JP4808012B2 - Toner, toner manufacturing method and process cartridge - Google Patents

Description

  The present invention relates to a toner corresponding to an oilless fixing process, a toner manufacturing method, and a process cartridge using the toner.

With the development of electrophotographic technology, image forming apparatuses based on electrophotography such as laser printers, copiers and multi-function peripherals (hereinafter referred to as MFPs) equipped with electrophotographic technology are increasingly used in offices and the like. It has become like this.
In the process, there is a demand for a device that is less expensive than before, can be easily maintained by the user, and has a compact size that does not cause a feeling of pressure even when installed on the desk side. There has also been a demand for a device that can easily output an appealing color image as an output image.

Many electrophotographic image forming apparatuses use toner containing at least a binder resin and a colorant.
(1) A latent image carrier called a photosensitive drum or photosensitive belt is uniformly charged using a charging roller, a charging brush, or other charging means, and then (charging process)
(2) A latent image is created by discharging any part of the latent image carrier by exposure with a light source such as a laser or a light-emitting diode (exposure process)
(3) Next, the latent image on the latent image carrier is developed with toner by bringing a toner carrier called a developing roller, a developing sleeve, etc. close to or in contact with the latent image carrier, and (development process)
(4) The toner image on the latent image carrier is transferred to a transfer member such as an intermediate transfer roller or an intermediate transfer belt as necessary (transfer process).
(5) Transfer the toner image on the latent image carrier or transfer member to a recording member such as paper or OHP (transfer process)
(6) The toner image on the recording member is melted by being pressed and heated by a fixing member such as a fixing roller or a fixing belt, and impregnated and fused on the recording member (fixing process).
Process in order.

  To obtain a color image, prepare two or more toner carriers having different color toners, repeat exposure, development, and transfer to create a color toner image on the transfer member or recording member. 2 or more sets of toner carriers having different color toners and corresponding latent image carriers, and exposing and developing each latent image carrier, There is a method of performing a subsequent process (tandem method) after creating a color toner image by transferring to a transfer member or a recording member.

One means for achieving a compact and inexpensive electrophotographic image forming apparatus that can be easily maintained by the user is a so-called oil-less fixing process that does not use oil in the fixing process.
Normally, when the toner is melted in the fixing process, the toner adheres closely to the fixing member, and a phenomenon (jam) in which the recording member is not output without the recording member being separated from the fixing member occurs. In order to prevent this, a mechanism for applying oil such as silicon oil to the fixing member is provided so that the recording member is released from the fixing member. However, the oil application mechanism has a large occupied volume in the apparatus, and the apparatus In addition to being a hindrance to downsizing, the oil is consumed by the use of the device, which requires the user to purchase and replenish the oil. Therefore, instead of applying oil, a wax component is included in the toner, and in the fixing process, the wax oozes between the toner and the fixing member when the toner is melted, thereby reducing the adhesive force between the fixing member and the toner interface. As a result, a method for ensuring release (fixing separation property) between the fixing member and the recording member has been widespread. This is the oilless fixing process.

  As described above, in order to ensure fixing separation in the oilless fixing process, it is necessary to disperse the wax in the toner. However, the wax has a low polarity and is generally not a binder resin for a toner having a polar group. Since they are compatible, they are easily exposed to the toner surface layer or dissociated from the toner during the production of the toner, and the wax released from the toner is liable to adversely affect processes such as developing member contamination and developer lock due to poor fluidity. Furthermore, as a developing process, the toner carrying member is driven with a constant pressure applied to the toner carrying member by a regulating member such as a regulating blade, so that the toner on the toner carrying member is uniformly charged while being uniformly charged. When a so-called one-component development process that forms the conveyance surface is adopted, a phenomenon that the wax component or fluidizing agent adheres to the regulating blade (blade fixation) occurs, the toner conveyance surface is disturbed, and the image quality is greatly reduced. Resulting in.

Various proposals have been made so far to solve the above problems.
For example, a method of reducing the amount of wax in the toner and improving the elasticity of the binder resin may be employed. However, the toner is difficult to melt, poor fixing occurs, or the gloss of the image is lowered particularly in a color image. And the print quality is greatly impaired.
Therefore, as a method for causing the toner to contain a wax amount that does not have an adverse effect on the development process and can sufficiently exhibit the fixing separation property, a method using a resin containing a wax in advance as a binder resin has been proposed. .
For example, Patent Document 1 discloses that in this technique, the melting point of the wax is high, and particularly in the region where the fixing temperature is low, the melting of the wax is slow and the wax does not sufficiently ooze out from the toner, so that the function of improving the fixing separation property is not effective. It is enough. When a toner having a high outflow end temperature as in Patent Document 2 or a toner having a large ratio of a resin having a high melt viscosity as in Patent Document 4, the gloss of the image is low, particularly in a color image, the image quality is poor, There is also a problem that the fixing strength of the image is insufficient. As in Patent Document 3, when the softening point of the resin to which the wax is internally added is low, a large amount of the wax is exposed on the surface during the toner production process, and the adverse effect on the process becomes obvious.
JP 2001-117261 A JP 2002-148844 A Japanese Patent Laid-Open No. 2003-255587 JP 2003-270859 A

  The present invention relates to fixing performance in an oilless fixing process, in particular, separation between a recording member and a fixing member, adhesion required for practical use with a recording member after fixing, and an image on a recording member after fixing. An object of the present invention is to provide a toner that has excellent image quality and is free from contamination of a photoreceptor, a regulating blade, and the like.

In order to solve the above-described problems, the present invention is characterized in that the toner has a specific resin / wax composition and specific rheological characteristics, and specifically comprises the following constitution.
(1) In a toner comprising at least a resin internally added with wax (resin A), a resin not internally added with wax (resin B), and a colorant,
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner characterized in that an outflow end temperature Tend of the toner measured by a constant load extrusion type capillary rheometer is 135 ° C. or less.

(2) The toner according to (1), wherein the toner contains a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A.
(3) The toner according to (1) or (2), wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.
(4) The toner according to any one of (1) to (3), wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.
(5) The toner according to any one of (1) to (4), wherein the toner has an acid value of 10 or more and 40 or less.
(6) The half-value width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less, according to (1) to (5) above The toner according to any one of the above.
(7) The toner as described in any one of (1) to (6) above, wherein a part or all of at least one of the resin A or the resin B has a polyester skeleton.
(8) The toner according to any one of (1) to (7) above, which contains a wax dispersant.
(9) Any of (1) to (8) above, wherein the resin A is obtained by polymerizing at least a raw material monomer (monomer A) of the resin constituting the resin A and a mixture containing the wax The toner described in 1.
(10) The toner according to (9) above, wherein the monomer A contains 0.1 to 5% by mass of a tri- or higher functional monomer.

(11) At least a resin internally added with wax (resin A), a resin not internally added with wax (resin B), a colorant is supplied to a raw material mixer, mixed, kneaded, rolled and cooled, and then crushed. In the method for producing toner to be classified,
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner production method, wherein the outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less.

(12) The method for producing a toner according to (11), wherein the toner includes a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A. .
(13) The toner production method as described in (11) or (12) above, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.
(14) The method for producing a toner according to any one of (11) to (13), wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.
(15) The toner production method as described in any one of (11) to (14) above, wherein the toner has an acid value of 10 or more and 40 or less.
(16) The half width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less. A method for producing the toner according to any one of the above.
(17) The method for producing a toner as described in any one of (11) to (16) above, wherein a part or all of at least one of the resin A or the resin B has a polyester skeleton.
(18) The toner production method as described in any one of (11) to (17) above, which contains a wax dispersant.
(19) The resin A is
The method for producing a toner according to any one of (11) to (18), wherein the toner is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.
(20) The method for producing a toner according to (19), wherein the monomer A contains 0.1 to 5% by mass of a trifunctional or higher functional monomer.

(21) Toner obtained through a process of aggregating at least resin particles of resin (resin A) internally added with wax, resin particles of resin (resin B) not internally added with wax, and colorant particles in an aqueous medium In the manufacturing method of
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner production method, wherein the outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less.

(22) The method for producing a toner according to (21), wherein the toner contains a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A. .
(23) The toner production method as described in (21) or (22) above, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.
(24) The toner production method as described in any one of (21) to (23) above, wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.
(25) The method for producing a toner according to any one of (21) to (24), wherein the toner has an acid value of 10 or more and 40 or less.
(26) The half-width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less, wherein (21) to (25) A method for producing the toner according to any one of the above.
(27) The method for producing a toner according to any one of (21) to (26) above, wherein a part or all of at least one of the resin A or the resin B has a polyester skeleton.
(28) The toner production method as described in any one of (21) to (27) above, which comprises a wax dispersant.
(29) The resin A is
The method for producing a toner according to any one of (21) to (28), wherein the toner is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.
(30) The method for producing a toner according to (29), wherein the monomer A contains 0.1 to 5% by mass of a tri- or higher functional monomer.

(31) In a process cartridge that is detachably attached to an image forming apparatus main body,
At least a latent image carrier;
A charging member that contacts and charges the latent image carrier;
A drum unit comprising: a cleaning member that removes and collects transfer residual toner on the latent image carrier;
At least toner;
A developing container for containing the toner;
Toner transporting means for rotating and stirring the fixed shaft in the developing container to stir and transport the toner;
A toner carrier in contact with the latent image carrier;
A toner regulating member in contact with the toner carrying member via toner;
A process cartridge in which a toner unit comprising a toner supply roller for supplying toner to the toner carrier is integrated;
The toner is
At least in a toner comprising a resin internally added with wax (resin A), a resin not internally added with wax (resin B), and a colorant,
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A process cartridge characterized in that an outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less.

(32) The process cartridge according to (31), wherein the toner contains a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A.
(33) The process cartridge according to (31) or (32), wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.
(34) The process cartridge according to any one of (31) to (33), wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.
(35) The process cartridge according to any one of (31) to (34), wherein the toner has an acid value of 10 or more and 40 or less.
(36) The half-value width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less, wherein (31) to (35) One of the process cartridges.
(37) The process cartridge according to any one of (31) to (36), wherein a part or all of at least one of the resin A or the resin B has a polyester skeleton.
(38) The process cartridge as described in any one of (31) to (37) above, which contains a wax dispersant.
(39) The resin A is
The process cartridge according to any one of (31) to (38), which is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.
(40) The process cartridge according to (39), wherein the monomer A contains 0.1 to 5% by mass of a tri- or higher functional monomer.

That is, the present invention achieves the intended object by having the toner have a specific resin and wax composition and specific rheological properties.
The present invention is characterized by using a resin internally added with wax. The resin internally added with the wax used in the present invention is not particularly limited as long as the wax is internally added to the resin, and the resin is generally used as a resin for toner.
Specific examples include polyester, polyurethane, polyurea, epoxy resin, vinyl resin, and copolymers thereof. Of these, polyesters, vinyl resins, block polymers, and graft polymers thereof are preferable.

Examples of the polyester include a polycondensate of polyol (1) and polycarboxylic acid (2).
Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbons:
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene, isoprene, 1 , 4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene and the like.
Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and salts thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-24) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms, such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino- 2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3 -(Meth) acrylamide-2-hydride Roxypropane sulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfate [Poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2 -Acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
Amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, Morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like.
Quaternary ammonium cation group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Halogen element-containing vinyl monomers:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two The alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxy] Ethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) mono Acrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate Lauryl alcohol ethylene oxide 30 mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]. Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dihumanro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene. Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(10) Other vinyl monomers:
Isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

  Examples of the vinyl monomer copolymer include a polymer obtained by copolymerizing any of the above-mentioned monomers (1) to (10) with two or more in an arbitrary ratio, for example, styrene. -(Meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- ( A meth) acrylic acid copolymer, a styrene- (meth) acrylic acid, a divinylbenzene copolymer, a styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

  If necessary, polyester and vinyl resin, or polyesters or vinyl resins may be combined to form a block or graft. For blocking and grafting, a known method may be used. For example, a hydroxyl group or a carboxylic acid is used to polymerize a vinyl resin in the presence of a polyester having a vinyl group, an allyl group, or a (meth) acryloyl group. Polymerization of polyester in the presence of a vinyl resin having a group, an amino group, etc., having a vinyl monomer, polyol, polycarboxylic acid, and at least one group among a carboxyl group, a hydroxyl group, an amino group, and an epoxy group Examples thereof include a method in which addition polymerization and condensation polymerization are performed in parallel or sequentially in the presence of a vinyl monomer.

As a method for producing a resin internally added with wax used in the present invention,
(1) A monomer (polyol, polycarboxylic acid, vinyl monomer) in which wax is dissolved or dispersed is polymerized.
(2) The wax and resin are dissolved in a solvent, and the solvent is removed while the wax is finely dispersed.
(3) Melting and kneading wax and resin.
And the like.
Regarding the method (1), it may be carried out simultaneously with blocking and grafting.
In order to uniformly disperse the wax in the resin and to improve the inclusion of the wax, it is preferable to give the resin a crosslinked structure to some extent.

  The content of the wax in the resin containing the wax is 6 to 30% by mass, preferably 8 to 27% by mass, and more preferably 9 to 25% by mass. When the content of the wax is less than 6% by mass, the ratio of the resin with the wax added therein is large with respect to the wax. The amount of wax that can escape is small, and the wax separability cannot be exhibited. On the other hand, when the amount exceeds 30% by mass, the resin containing the wax does not have sufficient ability to include the wax, so that the result is the same as that of using the wax not internally added to the resin, that is, exposed to the surface. The amount of wax increases, causing contamination of the developing member and the photoreceptor.

  The resin internally added with the wax of the present invention has a T1 / 2 (T1 / 2 (A)) measured by a constant load extrusion capillary rheometer in the range of 120 ° C to 150 ° C, preferably in the range of 120 to 140 ° C. When the temperature is lower than 120 ° C., the wax inclusion property is deteriorated, and the wax is easily exposed on the surface of the toner. On the other hand, when T1 / 2 is higher than 150 ° C., the meltability of the toner deteriorates, and the fixing performance is adversely affected.

The resin not internally added with the wax used in the present invention is not particularly limited as long as it is generally used as a resin for toner. Specifically, polyester, polyurethane, polyurea, epoxy resin, vinyl resin And copolymers thereof. Of these, polyesters, vinyl resins, block polymers, and graft polymers thereof are preferable.
The resin to which the wax of the present invention is not internally added has a T1 / 2 (T1 / 2 (A)) measured by a constant load extrusion capillary rheometer in the range of 100 to 130 ° C, preferably in the range of 105 to 120 ° C. And 3 ° C. or more, preferably 5 ° C. or more, and more preferably 7 ° C. or more lower than the resin containing the wax.
In order to improve the wax inclusion property, it is necessary to design the resin having a wax added therein to have a slightly high viscosity. To satisfy the fixing strength, the viscosity of the resin not containing the wax is added to the wax. It must be designed to be 3 ° C lower than the resin.
In addition, when T1 / 2 of the resin not internally containing wax is lower than 100 ° C., the storage stability is reduced, for example, toner particles are fused with each other in a high-temperature and high-humidity environment. When the temperature is higher than 130 ° C., the meltability of the toner is deteriorated and the fixing performance is adversely affected.
The acid value of the toner is in the range of 10-40. If it is lower than 10, the fixing strength decreases, and if it exceeds 40, the environmental fluctuation becomes remarkable.

Next, the wax used in the present invention will be described.
Generally, the lower the polarity of the wax, the better the releasability from the fixing member roller. The wax used in the present invention is a hydrocarbon wax having a low polarity.
The hydrocarbon wax is a wax composed of only carbon atoms and hydrogen atoms, and does not substantially contain an ester group, an alcohol group, an amide group, or the like.
Specific hydrocarbon waxes include polyolefin waxes such as polyethylene, polypropylene, copolymers of ethylene and propylene, petroleum waxes such as paraffin wax and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax. . Of these, polyethylene wax, paraffin wax, and Fischer-Tropsch wax are preferable in the present invention, polyethylene wax and paraffin wax are more preferable, and paraffin wax is most preferable.

The melting point of the wax in the present invention is an endothermic peak of the wax at the time of temperature rise measured by a differential scanning calorimeter (DSC), and needs to be in the range of 70 ° C to 90 ° C. If it is higher than 90 ° C., the melting of the wax in the fixing process becomes insufficient, and the releasability from the fixing member cannot be ensured. On the other hand, if the temperature is lower than 70 ° C., there is a problem in storage stability such that toner particles are fused in a high temperature and high humidity environment. In order to provide a sufficient margin for fixing separation at a low temperature, the melting point of the wax is preferably 70 ° C to 85 ° C, more preferably 70 ° C to 80 ° C.
Moreover, it is preferable that the half value width of the endothermic peak of the wax at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 7 ° C. or less. Since the melting point of the wax in the present invention is relatively low, a wax whose endothermic peak is broad, that is, melted from a low temperature range, adversely affects the storage stability of the toner.

The wax content in the toner of the present invention is in the range of 3 to 10% by mass, preferably 4 to 8% by mass, and more preferably 4 to 6.5% by mass. If the wax content is less than 3% by mass, the amount of wax that exudes between the molten toner and the fixing member in the fixing process is insufficient, and the adhesive force between the molten toner and the fixing member does not decrease. The recording member does not leave the fixing member. On the other hand, if the wax content exceeds 10% by mass, the amount of wax exposed on the toner surface increases, and the transfer efficiency from the developing unit to the photoconductor and from the photoconductor to the recording member increases due to the deterioration of the fluidity of the toner particles. This is not preferable because not only the image quality is significantly lowered, but also the wax on the surface of the toner is detached to cause contamination of the developing member and the photosensitive member.
In addition, the wax not internally added to the resin may be contained in addition to the wax internally added to the resin as long as the process resistance is not deteriorated.

  As the coloring agent of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline 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, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake , Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. In addition to the polyester and vinyl resins mentioned above, binder resins that are kneaded with the masterbatch production or masterbatch include rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic A group petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned, and these can be used alone or in combination.

  The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based 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, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be melt-kneaded with a masterbatch and resin, or may be externally added and mixed with a Henschel mixer or the like.

The toner of the present invention may contain a wax dispersant that helps to disperse the wax.
The wax dispersant is not particularly limited, and a known one can be used. A polymer, oligomer, or wax in which a unit having high compatibility with the wax and a unit having high compatibility with the resin exist as a block body. Polymer or oligomer in which one of highly compatible units and resin is highly grafted on the other, unsaturated hydrocarbon such as ethylene, propylene, butene, styrene, α-styrene, acrylic acid, Copolymers of α, β-unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride, their esters or anhydrides, vinyl resin and polyester blocks or grafts Examples include the body.

As the unit having high compatibility with the above wax, there are a long chain alkyl group having 12 or more carbon atoms, polyethylene, polypropylene, polybutene, polybutadiene and a copolymer thereof, and a unit having high compatibility with the resin. Examples thereof include polyester and vinyl resin.
The amount of the wax dispersant is 0.1 to 5 times, preferably 0.3 to 2.5 times that of the wax. If it is less than 0.1 times, the wax dispersion effect is not observed, and if it exceeds 5 times, the exudation of wax in the fixing process is suppressed and the toner has poor fixing separability.

As the external additive for assisting the fluidity, developability and chargeability of the toner obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 2 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

As a method for producing the toner of the present invention, conventionally known methods such as a pulverization method, an emulsion polymerization association method, and a suspension polymerization method can be applied.
When the toner is produced by the emulsion polymerization association method, at least wax is dissolved or dispersed in a vinyl monomer, and the wax is internally added to the vinyl resin dispersion by a method such as miniemulsion polymerization. It can be isolated by associating and fusing together with a vinyl resin dispersion, a pigment dispersion, etc. to obtain a toner slurry, and then collecting it by washing and filtration according to known methods and drying.
When the toner is manufactured by a pulverization method, at least a resin internally containing wax, a resin not containing wax internally, and a toner component of a coloring material are mechanically mixed and melt-kneaded according to conventionally known means. A toner production method including a process, a pulverizing process, and a classification process can be applied. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.
The mixing step of mechanically mixing at least the resin not containing wax internally and the toner component of the colorant may be performed under normal conditions using a normal mixer using a rotating blade, and is not particularly limited.

  When the mixing step is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used. It is important that this melt-kneading is performed under appropriate conditions that do not cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low from the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a developer having a predetermined particle size, for example, an average particle size of 5 to 20 μm.

T1 / 2 and outflow end temperature in the present invention are values measured by a flow tester CFT-500D manufactured by Shimadzu Corporation, the diameter of the extrusion port is 0.5 mm, the depth is 1 mm, and the temperature rise is 3 ° C./min. I went there. The load applied to the sample was set to 30 kgf.
The differential scanning calorimeter (DSC) uses a DSC6200 manufactured by Seiko Instruments Inc., heated up to 200 ° C., and cooled from the temperature to 0 ° C. at a cooling rate of 10 ° C./min. Measured in minutes.

The acid value was measured according to JIS K-0070. The specific operation procedure is as follows.
(1) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (4/1: v / v) is added and dissolved.
(2) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH. For example, automatic titration using a potentiometric titrator AT-400 (win workstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.
(3) The amount of KOH solution used at this time is set to Sml, and a blank is measured at the same time, and the amount of KOH solution used at this time is set to Bml.
(4) The acid value is calculated by the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

Measurement of the particle diameter of the toner particles is performed by a Coulter counter method.
Examples of the measurement device for the particle size distribution of toner particles by the Coulter counter method include Coulter counter TA-II, Coulter multisizer II, and Coulter multisizer III (all manufactured by Coulter Co.). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of the measurement sample is further added as a solid content. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained. In this example, 5 mg of a measurement sample (ISOTON-II (manufactured by Coulter)) as a solid content is added to 100 ml of an electrolytic aqueous solution. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture. The number distribution was calculated. From the obtained distribution, the weight average particle diameter (Dv) and number average particle diameter (Dn) of the toner were determined.

  As a method for measuring the shape of the toner, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. . A toner with an average circularity of 0.960 or more, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of a real particle, produces a high-definition image having a reproducibility with an appropriate density. It turned out to be effective in forming. More preferably, the average circularity is 0.980 to 1.000. This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. As a specific measuring method, a surfactant, preferably an alkylbenzene sulfonate (10 wt% aqueous solution) is added as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance in a container. Add 5 ml and add about 0.1 to 0.5 g of the sample to be measured. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. . In this example, 0.3 ml of a 10 wt% solution of alkylbenzene sulfonate was added to 100 ml of water from which impure solids had been removed in advance using a flow type particle image analyzer FPIA-2000. About 3 g was added. The suspension in which the sample was dispersed was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser and measured.

  Based on T1 / 2, the resin material is divided into a higher one and a lower one, and a wax component is added in advance to the higher T1 / 2 resin material so that the toner has a specific resin / wax composition. And having specific rheological properties to prevent the wax from being exposed to the toner surface, preventing adverse effects on process resistance, and further improving the elasticity of the toner to fix the toner. The fixing strength can be ensured and sufficient image quality can be obtained without causing defects or gloss reduction. In addition, the manufacturing method of the present invention can reliably manufacture toner having such characteristics. By storing such toner in a process cartridge, it can be efficiently applied to an image forming apparatus.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the examples, all parts represent parts by mass.
≪Preparation of resin H1≫
As a vinyl monomer, 600 parts of styrene, 110 parts of butyl acrylate, 30 parts of acrylic acid and 30 parts of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel. Among polyester monomers, as polyols, 1230 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis ( 290 parts of 4-hydroxyphenyl) propane, 250 parts of isododecenyl succinic anhydride, 310 parts of terephthalic acid, 180 parts of 1,2,4-benzenetricarboxylic anhydride, 7 parts of dibutyltin oxide as an esterification catalyst, and W1 (paraffin wax as a wax) , Melting point 73.3 ° C., half-width of endothermic peak at the time of temperature rise measured by differential scanning calorimeter is 3.9 ° C.) 460 parts (15.1 parts by mass with respect to 100 parts by mass of charged monomer) , Put in a reaction vessel equipped with a thermometer, stainless steel stirrer, flow-down condenser and nitrogen inlet tube, With stirring at ℃ temperature, it was added dropwise over one hour a mixture of the vinyl monomer resins and the polymerization initiator from the dropping funnel. The addition polymerization reaction was aged for 2 hours while maintaining the temperature at 160 ° C., and then the temperature was raised to 230 ° C. to perform the condensation polymerization reaction. The degree of polymerization was tracked by the softening point measured using a constant load extrusion capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain Resin H1.

  Regarding the resin H2, the resin H3, the resin H6, the resin H7, the resin H9, and the resin H10, the material composition was prepared according to Table 1 in the same manner as the resin H1. Further, regarding the resin H5, the resin H8, and the resin L2, the composition of the materials was prepared according to Table 1 in the same manner as the resin H1 except that no wax was added.

Abbreviations for wax in Table 1 are as follows.

The meanings of the abbreviations described in the headings in Table 1 are as follows.

≪Preparation of resin H4≫
As polyol, 2210 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 850 parts of terephthalic acid, 120 parts of 1,2,4-benzenetricarboxylic anhydride and dibutyl as esterification catalyst 0.5 parts of tin oxide, 350 parts of W1 (paraffin wax, melting point 73.3 ° C., half-width of endothermic peak at the time of temperature rise measured by a differential scanning calorimeter is 3.9 ° C.) 11.0 parts by mass with respect to 100 parts by weight) is put in a reaction vessel equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen introduction tube, and the temperature is raised to 230 ° C. in a nitrogen atmosphere to perform the condensation polymerization reaction. I did it. The degree of polymerization was tracked by the softening point measured using a constant load extrusion capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain Resin H4.
Regarding the resin L1, the composition of the material was prepared according to Table 1 in the same manner as the resin H4 except that no wax was added.

Example 1
Resin H1 30 parts Resin L1 70 parts Charge control agent (metal salt of salicylic acid derivative) 1 part Colorant (copper phthalocyanine blue pigment) 2.5 parts After sufficiently mixing the above materials in a blender, the mixture is kneaded in a twin screw extruder, After cooling, pulverization and classification were performed to obtain a cyan base toner having a volume average particle diameter of about 7.5 μm.
To 100 parts of the base toner, 0.4 part of hydrophobic silica (surface-treated product with hexamethyldisilazane, average particle size of primary particles is 0.02 μm) as an external additive is mixed with a Henschel mixer. And a cyan toner was obtained. The wax content is 4.5% by mass.
The acid value of the toner was measured and found to be 22.4 KOH mg / g, T1 / 2 was 120 ° C., Tend was 127 ° C., and the circularity was 0.922.

The following evaluations (a) to (e) were performed on this toner.
(A) Fixing Separation A two-component developer prepared by mixing and stirring 5 parts of toner and 95 parts of a silicone resin coated carrier is placed in a modified machine from which the Ricoh ipsio CX7500 fixing machine is removed, and transfer paper (Ricoh type) 6200Y eye paper) was adjusted so that 1.1 ± 0.1 mg / cm ² of toner was developed with a solid image having a vertical tip margin of 3 mm, and 6 unfixed transfer sheets were output. .
Only the fixing part of Ricoh ipsio CX2500 was taken out, and the fixing belt temperature and the belt linear velocity were modified to the desired values, and the belt linear velocity was set to 125 mm / sec. The transfer paper was fixed from the end margin of 3 mm at a temperature of 10 ° C. in the range of 140 ° C. to 190 ° C. The transfer paper was evaluated based on the following criteria based on the number of sheets that could be fixed normally without winding around the fixing belt or clogging like a bellows at the exit of the fixing machine.
A: Six sheets were successfully fixed.
○: The number of sheets successfully fixed is 5.
Δ: 3 to 4 sheets successfully fixed.
X: The number of sheets successfully fixed is 2 or less.
“◎” and “◯” were accepted.

(B) Fixing strength A two-component developer prepared by mixing and stirring 5 parts of toner and 95 parts of a silicone resin-coated carrier is placed in a modified machine from which the Ricoh ipsio CX7500 fixing machine is removed, and transfer paper (Ricoh type 6200Y) is prepared. The sheet was adjusted so that 1.1 ± 0.1 mg / cm ² of toner was developed in a solid image having a vertical margin of 100 mm in the vertical direction, and an unfixed transfer sheet was output.
Only the fixing part of Ricoh's ipsio CX2500 was taken out, and the fixing belt temperature and belt linear velocity were modified to the desired values, and the belt linear velocity was set to 125 mm / sec and the fixing belt temperature was set to 140 ° C. After fixing the transfer paper, the drawing tester AD-401 manufactured by Ueshima Seisakusho was used, and the sapphire was run on the evaluation image in contact with the sapphire needle 125 μR, the needle rotation diameter 8 mm, and the load 1 g. The running surface of the tip of the needle point was visually observed to evaluate the occurrence of scratches (running traces) according to the following rank.
A: No trace (line) traveled is recognized.
○: Slight lines are recognized.
Δ: The line is slightly observed when observed from directly above the image, but when observed from 45 degrees obliquely
It is not clearly recognized.
X: A line is clearly recognized when observed from directly above the image.
“◎” and “◯” were accepted.

(C) Glossiness Only the fixing part of Ricoh ipsio CX2500 was taken out, and the fixing belt temperature and the belt linear velocity were modified to the desired values. The temperature was set to 160 ° C., and the unfixed transfer paper output in the same manner as in the evaluation of “(b) Fixing strength” was fixed. The glossiness of the image after fixing was measured at an incident angle of 60 ° with a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. As a full color image used in an office, moderate gloss is preferred, and about 5 to 15% is preferable.

(D) Adhering to regulating blade Using Ricoh's ipsio CX3000, the developer was developed after a continuous print of 2000 sheets in a N / N environment (23 ° C., 45%) (after endurance) with an N / N environment (23 ° C., 45%). The state of the developing roller and the copy image were visually observed and evaluated. Judgment criteria are as follows.
A: No streak or unevenness occurred on the developing roller.
○: Although there are some streaks or unevenness on the developing roller,
There were no vertical stripes on the copied image, and there was no problem in practical use.
×: Many streaks or irregularities occur on the developing roller,
Vertical streaky omissions occurred on the copied image, causing a problem in practical use.
“◎” and “◯” were accepted.

(E) Filming A predetermined print pattern with a printing rate of 6% was continuously printed in an N / N environment (23 ° C., 45%) using Ripoh's ipsio CX3000. After continuous printing (after endurance) in an N / N environment, the photosensitive member and the intermediate transfer belt were visually observed and evaluated. Judgment criteria are as follows.
A: There was no filming on the photosensitive member and the intermediate transfer member, and there was no problem at all.
○: Filming was observed on either the photoconductor or the intermediate transfer member.
It was not visible on the copied image, and there was no practical problem.
X: Filming occurs on the photoreceptor and / or the intermediate transfer member,
It could be confirmed on the image, and there was a problem in practical use.
“◎” and “◯” were accepted.

又、各トナーの評価結果は表５にまとめて示す。 Table 4 shows blending examples of the resin and wax of Example 1 and Examples 2 to 8 and Comparative Examples 1 to 5 described below.

The evaluation results for each toner are summarized in Table 5.

Examples 2-6 , 8
In the same manner as in Example 1, toners 2 to 6 and 8 having the resin / wax compositions shown in Table 4 were prepared and evaluated in the same manner as in Example 1.
Comparative Examples 1-5
Similarly to Example 1, toners 101 to 105 were prepared with the resin / wax compositions shown in Table 4 and evaluated in the same manner as in Example 1.
The evaluation results of Examples 2 to 6 and 8 and Comparative Examples 1 to 5 are shown in Table 5.

Example 7
<Cyan colorant dispersion>
Pigment C.I. I. Pigment Blue 15: 3 50 parts Sodium dodecyl sulfate 10 parts Ion-exchanged water 200 parts The above was dispersed with a sand grinder mill to obtain a cyan colorant dispersion having a volume average particle size (D50) of 170 nm.
<Preparation of latex>
(Preparation of latex 1L)
(Dispersion medium)
Sodium dodecyl sulfate 4.05 parts Ion-exchanged water 2500 parts The above dispersion medium is charged into a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet, and stirred at a stirring speed of 230 rpm under a nitrogen stream. The temperature in the flask was raised to 80 ° C.
Styrene 612 parts n-butyl acrylate 156 parts methacrylic acid 32 parts n-octyl mercaptan 13 parts Initiator solution prepared by dissolving 9.62 parts of a polymerization initiator (potassium persulfate) in 200 parts of ion-exchanged water in this activator solution Was added dropwise over 90 minutes, and the system was heated and stirred at 80 ° C. for 2 hours to perform polymerization (first stage polymerization) to prepare a latex. This is referred to as “latex (1 L)”. The T1 / 2 of the dried latex (1 L) was 124 ° C.

(Preparation of latex 1HML)
(1) Preparation of core particles (first stage polymerization)
(Dispersion medium 1)
Sodium dodecyl sulfate 4.05 parts Ion-exchanged water 2500.00 parts The above dispersion medium 1 is charged into a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a condenser tube, and a nitrogen introduction device, and a stirring speed of 230 rpm under a nitrogen stream The temperature in the flask was raised to 80 ° C. while stirring at.
Styrene 568.00 parts n-Butyl acrylate 164.00 parts Methacrylic acid 68.00 parts n-Octyl mercaptan 16.51 parts Into this activator solution, 9.62 parts of a polymerization initiator (potassium persulfate) are added to ion-exchanged water 200. The initiator solution dissolved in part is added, and the above monomer solution is added dropwise over 90 minutes, and the system is heated and stirred at 80 ° C. for 2 hours to perform polymerization (first stage polymerization). And latex was prepared. This is referred to as “latex (1H)”. The weight average particle diameter of the latex (1H) was 68 nm.

(2) Formation of intermediate layer (second stage polymerization)
(Monomer solution 2)
Styrene 123.81 parts n-Butyl acrylate 39.51 parts Methacrylic acid 12.29 parts n-Octyl mercaptan 0.72 parts Wax W1 75.0 g parts In a flask equipped with a stirrer, the above monomer solution 2 was added. The monomer solution was prepared by heating and dissolving at 80 ° C.

(Dispersion medium 2)
C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ OSO ₃ Na 0.60 parts Ion-exchanged water 2700.00 parts On the other hand, the dispersion medium 2 is heated to 98 ° C., and this dispersion medium is a dispersion medium for core particles. After 32 parts of the latex (1H) is added in terms of solid content, the monomer solution 2 is mixed for 8 hours using a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. Dispersed to prepare a dispersion (emulsion) containing emulsified particles (oil droplets).
Next, an initiator solution prepared by dissolving 6.12 parts of a polymerization initiator (potassium persulfate) in 250 ml of ion-exchanged water is added to the dispersion (emulsion), and the system is heated at 82 ° C. for 12 hours. Polymerization (second stage polymerization) was carried out by stirring to obtain latex (a dispersion of composite resin particles having a structure in which the surface of latex (1H) particles was coated). This is referred to as “latex (1HM)”.

(3) Formation of outer layer (third stage polymerization)
(Monomer solution 3)
Styrene 350 parts n-Butyl acrylate 95 parts Methacrylic acid 5 parts n-Octyl mercaptan 6.1 parts To the latex (1HM) obtained as described above, 8.8 parts of a polymerization initiator (KPS) is added to 350 ml of ion-exchanged water. The initiator solution dissolved in was added, and the monomer solution 3 was added dropwise over one hour under a temperature condition of 82 ° C. After completion of the dropping, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, followed by cooling to 28 ° C. and an intermediate layer made of latex (latex (1H) and a second stage polymerization resin). And an outer layer made of a third-stage polymerization resin, and a dispersion of a composite resin in which wax is contained in the second-stage polymerization resin layer). This latex is referred to as “latex (1HML)”. The amount of the wax W1 charged into the latex (1HML) was 12.5% by mass relative to the monomer, and the T1 / 2 of the dried latex (1L) was measured to be 131 ° C.

<Preparation of toner particles>
240.0 parts of latex (1 L) (converted to solid content), 180.0 parts of latex (1 HML) (converted to solid content), 900 parts of ion-exchanged water, and 150 parts of the cyan colorant dispersion, The mixture was stirred in a reaction vessel (four-necked flask) equipped with a temperature sensor, a condenser, a nitrogen introducing device, and a stirring device. After adjusting the temperature in a container to 30 degreeC, 5N sodium hydroxide aqueous solution was added to this solution, and pH was adjusted to 8-10.0.
Next, an aqueous solution in which 65.0 parts of magnesium chloride hexahydrate was dissolved in 1000 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, the temperature was raised to 92 ° C. to produce aggregated particles. In this state, the particle diameter of the aggregated particles was measured with “Coulter Counter TA-II”. When the number average particle diameter reached 6.6 μm, 80.4 parts of sodium chloride was dissolved in 1000 ml of ion-exchanged water. Particle growth was stopped by adding an aqueous solution, and further, as a ripening treatment, the mixture was heated and stirred at a liquid temperature of 94 ° C. to continue particle fusion and crystalline phase separation (ripening step). In this state, the shape of the fused particles was measured with “FPIA-2000”, and when the shape factor reached 0.952, the mixture was cooled to 30 ° C. and stirring was stopped. The produced fused particles were filtered, repeatedly washed with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. to obtain a base toner.
When the number average particle diameter and the shape factor of the base toner were measured again, they were 6.5 μm and 0.954, respectively.

To 100 parts of the base toner, 0.4 part of hydrophobic silica (surface-treated product with hexamethyldisilazane, average particle size of primary particles is 0.02 μm) as an external additive is mixed with a Henschel mixer. As a result, cyan toner 7 was obtained.
The acid value of Toner 7 was measured and found to be 25.1 KOHmg / g. T1 / 2 measured by a constant load extrusion capillary rheometer was 127 ° C and Tend was 135 ° C.
Table 5 shows the results of evaluation performed on the toner 7.

Comparative Example 6
Reaction in which 420.0 parts of latex (1HML) (in terms of solid content), 900 parts of ion-exchanged water, and 150 parts of the cyan colorant dispersion were attached with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device. It stirred in the container (four necked flask). After adjusting the temperature in a container to 30 degreeC, 5N sodium hydroxide aqueous solution was added to this solution, and pH was adjusted to 8-10.0.
Next, an aqueous solution in which 65.0 parts of magnesium chloride hexahydrate was dissolved in 1000 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, the temperature was raised to 92 ° C. to produce aggregated particles. In this state, the particle diameter of the aggregated particles was measured with “Coulter Counter TA-II”. When the number average particle diameter reached 6.6 μm, 80.4 parts of sodium chloride was dissolved in 1000 ml of ion-exchanged water. Particle growth was stopped by adding an aqueous solution, and further, as a ripening treatment, the mixture was heated and stirred at a liquid temperature of 94 ° C. to continue particle fusion and crystalline phase separation (ripening step).
In this state, the shape of the fused particles was measured with “FPIA-2000”, and when the shape factor reached 0.952, the mixture was cooled to 30 ° C. and stirring was stopped. The produced fused particles were filtered, repeatedly washed with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. to obtain a base toner. When the number average particle diameter and the shape factor of the base toner were measured again, they were 6.5 μm and 0.953, respectively.

To 100 parts of the base toner, 0.4 part of hydrophobic silica (surface-treated product with hexamethyldisilazane, average particle size of primary particles is 0.02 μm) as an external additive is mixed with a Henschel mixer. As a result, cyan toner 106 was obtained.
The acid value of the toner 106 was measured and found to be 25.6 KOH mg / g. T1 / 2 measured by a constant load extrusion capillary rheometer was 132 ° C. and Tend was 140 ° C.
Table 5 shows the results of evaluation performed on the toner 106.

Claims (40)

At least in a toner comprising a resin internally added with wax (resin A), a resin not internally added with wax (resin B), and a colorant,
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner characterized in that an outflow end temperature Tend of the toner measured by a constant load extrusion type capillary rheometer is 135 ° C. or less. 2. The toner according to claim 1, wherein the toner contains a hydrocarbon-based wax not internally added to the resin, in addition to the wax internally added to the resin A. 3.   The toner according to claim 1, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less with respect to the toner.   The toner according to claim 1, wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.   The toner according to claim 1, wherein the toner has an acid value of 10 or more and 40 or less.   6. The toner according to claim 1, wherein the half-value width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less. .   The toner according to claim 1, wherein at least one of the resin A and the resin B has a polyester skeleton.   The toner according to claim 1, comprising a wax dispersant. The resin A is
The toner according to claim 1, wherein the toner is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.   The toner according to claim 9, wherein the monomer A contains a tri- or higher functional monomer in an amount of 0.1 to 5% by mass. At least a resin that internally contains wax (resin A), a resin that does not contain wax (resin B), and a colorant are supplied to a raw material mixer, mixed, kneaded, rolled and cooled, and then pulverized and classified. In the manufacturing method of
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner production method, wherein the outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less. 12. The method for producing a toner according to claim 11, wherein the toner contains a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A.   The method for producing a toner according to claim 11 or 12, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less with respect to the toner.   The toner production method according to claim 11, wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.   The toner production method according to claim 11, wherein the toner has an acid value of 10 or more and 40 or less.   The toner according to any one of claims 11 to 15, wherein a half-value width of an endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C or less. Manufacturing method.   The method for producing a toner according to claim 11, wherein a part or all of at least one of the resin A and the resin B has a polyester skeleton.   The toner manufacturing method according to claim 11, further comprising a wax dispersant. The resin A is
The method for producing a toner according to claim 11, wherein the toner is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.   The method for producing a toner according to claim 19, wherein the monomer A contains a tri- or higher functional monomer in an amount of 0.1 to 5% by mass. Production method of toner obtained through a process of aggregating at least resin particles of resin (resin A) internally added with wax, resin particles of resin (resin B) not internally added with wax, and colorant particles in an aqueous medium In
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A toner production method, wherein the outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less. The method for producing a toner according to claim 21, wherein the toner contains a hydrocarbon-based wax not internally added to the resin, in addition to the wax internally added to the resin A.   23. The method for producing a toner according to claim 21, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.   24. The method for producing a toner according to claim 21, wherein the toner has a volume average particle diameter of 4 μm or more and 10 μm or less.   The toner production method according to claim 21, wherein the toner has an acid value of 10 or more and 40 or less.   26. The toner according to claim 21, wherein the half-width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C. or less. Manufacturing method.   27. The method for producing a toner according to claim 21, wherein a part or all of at least one of the resin A and the resin B has a polyester skeleton.   28. The toner production method according to claim 21, further comprising a wax dispersant. The resin A is
29. The method for producing a toner according to claim 21, wherein the toner is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.   30. The method for producing a toner according to claim 29, wherein the monomer A contains 0.1 to 5% by mass of a tri- or higher functional monomer. In a process cartridge that is detachably attached to the image forming apparatus main body,
At least a latent image carrier;
A charging member that contacts and charges the latent image carrier;
A drum unit comprising: a cleaning member that removes and collects transfer residual toner on the latent image carrier;
At least toner;
A developing container for containing the toner;
Toner transporting means for rotating and stirring the fixed shaft in the developing container to stir and transport the toner;
A toner carrier in contact with the latent image carrier;
A toner regulating member in contact with the toner carrying member via toner;
A process cartridge in which a toner unit comprising a toner supply roller for supplying toner to the toner carrier is integrated;
The toner is
At least in a toner comprising a resin internally added with wax (resin A), a resin not internally added with wax (resin B), and a colorant,
T1 / 2 (T1 / 2 (A)) of the resin A by a constant load extrusion type capillary rheometer is 120 ° C. or more and 150 ° C. or less,
The content of the wax is 6% by mass or more and 30% by mass or less of the resin A,
The wax is a hydrocarbon wax;
The melting point of the wax is 70 ° C. or higher and 90 ° C. or lower,
T1 / 2 (T1 / 2 (B)) of the resin B measured by a constant load extrusion type capillary rheometer is 100 ° C. or higher and 130 ° C. or lower,
T1 / 2 (A) and T1 / 2 (B) satisfy the following relational expression:
T1 / 2 (A) ≧ T1 / 2 (B) +3
The mass ratio of the resin A and the resin B contained in the toner is in the range of 10/90 to 45/55,
A process cartridge characterized in that an outflow end temperature Tend of the toner by a constant load extrusion type capillary rheometer is 135 ° C. or less. 32. The process cartridge according to claim 31, wherein the toner contains a hydrocarbon wax not internally added to the resin, in addition to the wax internally added to the resin A.   The process cartridge according to claim 31 or 32, wherein the content of the hydrocarbon wax is 3% by mass or more and 10% by mass or less based on the toner.   34. The process cartridge according to claim 31, wherein a volume average particle diameter of the toner is 4 μm or more and 10 μm or less.   The process cartridge according to claim 31, wherein the toner has an acid value of 10 or more and 40 or less.   The process according to any one of claims 31 to 35, wherein the half-width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the hydrocarbon wax is 7 ° C or less. cartridge.   37. The process cartridge according to claim 31, wherein a part or all of at least one of the resin A and the resin B has a polyester skeleton.   The process cartridge according to any one of claims 31 to 37, further comprising a wax dispersant. The resin A is
The process cartridge according to any one of claims 31 to 38, which is obtained by polymerizing at least a raw material monomer (monomer A) constituting the resin A and a mixture containing the wax.   40. The process cartridge according to claim 39, wherein the monomer A contains 0.1 to 5% by mass of a tri- or higher functional monomer.