JP2011007857A - Development method - Google Patents

Abstract

[PROBLEMS] To stabilize the transportability of a two-component developer on a developing sleeve even when the temperature rises in the machine under high temperature and high humidity, and maintains the charging efficiency even before and after the temperature rise in the machine under high temperature and high humidity. Then, a developing method that does not generate a blank image is proposed.
An average interval Sm of irregularities based on JIS B0601 (1994) on the surfaces of developer carrying bodies 8 and 11 is 60 μm or more and 200 μm or less, and a ten-point average roughness Rz (μm) is 5.0 μm or more and 25.25. The toner is 0 μm or less, and the toner has a Tg1 (° C.) of the first temperature rise measured by a differential scanning calorimeter (DSC) after being left at 40 ° C. and 95% RH for 72 hours, and a temperature rise of 2 after the temperature fall. The relationship with the second Tg2 (° C.) satisfies the following formula (1).
0.0 ≦ Tg2−Tg1 ≦ 5.0 (1)
[Selection] Figure 1

Description

  The present invention relates to an electrophotographic method in which an electrostatic latent image formed on an electrophotographic photosensitive member or an electrostatic latent image carrier that is an electrostatic recording derivative is developed with a two-component developer to form an electrostatic latent image. The present invention relates to a developing method for forming a toner image on an image carrier.

  In recent years, development methods using two-component developers used in electrophotography need to meet market needs such as accelerated color shifts for office use, high definition for graphic markets, and high speed for light printing. is there. For this reason, further high image quality and high stability in performance are required.

  As the two-component development method, the following method is known. A magnetic brush of a two-component developer having a non-magnetic toner and a magnetic carrier is formed on a developer carrier (developing sleeve) containing a magnet, and the magnetic brush is predetermined by a developer layer thickness regulating member (developing blade). Is then transported to a development area facing the electrostatic latent image carrier (photosensitive drum). In the development area, the electrostatic latent image is used as a toner image by bringing the magnetic brush close to or in contact with the surface of the photosensitive drum while applying a predetermined developing bias between the photosensitive drum and the developing sleeve. It is a method of visualizing.

  In digital multi-function peripherals and full-color copiers that use two-component development methods, various improvements have been made in developing devices and two-component developers to cope with the recent improvement in image quality and stability. ing.

  In particular, in the two-component development method, a proposal for stabilizing the transport amount of the two-component developer on the developing sleeve is provided for the long-term durability issues such as high image quality and high stability. (Patent Document 1). This proposal defines the average particle diameter of the magnetic carrier contained in the two-component developer and the average interval Sm of the irregularities on the surface of the developing sleeve, and stabilizes the transport amount of the two-component developer over a long period of time. It is. The average spacing Sm of the irregularities on the surface of the developing sleeve tends to increase due to wear when used over a long period of time. For this reason, it is a proposal that the change in the transport of the two-component developer due to wear can be suppressed when the average particle size and the value of Sm of the magnetic carrier are in a preferable range. Such a conventional preferable value of Sm is usually set to 60 μm or less. However, considering the change in the transport amount of the two-component developer on the developing sleeve before and after the endurance, the larger the value of Sm, the smaller the change in the transportability of the two-component developer and the longer the long-term. A two-component developer that only develops sufficiently chargeable toner can be conveyed with respect to the latent image potential of the photosensitive drum.

  However, when the conventional Sm is increased, there are the following problems. In particular, in the case of digital multifunction peripherals and full-color copiers that require high durability, the Sm value also changes due to toner adhesion and fusion to the developing sleeve surface when the temperature inside the machine is high under high temperature and high humidity. It is a phenomenon that will end up. For example, toners used for two-component developers are widely used that contain at least a binder resin, a colorant, and a release agent. Due to the properties of the binder resin and the compatibility between the binder resin and the release agent, toner plasticization occurs when the temperature inside the machine is high under high temperature and high humidity, and the toner adheres to the surface of the developing sleeve and is fused. It becomes the cause of. As a result, the surface roughness of the developing sleeve surface changes due to the adhered or fused toner.

  On the other hand, this is a case where the curing of the toner occurs due to the temperature rise in the apparatus under high temperature and high humidity. This is a case where moisture is easily adsorbed as a characteristic of the toner. When the temperature rises in the machine under high temperature and high humidity, it is considered that the toner that has absorbed moisture releases moisture. As a result, a toner curing phenomenon occurs, and the charging amount for the latent image on the photosensitive drum also changes favorably without decreasing the transport amount on the developing sleeve. However, in this case, if the atmospheric humidity inside the machine returns to the surrounding environment after it has been durable, it will still adsorb moisture, resulting in plasticization of the toner. It changes greatly, and it becomes easy to generate a blank image due to a decrease in charging efficiency. Note that the whiteout image is an image in which the charge amount of the chargeable toner is insufficient with respect to the latent image potential on the photosensitive drum, and the dot is whitened for each dot. It tends to occur due to a decrease in the transport amount.

  Therefore, when the average interval Sm of the irregularities on the surface of the developing sleeve is large, the examination on the problem relating to the durability under high temperature and high humidity has not been sufficient.

JP 2002-062725 A

  The object of the present invention is to transport the two-component developer on the developing sleeve when the average interval Sm of the irregularities on the surface of the developing sleeve is large, even if the temperature rises in the machine under high temperature and high humidity, Sm does not change due to durability. A developing method that stabilizes the chargeability and maintains the charging efficiency even before and after the temperature rise in the apparatus under high temperature and high humidity, and does not generate a blank image.

  Said subject is achieved by the structure of the following this invention.

That is, according to the present invention, [1] a developer carrying member carries and conveys a two-component developer having toner and a magnetic carrier to a developing region facing the electrostatic latent image carrier, and a developer regulating member. A development method for regulating and developing a latent image formed on the electrostatic latent image carrier with a two-component developer,
The average interval Sm of irregularities based on JIS B0601 (1994) on the surface of the developer carrying member is 60 μm or more and 200 μm or less, and the ten-point average roughness Rz (μm) is 5.0 μm or more and 25.0 μm or less,
In addition, the toner has Tg1 (° C) of the first temperature rise measured by a differential scanning calorimeter (DSC) after being left at 40 ° C., 95% RH for 72 hours, and Tg2 (Tg2) of the second temperature rise after the temperature drop. The development method is characterized in that the relationship with the (° C.) satisfies the following formula (1).
0.0 ≦ Tg2−Tg1 ≦ 5.0 (1)
[2] The developing method according to [1], wherein the relationship between the Tg1 and the Tg2 satisfies the following formula (2).
0.0 ≦ Tg2−Tg1 ≦ 3.0 (2)
[3] The toner contains at least a binder resin having a polyester unit, a colorant, and a hydrocarbon wax,
The maximum endothermic peak temperature measured by DSC of the hydrocarbon wax is from 50 ° C. to 120 ° C., and relates to the developing method according to [1] or [2].
[4] Any one of [1] to [3], wherein the binder resin contains two or more kinds of resins, and each resin has at least a polyester unit and a vinyl copolymer unit. The developing method described in 1. above.
[5] The developing method according to any one of [1] to [4], wherein a tip angle α of the developer regulating member is 25 degrees or more and 50 degrees or less.

It is a schematic diagram which shows an example of the image development apparatus using the image development method of this invention. It is a schematic diagram which shows an example of the image development apparatus using the image development method of this invention. It is a schematic diagram which shows an example of the surface processing apparatus of the image development sleeve used for this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  In the developing method of the present invention, a two-component developer having toner and a magnetic carrier is carried and conveyed to a developing area facing the electrostatic latent image carrier (photosensitive drum) by a developer carrier (developing sleeve). In this developing method, the latent image formed on the photosensitive drum is regulated by a developer regulating member (developing blade) and developed with a two-component developer.

In the developing method of the present invention, the average interval Sm of the irregularities based on JIS B0601 (1994) on the surface of the developing sleeve is 60 μm to 200 μm, and the ten-point average roughness Rz (μm) is 5.0 μm to 25.0 μm. is there. The toner has Tg1 (° C) of the first temperature rise measured by a differential scanning calorimeter (DSC) after being left at 40 ° C, 95% RH for 72 hours, and Tg2 (° C) of the second temperature rise after the temperature drop. Satisfies the following formula (1).
0.0 ≦ Tg2−Tg1 ≦ 5.0 (1)

  By having the average spacing Sm (μm) and ten-point average roughness Rz (μm) of the irregularities on the surface of the developing sleeve within this range, it is possible to suppress the change in the transport amount of the two-component developer on the developing sleeve even before and after durability. High image quality can be maintained over a long period of time, and a highly stable development method can be obtained. In addition, the Tg1 (° C) of the first temperature rise measured by a differential scanning calorimeter (DSC) after the toner is left at 40 ° C and 95% RH for 72 hours, and the Tg2 (° C of the second temperature rise after the temperature drop) ) Satisfies the formula (1) to prevent toner adhesion and fusion to the developing sleeve surface due to toner plasticization at the time of temperature rise in the machine under high temperature and high humidity and humidity. A change in charging efficiency of the toner before and after the temperature rise can be suppressed.

  (Tg2−Tg1) of the toner is a value indicating the ratio of plasticization or curing in the heating and moisture adsorption of the toner. When (Tg2−Tg1) is less than 0.0, a toner plasticization phenomenon occurs due to heating. When (Tg2−Tg1) exceeds 0.0, it is considered that a curing phenomenon occurs when the moisture-adsorbed toner releases moisture by heating.

Therefore, if (Tg2-Tg1) is less than 0.0, the toner is plasticized, and toner adhesion and fusion are likely to occur on the surface of the developing sleeve, so that Sm and Rz on the surface of the developing sleeve change. As a result, the transport amount of the two-component developer changes, and the high image quality cannot be maintained for a long time. When (Tg2−Tg1) exceeds 5.0, the charge amount change of the toner before and after the temperature rise in the apparatus becomes large, the charging efficiency is lowered, the latent image potential on the photosensitive drum cannot be filled, and white spots are lost. It becomes easy to generate an image. A more preferable range of (Tg2-Tg1) is a range satisfying the following formula (2).
0.0 ≦ Tg2−Tg1 ≦ 3.0 (2)

  In the developing method of the present invention, the toner contains at least a binder resin having a polyester unit, a colorant, and a hydrocarbon wax, and the maximum endothermic peak temperature measured by DSC of the hydrocarbon wax is 50 ° C. or more. It is preferable that it is 120 degrees C or less. Conventionally, toner plasticization due to heat is caused by the compatibility of the binder resin and the wax. In the present invention, by using polyester as the binder resin and hydrocarbon wax as the wax, the compatibility between the binder resin and the wax can be prevented. The maximum endothermic peak temperature measured by DSC of the hydrocarbon wax is 50 ° C. or higher and 120 ° C. or lower, but it is preferably used because it does not cause wax adhesion or fusion on the developing sleeve surface. . When the endothermic peak temperature is less than 50 ° C., the wax itself may ooze out from the toner when the temperature rises in the machine under high temperature and high humidity. When the endothermic peak temperature exceeds 120 ° C., the wax dispersion in the toner becomes non-uniform, and the wax is exposed on the toner surface, which also causes adhesion and fusion to the developing sleeve surface. There is a case.

  In the developing method of the present invention, it is preferable that the binder resin for toner contains two or more kinds of resins, and each resin has at least a polyester unit and a vinyl copolymer unit. The toner curing phenomenon, which occurs when the temperature rises in the machine under high temperature and high humidity, is largely due to moisture adsorption of the polyester component. The vinyl copolymer component has a smaller amount of moisture adsorption than the polyester component. Therefore, by containing these two or more kinds of resins, the (Tg2-Tg1) of the toner is set within a predetermined range, and the object of the present invention can be effectively achieved.

  Further, in the developing method of the present invention, the tip angle α of the developing blade is preferably 25 degrees or more and 50 degrees or less. When the tip angle of the developing blade is within this range, when the magnetic brush of the two-component developer conveyed on the developing sleeve is regulated, it can be gradually regulated without applying a local shearing force. It is possible to suppress deterioration of the two-component developer and stabilize the transport amount over a long period of time. When the tip angle α of the developing blade is less than 25 degrees, local shearing force is applied, so that deterioration of the two-component developer is promoted. When the tip angle α of the developing blade exceeds 50 degrees, the shearing force applied to the entire magnetic brush becomes large, which also promotes the deterioration of the developer.

  Next, a developing device using the developing method of the present invention will be described.

  An example of a developing device using the developing method of the present invention is shown in FIG. The developer T accommodated in the developing container 2 in the developing device 1 is first arranged in the first developing sleeve including the first magnet roller 8 ′ disposed on the upstream side in the rotation direction “a” of the image carrier 10. 8 is carried and conveyed. Then, a developer layer is formed by a developing blade 9 disposed close to the developing sleeve 8. Here, in the present invention, Sm and Rz on the surface of the developing sleeve are adjusted to a predetermined roughness. The tip angle of the developing blade is preferably 25 degrees or more and 50 degrees or less. Thereafter, the developer T is conveyed by the developing sleeve 8 to a first developing area where the developing sleeve 8 and the image carrier 10 are opposed to each other. Then, in the region where the developing sleeve 8 and the second developing sleeve 11 arranged on the downstream side in the rotation direction a of the image carrier 10 are opposed to each other and pass through the developing region. Delivered. The developer T delivered to the developing sleeve 11 is carried and transported by the developing sleeve 11, transported to a second developing area where the developing sleeve 11 and the image carrier face each other, and used for development. Pass through and be collected in the developing container 2. As an example of the developing device, the description has been given with the example in which the developing sleeve is two, but the developing sleeve may be one or plural.

  Moreover, in order to control Sm and Rz on the surface of the developing sleeve within a predetermined range, any of a blasting apparatus that is a dry process, a honing apparatus that is a wet process, or a precision processing apparatus such as cutting can be used. As the abrasive grains used in the blasting apparatus and the honing apparatus, solid particles having a certain degree of hardness can be used as appropriate. For example, glass beads, silica, steel balls, ferrite particles, alumina particles, silicon carbide particles, zirconia particles, alumina zirconia particles, boron carbide particles, and solid solution particles such as alumina-titanium oxide, composites such as aluminum borate Examples thereof include oxide particles, and resin particles such as phenol, melamine, and nylon, and resin particles added with various fillers such as magnetic particles made of phenol and ferrite. By adjusting the size of these abrasive grains, the surface roughness of the developing sleeve surface can be adjusted as appropriate.

  The toner used in the present invention may be produced by any method such as a pulverization method, a polymerization method, an emulsion aggregation method, and a dissolution suspension method. Further, as the main component of the binder resin, it is preferable to use a polyester resin, a vinyl resin, or a hybrid resin. In order to effectively achieve the object of the present invention, it is particularly preferable to use a hybrid resin.

  When producing a polyester unit when a hybrid resin is used as the binder resin, a polyhydric alcohol, a polycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid ester, or the like can be used as a raw material monomer.

  Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component 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.

  Divalent acid components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides; Succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

  Among them, in particular, a bisphenol derivative represented by the following general formula (I) is used as a diol component, and a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner. .

  In the binder resin contained in the toner that can be used in the present invention, the “hybrid resin” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, it is a resin formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, preferably a vinyl polymer. A graft copolymer (or block copolymer) having a trunk polymer and a polyester unit as a branch polymer. In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group.

  Examples of vinyl monomers for producing vinyl copolymers or vinyl polymer units include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-phenyl styrene, p. -Ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn- Styrene derivatives such as decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; ethylene, propylene Unsaturated monoolefins such as butylene, butylene and isobutylene; butadiene, isoprene Unsaturated vinylenes such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluorides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate , Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl; methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, acrylate Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile, Examples include acrylic acid or methacrylic acid derivatives such as acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner that can be used in the present invention, the vinyl copolymer or vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.

  Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6-hexane. Examples include diol diacrylate, neopentyl glycol diacrylate and those obtained by replacing acrylate of the above compound with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, The thing which replaced the acrylate of the propylene glycol diacrylate and the above compound with the methacrylate is mentioned. Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2. , 2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing acrylate of the above compound with methacrylate.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  When producing the hybrid resin, it is preferable that a monomer component capable of reacting with the components of both resin units is contained in one or both of the vinyl polymer unit and the polyester unit. Examples of monomers that can react with the components of the vinyl polymer unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer unit, those capable of reacting with the components of the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, there is a polymer containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit listed above. A method obtained by carrying out the polymerization reaction of one or both resins is preferred.

  Examples of the polymerization initiator used for producing the vinyl copolymer or vinyl polymer unit usable in the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2 '-Azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2 Ethyl hexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, Acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaur Rate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy-2-ethyl Sanoeto, di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  Examples of the production method for preparing the hybrid resin used in the toner that can be used in the present invention include the production methods shown in the following (1) to (5).

  (1) After separately producing a vinyl polymer and a polyester resin, dissolve and swell in a small amount of an organic solvent, add an esterification catalyst and an alcohol, and heat to synthesize a hybrid resin. Method.

  (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer after the production thereof. The hybrid resin component is added as necessary to the reaction of a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (polyhydric alcohol, polycarboxylic acid), and the unit and monomer as necessary. Produced by reaction with polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester resin after the polyester resin is produced. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer, and a reaction between the unit and the monomer and a vinyl polymer unit added as necessary. . Also in this case, an organic solvent can be appropriately used.

  (4) After producing the vinyl polymer and the polyester resin, one or both of the vinyl monomer and the polyester monomer (polyhydric alcohol, polycarboxylic acid) were added in the presence of these polymer units, and added. A method for producing a hybrid resin component by performing a polymerization reaction under conditions according to the monomer. Also in this case, an organic solvent can be appropriately used.

  (5) A vinyl polymer unit, a polyester unit, and a hybrid resin component are obtained by mixing a vinyl monomer and a polyester monomer (polyhydric alcohol, polyvalent carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. How to manufacture. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit.

  The vinyl polymer or vinyl polymer unit in the present invention means a vinyl homopolymer or vinyl copolymer, a vinyl monopolymer unit or a vinyl copolymer unit.

  The toner used in the present invention preferably contains a wax component. Examples of the wax that can be used in the present invention include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or the like The block copolymer of these is mentioned. The maximum endothermic peak temperature measured by DSC of the wax that can be used in the present invention is preferably 50 ° C. or higher and 120 ° C. or lower.

  As the colorant used in the toner that can be used in the present invention, known dyes and / or pigments are used. A pigment alone may be used, but a dye and a pigment may be used in combination in terms of improving the sharpness.

  Examples of the color pigment for magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perlin compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 254, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

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

  Examples of the color pigment for cyan toner include C.I. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula (f).

〔式中、ｎは１乃至５の整数を示す。〕

[Wherein n represents an integer of 1 to 5. ]

  Examples of the colored pigment for yellow include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191, C.I. I. Bat yellow 1, 3, 20 and the like. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  As the black colorant that can be used in the present invention, carbon black, iron oxide particles, and those that are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  In addition, in the toner that can be used in the present invention, it is preferable to use a toner obtained by mixing a colorant in advance with the binder resin of the present invention into a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading the colorant master batch and other raw materials (binder resin, wax, etc.).

  The amount of the colorant used in the toner is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. This is preferable in terms of color reproducibility and developability.

  A known charge control agent can be used for the toner that can be used in the present invention in order to stabilize the chargeability. Although the charge control agent varies depending on the type of charge control agent and the physical properties of other toner particle constituent materials, it is generally preferable that the toner particle is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the binder resin. More preferably, the content is 0.1 to 5 parts by mass. As such a charge control agent, there are known one that controls the toner to be negatively charged and one that controls the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  Negatively chargeable charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene Etc. are available. As the positively chargeable charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner particles. In particular, the color toner that can be used in the present invention is preferably an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.

  Next, a method for producing the toner used in the present invention will be described.

  First, in the raw material mixing step, as a toner internal additive, at least a resin and a colorant are weighed and mixed in a predetermined amount and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Q-type mixer, and a nauter mixer.

  Further, the toner raw material mixed in the above composition is melted and kneaded to melt the binder resin, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In addition, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, PCM type twin screw extruder manufactured by Ikegai Seisakusho, KTK type twin screw extruder manufactured by Kobe Steel, Toshiba A TEM type twin screw extruder manufactured by Kikai Co., Ltd., a twin screw extruder manufactured by Kay Kay Kay, a co-kneader manufactured by Buss, etc. are generally used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like, and further, fine pulverization is performed by a known wind-type pulverizer or mechanical pulverizer. In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step.

  Further, the obtained finely pulverized product may be subjected to surface modification, that is, spheroidization treatment, in a surface modification step to obtain surface modified particles. After that, if necessary, the surface modified particles are classified into classifiers such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), or a high-voltage winder (new) Classification is performed using a sieving machine such as Tokyo Machine Co., Ltd. to obtain a toner having a weight average particle diameter of 3 to 11 μm.

  The toner that can be used in the present invention is preferably used after adjusting the fluidity of the toner by pulverizing and classifying, or after surface modification, and mixing the fluidizing agent with a mixer such as a Henschel mixer.

  Examples of the inorganic fine particles that can be used in the present invention include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, and dry process silica. There are powdered silica, treated silica obtained by subjecting them to surface treatment with a silane compound, an organosilicon compound, a titanium coupling agent, silicone oil and the like.

  As the silica that can be used in the present invention, both wet process silica and dry process silica can be used. Wet process silica is produced by a sol-gel method in which a solvent is removed from a silica sol suspension obtained by hydrolyzing and condensing a alkoxysilane with a catalyst in an organic solvent in which water is present, and then dried to form particles. There are silica particles. The silica particles produced by the sol-gel method have a sharp particle size distribution of the obtained particles, and approximately spherical particles are obtained, and particles having a desired particle size distribution can be obtained by changing the reaction time. Preferably used.

The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. . For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. .

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate are used. . As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

  As a method for hydrophobizing the inorganic fine powder, it is applied by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with the inorganic fine powder.

  As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. These are used alone or in a mixture of two or more.

  As inorganic fine particles that can be used in the present invention, the above-described wet process silica or dry process silica treated with a coupling agent having an amino group or silicone oil is used as necessary to achieve the object of the present invention. It doesn't matter. The added amount is 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidizing agent with respect to 100 parts by mass of the toner.

  Next, the magnetic carrier used in the present invention will be described. The magnetic carrier that can be used in the present invention preferably has at least a magnetic carrier core and a resin coating layer.

  As the magnetic carrier core, a magnetic carrier core such as a known ferrite particle, magnetite particle, or magnetic material-dispersed resin carrier core can be used.

  The magnetic carrier core is manufactured, for example, as described below.

  The magnetic carrier core is manufactured using a magnetic material. Magnetic materials include magnetic ferrite particles or magnetite particles containing one or more elements selected from iron, lithium, beryllium, magnesium, calcium, rubidium, strontium, nickel, copper, zinc, cobalt, manganese, and chromium. Is mentioned. Preferably, it is a magnetite particle or a magnetic ferrite particle having at least one element selected from copper, zinc, manganese, calcium, lithium and magnesium.

  Examples of the magnetic material for ferrite include the following. Ca—Mg—Fe ferrite, Li—Fe ferrite, Mn—Mg—Fe ferrite, Ca—Be—Fe ferrite, Mn—Mg—Sr—Fe ferrite, Li—Mg—Fe ferrite and Li— Ferrite magnetic material of iron oxide such as Mn-Fe ferrite.

  Ferrites of iron-based oxides can be obtained by mixing metal oxides, carbonates and nitrates in a wet or dry manner and pre-firing to obtain a desired ferrite composition. Next, the obtained iron-based oxide ferrite is pulverized to submicron. To the pulverized ferrite, 20 to 50% by mass of water for adjusting the particle size is added, and 0.1 to 10% by mass of, for example, polyvinyl alcohol (molecular weight 500 to 10,000) is added as a binder resin. Prepare. The slurry is granulated using a spray dryer and fired to obtain a ferrite core.

  Also, when obtaining a porous ferrite core, at the time of granulation, a pore adjuster such as sodium carbonate or calcium carbonate and various organic substances for controlling the pore density is added to form a slurry, It can be obtained by granulating and baking using a spray dryer. Further, by adding a material that inhibits the particle growth during the ferritization reaction, a complicated void can be formed inside the ferrite. Examples of such a material include silica.

  In order to produce a magnetic material-dispersed resin carrier core, for example, a vinyl-based or non-vinyl-based thermoplastic resin, a magnetic material, and other additives are sufficiently mixed by a mixer. The obtained mixture is melted and kneaded using a kneader such as a heating roll, a kneader, or an extruder. A magnetic material-dispersed resin carrier core can be obtained by pulverizing and classifying the cooled melt-kneaded product. The obtained magnetic material-dispersed resin carrier core may be further spheroidized thermally or mechanically. As another method, a monomer for forming the binder resin of the magnetic material-dispersed resin carrier core can be obtained by polymerizing in the presence of the magnetic material. Examples of the monomer for forming the binder resin include the following. Vinyl monomers, bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; ureas and aldehydes, melamine and aldehydes for forming urea resins are included.

  A method of synthesizing a phenol resin from phenols and aldehydes is particularly preferable. In this case, a magnetic substance, phenols and aldehydes are added to an aqueous medium, and the phenols and aldehydes in the aqueous medium are present in the presence of a basic catalyst. By polymerizing under the above, a magnetic material-dispersed resin carrier core can be produced.

  The phenols for producing the phenol resin may be compounds having a phenolic hydroxyl group in addition to phenol (hydroxybenzene). Examples of the compound having a phenolic hydroxyl group include alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, and bisphenol A; hydrogen of an aromatic ring (for example, benzene ring) or part of hydrogen of an alkyl group Or, halogenated phenols, all of which are substituted with chlorine atoms or bromine atoms.

  Examples of aldehydes for producing a phenol resin include the following. For example, formalin, formaldehyde in any form of paraformaldehyde, and furfural, more preferably formaldehyde.

  The molar ratio of aldehydes to phenols is preferably 1: 1 to 1: 4, more preferably 1: 1.2 to 1: 3.0. If the molar ratio of aldehydes to phenols is less than 1, particles are difficult to produce, and even if they are produced, the resin does not easily cure, and the strength of the particles produced tends to be weak. On the other hand, when the molar ratio of aldehydes to phenols is larger than 4, unreacted aldehydes remaining in the aqueous medium after the reaction tend to increase.

  The condensation of phenols with aldehydes can be performed using a basic catalyst. The basic catalyst may be any catalyst used in the production of ordinary resol type resins. Examples of the basic catalyst include aqueous ammonia, hexamethylenetetramine, dimethylamine, diethyltriamine, and alkylamines such as polyethyleneimine. Is included. The molar ratio of these basic catalysts to phenols is preferably 1: 0.02 to 1: 0.3.

  Next, the resin coating layer on the surface of the magnetic carrier core will be described.

  The resin coating layer used in the present invention contains at least a resin component. As the coating resin component, a thermoplastic resin is preferably used. Moreover, as a resin component, one type of resin may be sufficient and the combination of 2 or more types of resin may be sufficient.

  Examples of the thermoplastic resin as the coating resin component include polystyrene; acrylic resins such as polymethyl methacrylate and styrene-acrylic acid copolymer; styrene-butadiene copolymer; ethylene-vinyl acetate copolymer; polyvinyl chloride. Polyvinyl acetate, polyvinylidene fluoride resin, fluorocarbon resin, perfluorocarbon resin, solvent-soluble perfluorocarbon resin, polyvinyl alcohol, polyvinyl acetal, polyvinylpyrrolidone, petroleum resin, cellulose, cellulose acetate, cellulose nitrate, methylcellulose, hydroxymethylcellulose, hydroxymethylcellulose , Cellulose derivatives such as hydroxypropylcellulose; novolac resin; low molecular weight polyethylene; saturated alkyl polyester resin, polyethylene terephthalate Polybutylene terephthalate, such as polyarylate polyester resin; include polyether ketone resin; polyamide resin; polyacetal resin; polycarbonate resins; polyether sulfone resins; polysulfone resin; polyphenylene sulfide resin.

  The weight-average molecular weight Mw of the THF-soluble component of the resin component contained in the resin composition is 15,000 to 300,000 so that the adhesion to the magnetic carrier core and the magnetic carrier are particularly even when coated. This is preferable in that the core surface can be coated.

  Below, the measuring method concerning this invention is described in detail.

<Measurement of surface roughness (Sm, Rz) of developing sleeve>
The average interval Sm of unevenness based on JIS B0601 (1994) and the ten-point average roughness Rz (μm) were measured. The measurement points were obtained from an average value of a total of 6 points, 3 points in the axial direction of the developing sleeve and 2 points in the circumferential direction.

<Measurement of Tg1 and Tg2 of toner>
The Tg1 and Tg2 of the toner are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  As a pretreatment condition of the toner, a sample after being left at 40 ° C. and 95% RH for 72 hours is used.

  First, Tg1 (° C.) measurement at the first temperature increase is performed. About 10 mg of the pretreated toner is precisely weighed, put in an aluminum pan and sealed, and an empty aluminum pan is used as a reference. Measure in min. In the first temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature of the binder resin, that is, Tg1 (° C.) for the first temperature increase. Next, measurement is performed under the same conditions, and the glass transition temperature of the binder resin obtained in the second temperature raising process is set to Tg2 (° C.) for the second temperature raising.

  Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited thereto.

<Development sleeve production example 1>
As a base of the developing sleeve, surface processing was performed using an aluminum cylindrical tube made of aluminum and a blasting apparatus as shown in FIG. As abrasive grains, # 100 glass beads (average particle diameter: 120 μm) were used. The discharge pressure of the abrasive grains was 0.3 MPa. A magnet roll was inserted into the obtained blast sleeve, and then a flange was attached to obtain a developing sleeve (S-1). Table 1 shows the surface roughness of the obtained developing sleeve (S-1).

<Development sleeve production examples 2 to 3>
The developing sleeves (S-2) and (S-3) are the same as the developing sleeve manufacturing example 1 except that the abrasive grains used for blasting are manufactured in place of # 250 and # 60 in the developing sleeve manufacturing example 1. Got. Table 1 shows the surface roughness of the obtained developing sleeves (S-2) and (S-3).

<Example 1 of production of binder resin for toner>
As a monomer of the condensation polymerization resin, 40 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (18 parts by weight), terephthalic acid (8 parts by weight), trimellitic anhydride (5 parts by weight), fumaric acid (5 parts by weight) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. The polycondensation reaction was carried out for 1 hour under reduced pressure. Then, it cooled to 160 degreeC.

  As a monomer of addition polymerization resin, a mixture of 15 parts by mass of styrene and 4 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of acrylic acid as a reactive monomer and tertiary butyl peroxide as a polymerization initiator was stirred at 160 ° C. The solution was added dropwise over 1 hour. Furthermore, after maintaining the same temperature for 1 hour and performing addition polymerization reaction, it heated up to 200 degreeC and was further made to react under reduced pressure for 1 hour. Thereafter, 2 parts by mass of fumaric acid and 2 parts by mass of trimellitic anhydride were added to the reaction vessel, subjected to condensation polymerization reaction for 2 hours under normal pressure, and further reacted for 1 hour under reduced pressure to obtain a low softening point resin. The softening point of the low softening point resin was 95 ° C.

  Next, in the same manner as the method for producing a low softening point resin, a high softening point resin was obtained with a condensation polymerization reaction of 6 hours. The softening point of the high softening point resin was 135 ° C.

  The obtained low softening point resin and high softening point resin were blended at a mass ratio of 50:50 to obtain a binder resin (B-1). Table 2 shows the configuration of the binder resin.

<Example 2 of production of binder resin for toner>
As a monomer of the condensation polymerization resin, 40 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (18 parts by mass), terephthalic acid (8 parts by mass), trimellitic anhydride (5 parts by mass), fumaric acid (5 parts by mass) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. Thereafter, the reaction was further subjected to a condensation polymerization reaction under reduced pressure for 1 hour, and then cooled to 160 ° C.

  As a monomer of addition polymerization resin, a mixture of 15 parts by mass of styrene and 4 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of acrylic acid as a reactive monomer and tertiary butyl peroxide as a polymerization initiator was stirred at 160 ° C. The solution was added dropwise over 1 hour. Furthermore, after maintaining the same temperature for 1 hour and performing addition polymerization reaction, it heated up to 200 degreeC and was further made to react under reduced pressure for 1 hour. Thereafter, 2 parts by weight of fumaric acid and 2 parts by weight of trimellitic anhydride are put into a reaction vessel, subjected to a condensation polymerization reaction for 4 hours under normal pressure, and further reacted for 1 hour under reduced pressure to obtain a binder resin (B-2). Obtained. The softening point of the binder resin (B-2) was 115 ° C. Table 2 shows the configuration of the binder resin.

<Example 3 of production of binder resin for toner>
As a monomer of the condensation polymerization resin, 35 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (16 parts by mass), terephthalic acid (7 parts by mass), trimellitic anhydride (4 parts by mass), fumaric acid (4 parts by mass) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. Thereafter, the reaction was further subjected to a condensation polymerization reaction under reduced pressure for 1 hour, and then cooled to 160 ° C.

  As a monomer of the addition polymerization resin, a mixture of 23 parts by mass of styrene and 6 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of acrylic acid as a reactive monomer and tertiary butyl peroxide as a polymerization initiator was stirred at 160 ° C. The solution was added dropwise over 1 hour. Furthermore, after maintaining the same temperature for 1 hour and performing addition polymerization reaction, it heated up to 200 degreeC and was further made to react under reduced pressure for 1 hour. Thereafter, 2 parts by weight of fumaric acid and 2 parts by weight of trimellitic anhydride are put into a reaction vessel, subjected to a condensation polymerization reaction for 4 hours under normal pressure, and further reacted for 1 hour under reduced pressure to obtain a binder resin (B-3). Obtained. The softening point of the binder resin (B-3) was 116 ° C. Table 2 shows the configuration of the binder resin.

<Example 4 of production of binder resin for toner>
As monomers of the condensation polymerization resin, 45 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (20 parts by mass), terephthalic acid (9 parts by mass), trimellitic anhydride (6 parts by mass), fumaric acid (6 parts by mass) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. Thereafter, the reaction was further subjected to a condensation polymerization reaction under reduced pressure for 1 hour, and then cooled to 160 ° C.

  As a monomer of the addition polymerization resin, a mixture of 7.5 parts by mass of styrene and 2 parts by mass of 2-ethylhexyl acrylate, 0.5 part by mass of acrylic acid as a reactive monomer and 160 parts of tertiary butyl peroxide as a polymerization initiator is used. The mixture was added dropwise with stirring at 1 ° C over 1 hour. Furthermore, after maintaining the same temperature for 1 hour and performing addition polymerization reaction, it heated up to 200 degreeC and was further made to react under reduced pressure for 1 hour. Thereafter, 2 parts by weight of fumaric acid and 2 parts by weight of trimellitic anhydride are put into a reaction vessel, subjected to a condensation polymerization reaction for 4 hours under normal pressure, and further reacted for 1 hour under reduced pressure to obtain a binder resin (B-4). Obtained. The softening point of the binder resin (B-4) was 114 ° C. Table 2 shows the composition of the binder resin.

<Example 5 of production of binder resin for toner>
As monomers of the condensation polymerization resin, 25 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (10 parts by mass), terephthalic acid (5 parts by mass), trimellitic anhydride (3 parts by mass), fumaric acid (3 parts by mass) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. Thereafter, the reaction was further subjected to a condensation polymerization reaction under reduced pressure for 1 hour, and then cooled to 160 ° C.

  As a monomer of addition polymerization resin, a mixture of 38 parts by mass of styrene and 10 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid as a reactive monomer and tertiary butyl peroxide as a polymerization initiator was stirred at 160 ° C. The solution was added dropwise over 1 hour. Furthermore, after maintaining the same temperature for 1 hour and performing addition polymerization reaction, it heated up to 200 degreeC and was further made to react under reduced pressure for 1 hour. Thereafter, 2 parts by weight of fumaric acid and 2 parts by weight of trimellitic anhydride are put into a reaction vessel, subjected to a condensation polymerization reaction for 4 hours under normal pressure, and further reacted for 1 hour under reduced pressure to obtain a binder resin (B-5). Obtained. The softening point of the binder resin (B-5) was 115 ° C. Table 2 shows the configuration of the binder resin.

<Example 6 of production of binder resin for toner>
A styrene-acrylic resin was prepared using the following raw materials.
Styrene 82.0 parts by mass n-butyl acrylate 17.0 parts by mass Di-tert-butyl peroxide 1.0 part by mass The above raw material was dropped into 200 parts by mass of xylene heated at 160 ° C. with stirring over 2 hours. did. Furthermore, the polymerization reaction was performed under reflux of xylene, the temperature was raised to 200 ° C., and the solvent was distilled off while further reducing the pressure to obtain a binder resin (B-6). The softening point of the binder resin (B-6) was 117 ° C. Table 2 shows the configuration of the binder resin.

<Example 7 of production of binder resin for toner>
As monomers of the condensation polymerization resin, 50 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4- Hydroxyphenyl) propane (22 parts by mass), terephthalic acid (10 parts by mass), trimellitic anhydride (9 parts by mass), fumaric acid (9 parts by mass) and dibutyltin oxide were reacted in a nitrogen atmosphere at 230 ° C. and normal pressure for 8 hours. The binder resin (B-7) was obtained by a condensation polymerization reaction under reduced pressure for 1 hour. The softening point of the binder resin (B-7) was 113 ° C. Table 2 shows the configuration of the binder resin.

<Toner Production Example 1>
Toner (T-1) was prepared using the following materials.
Binder resin (B-1) 100 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by mass Normal paraffin wax (maximum endothermic peak: 80 ° C.) 7 parts by mass It melt-kneaded with the set twin-screw extruder (PCM-30 type, made by Ikegai). The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized toner. The obtained coarsely pulverized toner was finely pulverized using a mechanical pulverizer (T-300 type, manufactured by Turbo Kogyo). As pulverization conditions, pulverization was performed with the rotational speed of the rotor being 120 s ⁻¹ .

Next, the obtained finely pulverized product is removed at 60 ° C. with a dispersed rotor rotation speed of 100 s ⁻¹ (rotational peripheral speed is 130 m / sec) while removing fine particles at a classification rotor rotation speed of 120 s ⁻¹ using a surface modification apparatus. Surface treatment was performed for 2 seconds to obtain a toner classified product.

Then, 1.0 part by mass of rutile type titanium oxide having a BET specific surface area of 100 m ² / g and 1.0 part by mass of hydrophobic silica having a BET specific surface area of 130 m ² / g are added to 100 parts by mass of the obtained toner classified product. The toner (T-1) was obtained by mixing with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 for 10 minutes. Table 3 shows the structure of the obtained toner (T-1). Further, Tg2-Tg1 of the toner (T-1) was 1.5 ° C.

<Toner Production Examples 2 to 12>
In Toner Production Example 1, toners (T-2) to (T-12) were obtained in the same manner as in Toner Production Example 1, except that the materials used were changed as shown in Table 3.

<Example of magnetic carrier production>
A magnetic carrier core was produced using the materials shown below.
Phenol 10 parts by mass Formaldehyde solution (37% by mass aqueous solution) 6 parts by mass Magnetite particles (number average particle size 0.3 μm) 84 parts by mass The above materials, 5 parts by mass of 28% by mass ammonia water, and 25 parts by mass of water are placed in a flask. The mixture was heated and maintained at 85 ° C. for 30 minutes with mixing, and was cured by polymerization for 3 hours. Then, after cooling to 30 ° C. and further adding water, the supernatant was removed, and the precipitate was washed with water and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic carrier core of a magnetic fine particle dispersed type in which magnetite particles were dispersed in a phenol resin.

Next, a magnetic carrier was produced using the following materials.
The obtained magnetic carrier core 100 parts by mass Acrylic resin 1.0 part by mass First, the acrylic resin was dissolved in toluene to a solid content of 10%. Subsequently, coating was performed using a fluidized bed coating apparatus (SFP-01 type: manufactured by POWREC), and after heating and drying in a vacuum dryer at 100 ° C. for 4 hours, sieving was performed using a # 200 mesh to obtain magnetic properties. Carrier C was obtained.

<Example 1>
A two-component developer was prepared using toner (T-1) and magnetic carrier C. Mixing was performed using a V-type mixer so that the toner concentration was 10% by mass. As a replenisher, toner (T-1) and magnetic carrier C were mixed using a V-type mixer so that the toner concentration was 90% by mass.

  Next, the obtained two-component developer was accommodated in the developing device shown in FIG. Further, a developing sleeve (S-1) was attached to the developing device shown in FIG. 2, and the developing blade was attached so that the tip angle was 35 degrees. Table 4 shows the configuration of the developing device. Using this developing device and the above-described replenisher, image output evaluation was performed with a Canon copier imagePRESS C7000VP. Evaluation was performed under an environment of 30 ° C./80% RH (H / H), with an image printing ratio of 30%, and durability up to 50,000 sheets. In addition, after the endurance of 50,000 sheets, it was left for 3 days and evaluated again. The evaluation results are shown in Table 5. The evaluation criteria are shown below.

<Evaluation items>
[Image density]
The obtained image was subjected to density measurement with a densitometer X-Rite 500 type, and an average value of 6 points was taken as an image density.

[Charging efficiency]
The charging efficiency was calculated as follows.
Charging efficiency = (Latent image potential on photosensitive drum−Surface potential when developing toner) / (Latent image potential on photosensitive drum−Developing potential) × 100

  The potential was measured by attaching a surface potentiometer (TREK MODEL 344) and a probe.

[Outline evaluation]
The initial 100 images, 100 images after endurance of 50,000 images, and 100 images after being left out were checked and judged according to the following indicators.
A: Less than 3 white areas / 100 sheets B: 3 or more white areas, less than 5/100 sheets C: 5 or more white areas, less than 7/100 sheets D: White areas 7 or more, less than 10/100 sheets E; 10 or more white spots

<Examples 2 to 13 and Comparative Examples 1 to 4>
In Example 1, each evaluation was performed in the same manner as in Example 1 except that the configuration of the developing device was changed as shown in Table 4. The obtained evaluation results are shown in Table 5.

  DESCRIPTION OF SYMBOLS 1 Developing device, 2 Developing container, 8 First developing sleeve, 10 Image carrier, 11 Second developing sleeve, T Developer

Claims (5)

With the developer carrier, the two-component developer having toner and magnetic carrier is carried and transported to the development area facing the electrostatic latent image carrier, and regulated by the developer regulating member. A developing method for developing a latent image formed on a body with a two-component developer,
The average interval Sm of irregularities based on JIS B0601 (1994) on the surface of the developer carrying member is 60 μm or more and 200 μm or less, and the ten-point average roughness Rz (μm) is 5.0 μm or more and 25.0 μm or less,
In addition, the toner has Tg1 (° C) of the first temperature rise measured by a differential scanning calorimeter (DSC) after being left at 40 ° C., 95% RH for 72 hours, and Tg2 (Tg2) of the second temperature rise after the temperature drop. The developing method is characterized in that the relationship with the temperature (° C.) satisfies the following formula (1).
0.0 ≦ Tg2−Tg1 ≦ 5.0 (1) 2. The developing method according to claim 1, wherein the relationship between Tg1 and Tg2 satisfies the following formula (2).
0.0 ≦ Tg2−Tg1 ≦ 3.0 (2) The toner contains at least a binder resin having a polyester unit, a colorant, and a hydrocarbon wax,
3. The developing method according to claim 1, wherein a maximum endothermic peak temperature measured by DSC of the hydrocarbon wax is 50 ° C. or higher and 120 ° C. or lower.   4. The developing method according to claim 1, wherein the binder resin contains two or more kinds of resins, and each resin has at least a polyester unit and a vinyl copolymer unit. .   The developing method according to claim 1, wherein a tip angle α of the developer regulating member is 25 degrees or more and 50 degrees or less.

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