. or lower.

According to a third aspect of the present invention, in the developer manufacturing method according to the first or second aspect , the developer further includes inorganic particles.

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

The invention according to claim 5 is the method for producing a developer according to claim 3 or 4 , wherein the developer has a content of the inorganic particles of 1.5% by mass or more and 5% by mass. And

A sixth aspect of the present invention is the method for producing a developer according to any one of the first to fifth aspects, wherein the developer has a volume average particle diameter of 5 μm or more and 12 μm or less.

That the invention according to claim 7, in the manufacturing method of the developer according to any one of claims 1 to 6, wherein the developer has an average circularity is 0.89 to 0.95 Features.

According to the present invention, it is possible to provide a manufacturing how the non-magnetic one-component developer which is excellent in low-temperature fixability and sticking resistance.

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

The developer production method of the present invention is a method for producing a developer comprising a non-magnetic toner having base particles, and kneading by melting and kneading a toner material containing a binder resin, a colorant and a release agent. A binder resin having a step of obtaining a product, a step of cooling the obtained kneaded product, a step of pulverizing the cooled kneaded product, and a step of obtaining base particles by classifying the crushed kneaded product Contains components that are not soluble in THF. At this time, when a shear stress of 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6.13 × 10 ⁵ Pa was applied to the binder resin, the melt viscosity was 2.0 × 10 ³ Pa · sec. Are T _r-1 [° C.], T _r-2 [° C.] and T _r-3 [° C.], respectively, 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6. The temperatures at which the melt viscosity becomes 2.0 × 10 ³ Pa · sec when a shear stress of 13 × 10 ⁵ Pa is applied are T _t-1 [° C.], T _t-2 [° C.], and T _{t-3, respectively.} Assuming [° C.], the formula 130 ≦ T _r−2 ≦ 145 (1)
10 ≦ T _r−1 −T _r−2 ≦ 30 (2)
| T _r−3 −T _r−2 | ≦ 3 (3)
115 ≦ T _t−2 ≦ 130 (4)
| T _t-1 −T _t-2 | ≦ 5 (5)
| T _t−3 −T _t−2 | ≦ 3 (6)
15 ≦ T _r−1 −T _t−1 (7)
10 ≦ T _r−2 −T _t−2 (8)
10 ≦ T _r−3 −T _t−3 (9)
Meet.

In addition, _Tr-1 , _{Tr-2, Tr-3} , _Tt-1 , _Tt-2, and _Tt-3 should be measured using a flow tester CFT-500 (manufactured by Shimadzu Corporation). Can do. Here, when the melt viscosity becomes 2.0 × 10 ³ Pa · second, the developer penetrates into the transfer material and the adhesive force with the fixing roller increases. Therefore, a temperature at which the melt viscosity becomes 2.0 × 10 ³ Pa · second when a shear stress is applied to the binder resin and the developer is used as an index indicating the fixing characteristics of the developer. Further, the shear stress applied when measuring the temperature at which the melt viscosity becomes 2.0 × 10 ³ Pa · second corresponds to the sheet passing speed and the pressing condition at the time of fixing. That is, the shear stresses of 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6.13 × 10 ⁵ Pa are respectively low when the paper passing speed is low and the fixing speed is low. This corresponds to the case where the fixing condition is medium pressure and the medium pressure, and the case where the sheet passing speed is high and the fixing condition is high pressure.

  The developer of the present invention is made of a nonmagnetic toner satisfying the formulas (4) to (6), and melt-kneaded a material containing a binder resin, a colorant, and a release agent satisfying the formulas (1) to (3). The resulting kneaded product is cooled, then crushed and classified, so that the non-magnetic toner and the binder resin satisfy the formulas (7) to (9). Thereby, at the time of melt-kneading, the binder resin containing a component that does not dissolve in THF is cut, and a component that dissolves in THF is generated. Furthermore, since the components dissolved in the generated THF are entangled with each other, a non-magnetic one-component developer excellent in low-temperature fixability and anti-sticking property can be obtained.

In Formula (1), when T _r-2 is less than 130 ° C., the binder resin has a small content of components that do not dissolve in THF and has a low molecular weight, so that the developer is easily fixed to the blade. On the other hand, if T _r-2 exceeds 145 ° C., the binder resin has a large content of components that do not dissolve in THF and has a large molecular weight, so that the low-temperature fixability of the developer becomes insufficient.

In Formula (2), when T _r-1 -T _r-2 is less than 10 ° C., the binder resin has a small content of components that do not dissolve in THF and has a low molecular weight, so that the developer adheres to the blade. It becomes easy to do. On the other hand, when T _r-1 -T _r-2 exceeds 30 ° C., the binder resin has a large content of components that do not dissolve in THF and has a large molecular weight, so that the low-temperature fixability of the developer becomes insufficient. .

In the formula (3), when T _r-2 - _Tr-3 exceeds 3 ° C., the binder resin has a small content of components that do not dissolve in THF and has a large molecular weight, so that the developer adheres to the blade. It becomes easy. On the other hand, when T _r-3- T _r-2 exceeds 3 ° C., the binder resin has a large content of components that do not dissolve in THF and has a large molecular weight, so that the low-temperature fixability of the developer becomes insufficient. .

In the formula (4), when T _t-2 is less than 115 ° C., the developer has a small molecular weight, and therefore, it tends to adhere to the blade. On the other hand, when T _t-2 exceeds 130 ° C., the developer has a high molecular weight, so that the low-temperature fixability becomes insufficient.

In the formula (5), when T _t−2 −T _t−1 exceeds 5 ° C., the developer has a low molecular weight, so that the developer tends to adhere to the blade. On the other hand, when T _t-1 −T _t-2 exceeds 5 ° C., the developer has a high molecular weight, so that the low-temperature fixability becomes insufficient.

In Formula (6), when T _t−2 −T _t−3 exceeds 3 ° C., the developer has a low molecular weight, and therefore, it tends to adhere to the blade. On the other hand, when T _t−3 −T _t−2 exceeds 3 ° C., the developer has a high molecular weight, so that the low-temperature fixability becomes insufficient.

In the formula (7), if T _r-1 -T _t-1 is less than 15 ° C., the binder resin is not sufficiently cut during melt-kneading, so that the developer has insufficient low-temperature fixability. .

In the formula (8), if T _r-2 - _Tt-2 is less than 10 ° C., the binder resin is not sufficiently cut during melt-kneading, so that the developer has insufficient low-temperature fixability. .

In Formula (9), if T _r-3 - _Tt-3 is less than 10 ° C., the binder resin is not sufficiently cut during melt-kneading, so that the developer has insufficient low-temperature fixability. .

  In the present invention, the binder resin preferably has a content of a component not dissolved in THF of 15 to 30% by mass. If the content of the component that does not dissolve in THF is less than 15% by mass, the developer may easily adhere to the blade. If the content exceeds 30% by mass, the developer may have insufficient low-temperature fixability. There is.

  Moreover, it is preferable that the content of the component which does not melt | dissolve in the developer of this invention is 0-1 mass%. When the content of the component not dissolved in THF exceeds 1% by mass, the developer has insufficient low-temperature fixability. Sometimes.

  In the present invention, when the toner material is melt-kneaded, a twin-screw extruder, a kneader, a two-roll, a three-roll, etc. can be used, but since a high shear force can be applied, a continuous open roll kneading Machine is preferred.

  The continuous open roll type kneader means that the melt kneading part is an open type, and can easily dissipate the kneading heat generated when melt kneading. Moreover, it is preferable that a continuous open roll type kneader has at least two rolls and has a high temperature roll that can be set to a high temperature and a cooling roll that can be cooled. At this time, from the viewpoint of dispersibility, it is preferable that the rotation speed of the high-temperature roll is larger than the rotation speed of the cooling roll.

  In the present invention, when the toner material is melt-kneaded using a continuous open roll kneader, the temperature of the kneaded material is 50 ° C. lower than the softening point of the binder resin to the softening point of the binder resin. The temperature is preferably 20 ° C lower, more preferably 40 ° C lower than the softening point of the binder resin to 20 ° C lower than the softening point of the binder resin. If the temperature of the kneaded product is less than 40 ° C. lower than the softening point of the binder resin, the toner material does not melt sufficiently, so that the kneaded product is not sufficiently dispersed or the kneaded product is peeled off from the roll. Sometimes. On the other hand, when the temperature of the kneaded material exceeds 20 ° C. lower than the softening point of the binder resin, the shear stress is not sufficiently applied to the toner material, so that the binder resin is not sufficiently cut and low-temperature fixability is not good. It may become sufficient, or the dispersion diameter of the release agent may increase. The temperature of the kneaded material means the temperature of the surface of the kneaded material adhering to the end portion on the discharge side of the roll, and is measured using a non-contact type laser thermometer IT-540 type (manufactured by HORIBA). be able to. In addition, the softening point of the binder resin was determined by using a flow tester CFT-500 (manufactured by Shimadzu Corporation), a heating rate of 3.0 ° C./min, a preheating time of 180 seconds, a load load of 30 kg, and a measurement temperature range. Is a temperature at which half of the resin flows out when 1.5 g of binder resin is extruded from a die having a diameter of 1.0 mm and a height of 1.0 mm.

  The temperature of the kneaded material is preferably a temperature at which the temperature of the kneaded product is 50 ° C. lower than the softening point of the binder resin to 20 ° C. lower than the softening point of the binder resin. Moreover, it is preferable that a cooling roll is 0-60 degreeC, and 10-40 degreeC is further more preferable. At this time, the temperature of the roll can be controlled by circulating a heat medium and / or a refrigerant inside the roll. The temperature of the roll may be controlled for the entire roll, but the heating medium and / or the refrigerant is divided into two at the center of the roll, and the temperature is controlled independently on the toner material supply side and the kneaded product discharge side. It is preferable to form a temperature gradient. Thereby, a high shearing force can be applied.

  The toner material supplied to the continuous open roll type kneader is preferably one that is uniformly mixed and then melted. Thereby, it is possible to apply a high shear force and to suppress the toner material from falling between the rolls.

  In the present invention, when the obtained kneaded product is cooled, a press roller, a single belt cooler, a double belt cooler, a drum cooler, or the like can be used.

  Further, when the cooled kneaded product is pulverized, a counter jet mill, a swirling jet mill, a jet mill, a micron mill, a fine mill, a turbo mill, a kryptron pulverizer, or the like can be used.

  Furthermore, when classifying the pulverized kneaded product, an airflow classifier, a DS classifier, a turboplex, a teaplex, a micron separator, a whitzer separator, or the like can be used.

  In the present invention, the endothermic curve obtained by differential thermal analysis measurement of the developer preferably has a maximum endothermic peak of 30 ° C. to 200 ° C. at 65 to 85 ° C., and preferably 70 to 85 ° C. Further preferred. When the maximum endothermic peak is less than 65 ° C., the developer tends to adhere to the blade, and when it exceeds 85 ° C., the low-temperature fixability of the developer may deteriorate.

  In the present invention, the toner material includes a binder resin, a colorant, and a release agent, but may further include a dispersant for dispersing the release agent, a charge control agent, and the like.

  The binder resin is not particularly limited, and examples thereof include polyester, (meth) acrylic resin, styrene- (meth) acrylic resin, epoxy resin, and cyclic olefin copolymer (for example, TOPAS (manufactured by Ticona)). You may use together.

  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 polyesters 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.

  In the present invention, the binder resin is preferably a polyester from the viewpoint of oilless fixing, and a polyester obtained by polycondensation of a bisphenol A alkylene oxide adduct, terephthalic acid and fumaric acid is particularly preferable.

  In addition, the binder resin preferably contains at least one low molecular weight substance and high molecular weight substance from the viewpoint of further improving the oilless fixing separability and offset resistance. The high molecular weight material is preferably a vinyl-based polyester, a vinyl obtained by polycondensation and radical polymerization of bisphenol A alkylene oxide adduct, terephthalic acid, trimellitic acid and succinic acid, styrene and butyl acrylate, and fumaric acid. Polyester is particularly preferable.

  The colorant is not particularly limited as long as it is a pigment or dye, but 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, bengara, red lead, lead vermilion, cadmium red, cadmium mercurial red, antimon vermilion, permanent red 4R, para red, fise red, parachloroortho Nitroani Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, 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, Poly Zored, Chrome Vermilion, 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, Phthalocyani N, Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon, etc., may be used in combination.

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

  The colorant can also be added as a master batch in which a pigment and a resin are combined. Resins used in the master batch include rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin in addition to the resin exemplified as the binder resin. A mold release agent etc. are mentioned, You may use 2 or more types together.

  Although it does not specifically limit as a mold release agent, A hydrocarbon type paraffin is mentioned. 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.

  The release agent may be added when the toner material is produced, or may be added when the binder resin is synthesized. When a polyester is synthesized as the binder resin, it can be subjected to polycondensation with a hydrocarbon paraffin added to a polyhydric alcohol and a polycarboxylic acid. In addition, when synthesizing a vinyl polyester resin as a binder resin, the vinyl resin raw material monomer is added dropwise with stirring and heating in a state where hydrocarbon paraffin is added to the polyester raw material monomer. The polymerization reaction and the radical polymerization reaction may be performed in parallel.

  The dispersing agent for dispersing the release agent is not particularly limited, but a block copolymer or graft copolymer (oligomer) having a segment having high compatibility with the release agent and a segment having high compatibility with the binder resin. Specifically, unsaturated hydrocarbons such as ethylene, propylene, butene, styrene, and α-styrene, and α, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid are used. (beta) -unsaturated carboxylic acid, its ester, its copolymer with an anhydride, vinyl-type polyester resin, etc. are mentioned.

  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 a highly compatible segment for the binder resin. Examples thereof include polyester and vinyl resin.

  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) Salt), alkylamides, phosphorus or phosphorus compounds, tungsten or tungsten compounds, fluorine-based surfactants, metal salts of salicylic acid, metal salts of salicylic acid derivatives, copper phthalocyanine, perylene, quinacridone, azo pigments, etc. Two or more species may be used in combination. Examples of the charge control agent other than these include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium base. Among these, those that control the base particles to negative polarity are preferable.

  Commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal Complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (from Hoechst), LRA-901, boron complex LR- 147 (made by Nippon Carlit Co., Ltd.).

  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.

  The developer of the present invention preferably further comprises 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 an average primary particle size of 10 to 50 nm. If the average primary particle size is less than 10 nm, the inorganic particles are less likely to be embedded in the base particles, and the image quality may be deteriorated. If the average primary particle size is more than 50 nm, the inorganic particles are detached from the developer, and the photosensitive member fills. May occur.

  The content of the inorganic particles in the developer of the present invention 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.

  The developer of the present invention preferably has a volume average particle size of 5 to 12 μm, 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. The volume average particle diameter of the developer can be measured using Multisizer III (manufactured by Coulter).

  The developer of the present invention preferably has an average circularity of 0.89 to 0.95, and 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.

  A toner image is obtained by developing the electrostatic latent image formed on the photosensitive member with the developer of the present invention using a known non-magnetic one-component developing type image forming apparatus. An image can be formed by transferring and fixing to a transfer medium. 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 acid anhydride and 0.5 g of dibutyltin oxide were added, and condensation polymerization was performed by raising the temperature to 230 ° C. using a mantle heater in a nitrogen atmosphere. At this time, using a flow tester CFT-500 (manufactured by Shimadzu Corporation), the degree of polymerization was tracked by measuring the softening point, and when the softening point reached 115 ° C., the reaction was terminated to obtain Resin A1. It was. Here, the measuring method of a softening point is the same as the measuring method of the softening point of resin A1 mentioned later.

  In addition, after heating up resin A1 to 200 degreeC using differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.), the sample cooled to 0 degreeC with the temperature-fall rate of 10 degree-C / min, temperature rising rate of 10 degreeC The glass transition point was 64.6 ° C. when the temperature was increased at a rate of 1 minute. In addition, using a flow tester CFT-500 (manufactured by Shimadzu Corporation), the heating rate was 3.0 ° C./min, the preheating time was 180 seconds, the load was 30 kg, the measurement temperature range was 80 to 160 ° C., and the diameter When 1.5 g of resin A1 was extruded from a die having a height of 1.0 mm and a height of 1.0 mm, the temperature at which half of the resin A1 had flowed out, that is, the softening point was 115.5 ° C. Furthermore, the content of a component that does not dissolve in THF was 0% by mass in Resin A1.

  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, 560 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic acid anhydride and 7 g of dibutyltin oxide were added, and a mantle heater was added under a nitrogen atmosphere. Was used for condensation polymerization by raising the temperature to 230 ° C. At this time, in the same manner as in the case of the resin A1, the degree of polymerization was tracked by measuring the softening point. When the softening point reached 150 ° C., the reaction was terminated to obtain a resin B1. Resin B1 had a glass transition point of 68.0 ° C., a softening point of 150.3 ° C., and a content of a component not dissolved in THF of 38% by mass.

  Next, 50 parts of C.I. I. Pigment Red 57-1 and 50 parts of resin A1 were mixed using a Henschel 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 obtain a master batch.

  8 parts of the obtained master batch, 40 parts of resin A1, 60 parts of resin B1 and 4 parts of release agent WEP-5 (manufactured by NOF Corporation) were mixed using a Henschel mixer to obtain a toner material.

  The obtained toner material is melted at 135 ° C. and then melted using a continuous open roll kneader Kneadex 160 (Mitsui Mining Co., Ltd.) having a roll having an outer diameter of 0.16 m and a length of 0.80 m. Kneaded. At this time, the temperature of the kneaded material was 105 ° C. The toner material is supplied at a rate of 8 kg / hour, the high temperature roll rotation speed is 50 rpm, the cooling roll rotation speed is 40 rpm, the high temperature roll supply side temperature is 90 ° C., and the high temperature roll discharge side temperature is 70 ° C. The roll supply side and discharge side temperatures were set to 20 ° C.

  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 teaplex type classifier type 50ATP (manufactured by Hosokawa Micron Co., Ltd.), a rotor type classifier, to obtain base particles.

  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 non-magnetic one-component developer.

In addition, using a flow tester CFT-500 (manufactured by Shimadzu Corporation), the heating rate was 3.0 ° C./min, the preheating time was 180 seconds, and the load was 10 kg (shear stress was 1.23 × 10 ⁵ Pa). The temperature at which the melt viscosity becomes 2.0 × 10 ³ Pa / sec when the measurement temperature range is 40 to 200 ° C. and 1.5 g of developer is extruded from a die having a diameter of 1.0 mm and a height of 1.0 mm. T _t-1 was 129.7 ° C. Moreover, when it measured similarly to _Tt-1 except having applied load 30 kg and 50 kg (shear stress was 3.68 * 10 < ⁵ > Pa and 6.13 * 10 < ⁵ > Pa), melt viscosity was 2.0. The temperatures T _t-2 and T _{t-3 at} which × 10 ³ Pa / sec were reached were 128.5 ° C. and 127.0 ° C., respectively.

  In addition, using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), the temperature of the developer was raised to 200 ° C. and then cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature was increased at a rate of 1 minute, and the endothermic curve was measured. As a result, a maximum endothermic peak of 30 to 200 ° C was present at 82.2 ° C.

  Further, the developer had a content of a component not dissolved in THF of 0.3% by mass, a volume average particle size of 9 μm, and an average circularity of 0.920.

  The volume average particle diameter of the developer 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 a developer 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, the volume average particle diameter of the developer was 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.

The average circularity of the developer was measured using a flow 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 a developer are added to 100 to 150 ml of water from which impure solids have been removed in advance. It was. Next, using a tabletop ultrasonic cleaner MODEL: VS-150, the dispersion is dispersed for 1 to 3 minutes, the concentration of the dispersion is 3 × 10 ³ to 1 × 10 ⁴ pieces / μl, and the average circularity of the developer is set. It was measured. Note that particles having a circularity of 0.40 to 1.00 were measured.

Using a blender ST-1 (manufactured by Oster), 4 g of resin A1 and 6 g of resin B1 were mixed to obtain a binder resin. The binder resin had a softening point of 135.4 ° C. Further, the measurement was performed in the same manner as T _t-1 , T _t-2 and T _t-3 except that a binder resin was used instead of the developer, and the melt viscosity was 2.0 × 10 ³ Pa / sec. The resulting temperatures T _r-1 , T _r-2 and T _r-3 were 174.1 ° C, 143.5 ° C and 144.8 ° C, respectively. Further, the binder resin had a content of a component not dissolved in THF of 25% by mass.

[Example 2]
Resin B2 was obtained in the same manner as Resin B1, except that the reaction was terminated when the softening point reached 138 ° C. Resin B2 had a glass transition point of 66.5 ° C., a softening temperature of 138.0 ° C., and a content of a component not dissolved in THF of 29% by mass.

A magenta nonmagnetic one-component developer was obtained in the same manner as in Example 1 except that the resin B2 was used instead of the resin B1, and the temperature on the supply side of the high temperature roll was set to 85 ° C. The temperature of the kneaded product was 100 ° C. Further, the developer had T _t-1 , T _t-2 and T _t-3 of 119.5 ° C., 118.8 ° C. and 117.6 ° C., respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.4 ° C. Further, the developer had a content of a component not dissolved in THF of 0% by mass, a volume average particle size of 9 μm, and an average circularity of 0.917.

Moreover, binder resin was obtained like Example 1 except having used resin B2 instead of resin B1. The binder resin has a softening point of 129.5 ° C., T _r-1 , T _r-2 and T _r-3 are 145.0 ° C., 133.2 ° C. and 132.8 ° C., respectively, and components that are not soluble in THF. The content was 19% by mass.

[Example 3]
50 parts of C.I. I. Pigment Red 57-1 and 50 parts of 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 obtain a master batch.

  8 parts of the obtained master batch, 60 parts of resin A1, 40 parts of resin B1 and 4 parts of release agent WEP-5 (manufactured by NOF Corporation) were mixed using a Henschel mixer to obtain a toner material.

A magenta non-magnetic one-component developer was obtained in the same manner as in Example 1 except that the obtained toner material was used and the temperature on the supply side of the high-temperature roll was set to 85 ° C. The temperature of the kneaded product was 95 ° C. The developers had T _t-1 , T _t-2 and T _t-3 of 117.2 ° C., 117.0 ° C. and 115.5 ° C., respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.8 ° C. Further, the developer had a content of components not soluble in THF of 0% by mass, a volume average particle size of 9 μm, and an average circularity of 0.918.

Further, a binder resin was obtained in the same manner as in Example 1 except that 6 g of the resin A1 and 4 g of the resin B1 were mixed. The binder resin has a softening point of 128.8 ° C., T _r−1 , T _r−2 and T _r−3 are 143.5 ° C., 130.1 ° C. and 132.0 ° C., respectively, and components that do not dissolve in THF. The content was 16% by mass.

[Comparative Example 1]
50 parts of C.I. I. Pigment Red 57-1 and 50 parts of 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 obtain a master batch.

  8 parts of the obtained master batch, 70 parts of resin A1, 30 parts of resin B1 and 4 parts of release agent WEP-5 (manufactured by NOF Corporation) were mixed using a Henschel mixer to obtain a toner material.

A magenta nonmagnetic one-component developer was obtained in the same manner as in Example 1 except that the obtained toner material was used. The temperature of the kneaded product was 101 ° C. Further, T _t-1 , T _t-2 and T _{t-3 of} the developer were 118.0 ° C, 114.0 ° C and 112.0 ° C, respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.1 ° C. Further, the developer had a content of components not soluble in THF of 0% by mass, a volume average particle size of 9 μm, and an average circularity of 0.921.

Further, a binder resin was obtained in the same manner as in Example 1 except that 7 g of the resin A1 and 3 g of the resin B1 were mixed. The binder resin has a softening point of 125.9 ° C., T _r−1 , T _r−2, and T _r−3 are 133.5 ° C., 125.3 ° C., and 122.8 ° C., respectively. The content was 12% by mass.

[Comparative Example 2]
50 parts of C.I. I. Pigment Red 57-1 and 50 parts of 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 obtain a master batch.

  8 parts of the obtained master batch, 30 parts of resin A1, 70 parts of resin B1 and 4 parts of release agent WEP-5 (manufactured by NOF Corporation) were mixed using a Henschel mixer to obtain a toner material.

A magenta nonmagnetic one-component developer was obtained in the same manner as in Example 1 except that the obtained toner material was used. The temperature of the kneaded product was 109 ° C. Further, the developer had T _t-1 , T _t-2 and T _t-3 of 146.9 ° C, 133.1 ° C and 131.0 ° C, respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.4 ° C. Further, the developer had a content of components not soluble in THF of 9% by mass, a volume average particle size of 9 μm, and an average circularity of 0.914.

A binder resin was obtained in the same manner as in Example 1 except that 3 g of the resin A1 and 7 g of the resin B1 were mixed. The binder resin has a softening point of 139.9 ° C., T _r−1 , T _r−2, and T _r−3 are 181.9 ° C., 148.0 ° C., and 146.0 ° C., respectively. The content was 31% by mass.

[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 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, 540 g of terephthalic acid, 200 g of 1,2,4-benzenetricarboxylic acid anhydride and 7 g of dibutyltin oxide were added, and a mantle heater was added under a nitrogen atmosphere. Was used for condensation polymerization by raising the temperature to 230 ° C. At this time, in the same manner as in the case of the resin A1, the degree of polymerization was tracked by measuring the softening point. When the softening point reached 155 ° C., the reaction was terminated to obtain a resin B3. Resin B3 had a glass transition point of 69.5 ° C., a softening point of 155.0 ° C., and a content of a component not dissolved in THF of 45% by mass.

A magenta non-magnetic one-component developer was obtained in the same manner as in Example 1 except that the resin B3 was used instead of the resin B1. The temperature of the kneaded product was 118 ° C. Further, the developer had T _t-1 , T _t-2 and T _t-3 of 145.3 ° C, 132.5 ° C and 130.1 ° C, respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.5 ° C. Further, the developer had a content of a component not dissolved in THF of 8% by mass, a volume average particle size of 9 μm, and an average circularity of 0.915.

Further, a binder resin was obtained in the same manner as in Example 1 except that the resin B3 was used instead of the resin B1. The binder resin has a softening point of 139.2 ° C., T _r−1 , T _r−2, and T _r−3 are 176.7 ° C., 146.0 ° C., and 145.5 ° C., respectively. The content was 33% by mass.

[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, 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 acid anhydride and dibutyltin oxide 7 g was added, and condensation polymerization was performed by raising the temperature to 230 ° C. using a mantle heater in a nitrogen atmosphere. At this time, in the same manner as in the case of the resin A1, the degree of polymerization was tracked by measuring the softening point. When the softening point reached 138 ° C., the reaction was terminated to obtain a resin B4. Resin B4 had a glass transition point of 65.0 ° C., a softening temperature of 138.2 ° C., and a content of a component not dissolved in THF of 5% by mass.

A magenta non-magnetic one-component developer was obtained in the same manner as in Example 1 except that the resin B4 was used instead of the resin B1, and the temperature on the supply side of the high temperature roll was set to 85 ° C. The temperature of the kneaded product was 94 ° C. Further, the developer had T _t-1 , T _t-2 and T _t-3 of 128.8 ° C, 126.5 ° C and 125.8 ° C, respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.7 ° C. Further, the developer had a content of components not soluble in THF of 0% by mass, a volume average particle size of 9 μm, and an average circularity of 0.920.

Moreover, binder resin was obtained like Example 1 except having used resin B4 instead of resin B1. The binder resin has a softening point of 129.1 ° C., T _r−1 , T _r−2, and T _r−3 are 130.5 ° C., 127.3 ° C., and 128.0 ° C., respectively. The content was 3% by mass.

[Comparative Example 5]
A magenta non-magnetic one-component developer was obtained in the same manner as in Example 1 except that the temperature on the supply side of the high temperature roll was set to 120 ° C. and the temperature on the discharge side of the high temperature roll was set to 90 ° C. The temperature of the kneaded product was 118 ° C. The developer had T _t-1 , T _t-2 and T _t-3 of 155.0 ° C, 138.0 ° C and 136.9 ° C, respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.5 ° C. Further, the developer had a content of a component not dissolved in THF of 22% by mass, a volume average particle size of 9 μm, and an average circularity of 0.916.

[Comparative Example 6]
In the same manner as in Example 1, except that resin B4 is used instead of resin B1, the temperature on the supply side of the high temperature roll is set to 70 ° C., and the temperature on the discharge side of the high temperature roll is set to 50 ° C. A one-component developer was obtained. The temperature of the kneaded product was 86 ° C. Further, the developer had T _t-1 , T _t-2 and T _t-3 of 127.0 ° C., 124.4 ° C. and 123.0 ° C., respectively. Further, when the endothermic curve of the developer was measured using a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.), a maximum endothermic peak of 30 to 200 ° C. was present at 82.1 ° C. Further, the developer had a content of components not soluble in THF of 0% by mass, a volume average particle size of 9 μm, and an average circularity of 0.914.

  Table 1 shows the properties of the binder resin.

表２に、非磁性一成分現像剤の特性を示す。

Table 2 shows the characteristics of the non-magnetic one-component developer.

なお、低温定着性及び耐固着性の評価方法を以下に示す。

In addition, the evaluation method of low temperature fixability and sticking resistance is shown below.

(Low temperature fixability)
An unfixed image was formed using a full color printer 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) was taken out, and the fixing temperature was determined at 130 to 200 ° C. using a fixing test device modified so that the fixing temperature and the linear velocity of the belt were the desired values. The ringtone image was fixed. About the obtained fixed image, the low temperature fixability was evaluated by conducting a smear property 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 state and the copied image were visually observed to evaluate the sticking resistance. At this time, the case where no streak or unevenness is generated in the sleeve is ○, and one or two streaks or unevenness is generated, but the case where no defect is observed on the image is Δ, and three or more streaks or unevenness is generated. Judgment was made as x.

Claims (7)

A method for producing a developer comprising a non-magnetic toner having base particles,
Using a continuous open roll type kneader to obtain a kneaded product by melt-kneading the toner material containing polyester , colorant and release agent;
Cooling the obtained kneaded product;
Crushing the cooled kneaded product;
Having the step of obtaining the base particles by classifying the pulverized kneaded product,
The polyester is obtained by polycondensation of an alkylene oxide adduct of bisphenol A, terephthalic acid and 1,2,4-benzenetricarboxylic anhydride, and the content of a component that does not dissolve in THF is 15% by mass or more and 30% by mass. % Or less ,
The developer has a content of a component that does not dissolve in THF of 0% by mass to 1% by mass,
The polyester 1.23 × ¹⁰ 5 Pa, the temperature of melt viscosity upon application of a shear stress of 3.68 × ¹⁰ 5 Pa and 6.13 × ¹⁰ 5 Pa is 2.0 × ¹⁰ 3 Pa · s, T _r-1 [° C.], T _r-2 [° C.] and T _r-3 [° C.], respectively, 1.23 × 10 ⁵ Pa, 3.68 × 10 ⁵ Pa and 6.13 × 10 in the developer. ^The temperatures at which the melt viscosity becomes 2.0 × 10 ³ Pa · sec when a shear stress of ⁵ Pa is applied are T _t-1 [° C.], T _t-2 [° C.] and T _t-3 [° C.], respectively. Then, the formula 130 ≦ T _r−2 ≦ 145
10 ≦ T _r−1 −T _r−2 ≦ 30
| T _r−3 −T _r−2 | ≦ 3
115 ≦ T _t−2 ≦ 130
| T _t-1 −T _t-2 | ≦ 5
| T _t−3 −T _t−2 | ≦ 3
15 ≦ T _r−1 −T _t−1
10 ≦ T _r−2 −T _t−2
10 ≦ T _r−3 −T _t−3
Meet the,
The temperature of the kneaded product when the toner material is melt-kneaded is not less than 50 ° C. below the softening point of the binder resin and not more than 20 ° C. below the softening point of the binder resin. A method for producing a developer. The developer, in the endothermic curve obtained by differential thermal analysis measurements, according to claim 1, characterized in that the maximum endothermic peak of 30 ° C. or higher 200 ° C. or less is present below 85 ° C. 65 ° C. or higher development Manufacturing method. The developer, method for producing a developing agent according to claim 1 or 2, characterized in that it further comprises inorganic particles. The method for producing a developer according to claim 3 , wherein the inorganic particles are silica particles . The developer, method for producing 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 developer, method for producing a developing agent according to any one of claims 1 to 5, wherein the volume average particle diameter is 5μm or more 12μm or less. The method for producing a developer according to any one of claims 1 to 6 , wherein the developer has an average circularity of 0.89 or more and 0.95 or less.