JP7395276B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to a toner used in electrophotography and electrostatic recording, and a method for producing the toner.

In recent years, laser beam printers (LBPs) have been required to have a longer service life than ever before, and the environments in which they are used are becoming more diverse. In order to meet these demands, further quality stability, that is, improvement in long-term durability is required under harsh environments.
Specifically, it is necessary to be able to print on more paper with one cartridge, and to maintain high image quality throughout durability. To this end, the toner is required to have no change in the surface of the toner throughout its life, and no change in the fluidity of the toner even at the end of its life. Furthermore, the cartridge is required to eliminate toner contamination and toner scratches on various members such as a charging roller and a photoreceptor drum.
Patent Document 1 discloses a toner that can suppress scratches on a photoreceptor drum by using hydrophobized amorphous silicone resin particles.
Patent Document 2 discloses that a polymethylsilsesquioxane fine particle containing an amorphous resin and a crystalline resin is used for the purpose of suppressing detachment of polymethylsilsesquioxane fine particles from toner base particles and improving image defects and contamination in an image forming apparatus. A toner is disclosed that includes toner base particles and an external additive containing polyorganosilsesquioxane fine particles having a number average particle diameter of 10 nm or more and less than 100 nm.

Publication of JP-A-10-186710 JP2017-122873 Publication

In the conventional techniques as described above, since the hardness of the silicone resin particles is not high, it is difficult to uniformly fix them to the toner base particles by dry mixing. Therefore, organosilicon polymer particles may be detached from the toner due to durability under harsh environments. As a result, the charging roller may be contaminated at the end of its life, causing charging problems, or the fluidity may be insufficient, resulting in insufficient frictional charging of the toner, resulting in fogging.
In other words, an object of the present invention is to provide a toner and a method for producing the toner that can exhibit stable developability without any adverse effects on images and maintain high image quality.

The present invention is a method for producing a toner comprising toner particles having toner base particles containing a binder resin, wax, and a colorant, and organosilicon polymer particles, the method comprising:
a step of mixing the toner base particles and the organosilicon polymer particles, and then subjecting the toner base particles to surface treatment with hot air;
The organosilicon polymer particles adhere to the surface of the toner base particles,
The adhesion rate of the organosilicon polymer particles to the toner base particles is 90% or more,
The organosilicon polymer particles have an intention hardness of 0.10 GPa or more and 1.50 GPa or less at a load of 2 μN, a number average diameter of primary particles of 35 nm or more and 300 nm or less, and a relative dielectric constant εra measured at 10 Hz. 3.5 or less.

According to the present invention, it is possible to uniformly adhere the organosilicon polymer particles to the toner by mixing toner base particles and organosilicon polymer particles and performing surface treatment with hot air. As a result, it becomes possible to maintain the organosilicon polymer particles on the surface of the toner base particles even during a long durability period. In other words, it is an object of the present invention to provide a method for producing a toner that can exhibit stable developability and maintain high image quality without any adverse effects on images.

FIG. 2 is a cross-sectional view of a surface treatment device using hot air.

A mode for carrying out the present invention will be described.

The present inventors have provided a method for producing a toner comprising toner particles having toner base particles containing a binder resin, wax, and a colorant, and organosilicon polymer particles, the method comprising: the organic silicon polymer particles have an intention hardness of 0.10 GPa or more and 1.50 GPa or less at a load of 2 μN. have found a method for producing a toner, characterized in that the number average diameter of primary particles is 35 nm or more and 300 nm or less, and the dielectric constant εra measured at 10 Hz is 3.5 or less.

According to studies by the present inventors, the organosilicon polymer particles and toner manufacturing method of the present invention make it possible to uniformly adhere the organosilicon polymer particles to the surface of the toner base particles. As a result, it is possible to exhibit stable developability without image defects and maintain high image quality. The details will be explained below.

As mentioned above, it is difficult to uniformly adhere organosilicon polymer particles to the surface of toner base particles. If the adhesion is insufficient, the organosilicon polymer particles may be detached from the toner particles during durability, or problems may occur due to segregation of fine particles. Therefore, it was not a drastic measure.

Therefore, the present inventors suppressed electrostatic aggregation between organosilicon polymer particles by adding organosilicon polymer particles that have a low dielectric constant and do not easily cause electrostatic aggregation. We devised a method to physically disperse the organosilicon polymer particles onto the toner base particles by mixing them beforehand, thereby making them more uniformly adhered to the toner base particles.

That is, the present inventors first focused on the mechanism of electrostatic aggregation.

In general, electrostatic aggregation of powder particles is thought to involve particles with different charging characteristics being charged positively and negatively, respectively, and attracted and agglomerated by Coulomb force. However, it is difficult to imagine that positively charged and negatively charged particles exist separately among fine particles that are compositionally homogeneous and uniform.

Therefore, the present inventors surmised that the electrostatic aggregation of organosilicon polymer particles is not due to the presence of positively or negatively charged particles, but is due to electrostatic interactions at a more microscopic level. Specifically, it was thought that this is due to the so-called van der Waals force, which is an electrostatic cohesive force due to permanent dipoles and excited dipoles at the molecular level. In the case of organosilicon polymer particles, the van der Waals force on the surface of the particles acts, which is thought to have caused the formation of agglomerates.

Therefore, the present inventors considered controlling the electrical properties of organosilicon polymer particles. Specifically, it was thought that if the polarization level of the permanent dipole/excited dipole is small, electrostatic aggregation is less likely to occur, and therefore electrostatic agglomerates of organosilicon polymer particles are less likely to form.

The present inventors focused on the dielectric constant as an index of the electrical properties of organosilicon polymer particles. Although it is difficult to directly measure the van der Waals force due to permanent dipoles and excited dipoles of molecules on the surface of organosilicon polymer particles, it is difficult to directly measure the van der Waals force due to permanent dipoles and excited dipoles of molecules on the surface of organosilicon polymer particles. It can be easily measured.

In addition, during actual durable development, an electric field such as a developing bias is applied around the toner carrier where the toner is most agitated and rubbed and the silicone on the toner particle surface moves, so the degree of polarization of molecules in the electric field is used as an indicator of electrostatic aggregation. In other words, the relative dielectric constant was considered to be appropriate. It is thought that if the relative permittivity is a small value, the desired effect will be exhibited and high image quality will be achieved.

Next, the present invention will be explained in more detail.

When the intention hardness of the organosilicon polymer particles at a load of 2 μN is 0.10 GPa or more and 1.50 GPa or less, stable fluidity can be maintained throughout durability while suppressing scratches on the drum. When the intention hardness is less than 0.10 GPa, the organosilicon polymer particles are soft and deform due to durability, so fluidity tends to deteriorate. On the other hand, if the intention hardness is higher than 1.50 GPa, the drum may be damaged in long-term durable image output.

It is preferable that the number average particle diameter of the organosilicon polymer particles is 35 nm or more and 300 nm or less because toner deterioration can be suppressed when the toner is rubbed during durable development. Specifically, it is preferable because the organosilicon polymer particles are less likely to be detached or embedded when the toner is subjected to stress. More preferably, it is 40 nm or more and 250 nm or less.

If it is smaller than 35 nm, fine particles will be embedded when the toner is rubbed, resulting in poor fluidity and insufficient frictional charging between the developing roller and the developing blade. As a result, fog occurs where the toner is developed in areas other than the image forming area, and transfer residual ghosts also occur. On the other hand, if it is larger than 300 nm, the organosilicon polymer particles cannot be stably fixed to the surface of the toner base particles even if surface treatment is performed using hot air. As a result, this is not preferable because it causes contamination of the developing roller.

It is preferable that the relative permittivity ε _ra of the organosilicon polymer particles measured at 10 Hz is 3.5 or less because the particles themselves are unlikely to cause electrostatic aggregation in an electric field. If it is larger than 3.5, the van der Waals force due to permanent dipoles and excited dipoles in the electric field becomes excessive, and the organosilicon polymer particles aggregate with each other, making it impossible to exhibit the desired crushing effect, which is not preferable.

The organosilicon polymer particles are preferably blended in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the toner base particles in order to obtain the effects of the present invention. When the amount is less than 0.5 part by mass, it becomes difficult to exhibit stable developability and maintain high image quality. When the amount is more than 6.0 parts by mass, particles that cannot be fixed are likely to be generated, making it difficult to obtain the effects of the present invention. More preferably, it is 1.0 parts by mass or more and 4.0 parts by mass or less. More preferably, it is 1.5 parts by mass or more and 3.5 parts by mass or less.

It is preferable that the shape factor SF-1 of the organosilicon polymer particles is 114 or less because the fluidity of the toner during durable development can be maintained. The shape factor SF-1 is an index representing the degree of roundness of a particle, and a value of 100 indicates a perfect circle, and a larger value indicates that the particle becomes farther from a circle and has an amorphous shape.

The organosilicon polymer particles used in the present invention will be specifically explained below.

The method for producing organosilicon polymer particles is not particularly limited. For example, at least two types of silane compounds are added dropwise to water, hydrolyzed and condensed using a catalyst, and the resulting suspension is filtered and dried. obtain. The particle size can be controlled by the type of catalyst, blending ratio, reaction initiation temperature, dropping time, etc.

Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, etc., and examples of basic catalysts include aqueous ammonia, sodium hydroxide, potassium hydroxide, etc., but are not limited to these.

The organosilicon polymer particles are obtained from a silane compound having two or more units selected from the group consisting of units represented by the following formula (1), formula (2), formula (3), and formula (4). It will be done.

Examples of the compound having the unit structure represented by formula (1) include tetramethoxysilane and tetraethoxysilane. It is not particularly limited as long as it has the unit structure of formula (1).

Examples of compounds having a unit structure represented by formula (2) include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. , methyltrichlorosilane and the like. There is no particular limitation as long as it has the unit structure of formula (2).

Examples of the compound having the unit structure represented by formula (3) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipropylmethoxysilane, and dibutylmethoxysilane. There is no particular limitation as long as it has the unit structure of formula (3).

Examples of compounds having a unit structure represented by formula (4) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, and trimethylchlorosilane. Can be mentioned. There is no particular limitation as long as it has the unit structure of formula (4).

In the organosilicon polymer particles of the present invention, it is preferable that X is 0.70 or more when W+X+Y+Z=1.00. Even if the toner continues to be subjected to load from a developing device or the like during long-term use, the organosilicon polymer particles have appropriate elasticity, making it possible to suppress scratches on the drum.

It is more preferable that the organosilicon polymer particles are composed only of trifunctional structures (X is 1.00). Silicone composed only of trifunctional structures is called silsesquioxane [(R ^a SiO _3/2 ) _n ]. When the organosilicon polymer particles are silsesquioxane particles, the charge distribution of the composite particles tends to be uniform, and the uneven transfer of the composite particles from the toner particle surface to the latent image carrier surface is suppressed. Since the body-blocking layer has a more uniform composition, good cleaning performance is achieved.

Here, in the above structure, a structure in which four oxygen atoms are bonded to Si is tetrafunctional, a structure in which three oxygen atoms are bonded to Si is trifunctional, and a structure in which two oxygen atoms are bonded to Si is trifunctional. A structure in which one oxygen atom is bonded to Si is called monofunctional.

The organosilicon polymer fine particles have a structure in which silicon atoms and oxygen atoms are alternately bonded, and some of the silicon atoms may have a T unit structure represented by R ^a SiO _3/2 . preferable. Note that R ^a is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.

In addition, in ²⁹ Si-NMR measurements using the chloroform-insoluble fraction of organosilicon polymer fine particles, the ratio of the peak area derived from silicon having a T unit structure to the total area of the peaks derived from all silicon elements contained in the chloroform-insoluble fraction The area ratio of the peak is preferably 0.50 or more and 1.00 or less, and more preferably 0.90 or more and 1.00 or less from the viewpoint of suppressing scratches on the drum. Furthermore, agglomeration of fine particles is suppressed, and they can be uniformly fixed to toner base particles, and stable fluidity can be maintained throughout durability.

Next, as for the binder resin used in the toner base particles of the present invention, the following polymers can be used.

For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers , styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin-modified maleic acid resin, Acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron-indene resin, petroleum resin, etc. can be used.

Among the above, polyester resin is preferably used from the viewpoint of low-temperature fixability and chargeability.

The glass transition temperature (Tg) of the polyester resin is preferably 45°C or more and 70°C or less from the viewpoint of storage stability and durability stability. The softening point of the polyester resin is preferably 80° C. or more and 130° C. or less, more preferably 90° C. or more and 120° C. or less, from the viewpoint of low-temperature fixability of the toner. In addition, when using a polyester resin in combination with a low molecular weight resin and a high molecular weight resin, from the viewpoint of low-temperature fixing properties of the toner, the softening point of the low molecular weight resin is 80°C or higher and 110°C or lower, and the softening point of the high molecular weight resin is 80°C or higher and 110°C or lower. , preferably 120°C or more and 150°C or less.

The polyester resin used is one obtained by condensation polymerization of an alcohol monomer and a carboxylic acid monomer.

Examples of alcohol monomers include the following.

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-bis(4-hydroxyphenyl)propane, polyoxypropylene (6) Alkylene oxide adducts of bisphenol A such as -2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Tetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene .

On the other hand, examples of carboxylic acid monomers include the following.

Aromatic dicarboxylic acids or anhydrides thereof such as phthalic acid, isophthalic acid and terephthalic acid; Alkyl dicarboxylic acids or anhydrides thereof such as succinic acid, adipic acid, sebacic acid and azelaic acid; Alkyl groups having 6 to 18 carbon atoms; Succinic acid or its anhydride substituted with an alkenyl group; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or their anhydride.

In addition, the following monomers can also be used.

Polyhydric alcohols such as glycerin, sorbitol, sorbitan, and oxyalkylene ethers of novolac type phenolic resin; polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride.

Among them, in particular, a bisphenol derivative represented by the following formula (5) is used as a dihydric alcohol monomer component, and a carboxylic acid component consisting of a dihydric or higher carboxylic acid, an acid anhydride thereof, or a lower alkyl ester thereof (for example, A resin obtained by condensation polymerization with these polyester unit components using fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid monomer component is preferable because it has good charging characteristics. .

（式中、Ｒはエチレン基またはプロピレン基を示し、ｘおよびｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２以上１０以下である。）

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x+y is 2 or more and 10 or less.)

The wax used in the present invention is not particularly limited, and any known wax can be used. From the viewpoint of low-temperature fixability, waxes with low melting points are preferred. Specifically, it is a wax with a melting point of 50°C or more and 110°C or less. Furthermore, from the viewpoint of ease of dispersion in the toner and high mold releasability, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferred. If necessary, two or more waxes may be used in combination.

Specific examples of the wax include the following: Viscole (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries, Ltd.), Hiwax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ), Sasol H1, H2, C80, C105, C77 (Schumann Sasol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seizu Co., Ltd.) , Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite Co., Ltd.), wood wax, beeswax, rice wax, candelilla Wax, carnauba wax (available from Cerarica NODA Co., Ltd.).

When producing toner by a pulverization method, wax is preferably added during melt-kneading. Further, wax may be added during production of the binder resin.

The toner preferably contains 1 part by mass or more and 20 parts by mass or less of wax based on 100 parts by mass of the binder resin.

The colorant used in the toner base particles of the present invention is not particularly limited, and any known colorant can be used. Specifically, the following can be mentioned. As the coloring agent, a pigment may be used alone, but it is more preferable to use a combination of a dye and a pigment to improve the clarity from the viewpoint of the image quality of a full-color image.

Examples of the black colorant include carbon black; a magnetic material; and a color toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

Coloring pigments for magenta toner include the following. C. 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, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 81:2, 81:3, 81:4, 81:5, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 185, 202, 206, 207, 209, 238, 269, 282; C. I. Pigment Violet 19; C. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of dyes for magenta toner include the following. C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Dispersed Red 9; C. 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. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Coloring pigments for cyan toner include the following. C. I. Pigment Blue 2, 3, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6;C. I. Acid Blue 45, a copper phthalocyanine pigment with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. As the cyan coloring dye, C.I. I. There is Solvent Blue 70.

Examples of yellow colored pigments include the following. C. 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, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C. I. Bat yellow 1, 3, 20. As a coloring dye for yellow, C. I. There is Solvent Yellow 162.

The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the binder resin.

It is also possible to add a charge control agent to the toner base particles of the present invention. Effective charge control agents for negative charging include, for example, organometallic complexes and chelate compounds, such as monoazo metal complexes; acetylacetone metal complexes; metal complexes of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids; Examples thereof include metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

On the other hand, as charge control agents for positive charging, modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; and their analogues, onium salts such as phosphonium salts, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannins); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin Examples include organotinborates such as borate.

These charge control agents can be used alone or in combination of two or more. The amount of these charge control agents used is preferably 0.1 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the binder resin.

The toner of the present invention contains the organosilicon polymer particles in toner particles containing at least a binder resin, a colorant, and a wax, and further contains inorganic fine powder as an external additive to improve fluidity. May be added.

As the external additive, inorganic fine powder such as silica and aluminum oxide is preferred. Preferably, the inorganic fine powder is hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

The method for producing the toner of the present invention includes the step of preparing toner base particles containing wax and a colorant, mixing them with organosilicon polymer particles, and then subjecting the toner base particles to surface treatment with hot air. is not particularly limited, and conventionally known manufacturing methods such as kneading and pulverization methods, suspension polymerization methods, dissolution suspension methods, emulsion polymerization aggregation methods, and emulsion aggregation methods can be used.

Here, a procedure for producing toner using a pulverization method will be described.

In the raw material mixing step, predetermined amounts of a binder resin, a colorant, a wax, and, if necessary, other components such as a charge control agent are weighed out, blended, and mixed as materials constituting the toner particles. Examples of the mixing device include a double con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.).

Next, the mixed materials are melted and kneaded to disperse wax and the like in the binder resin. In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous-type kneader can be used. Single-screw or twin-screw extruders are the mainstream because of their advantage in continuous production. For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machinery Co., Ltd.), PCM kneader (manufactured by Ikegai Tekko Co., Ltd.), twin screw extruder (manufactured by Ikegai Iron Works Co., Ltd.), (manufactured by K.C.K. Co., Ltd.), Co-kneader (manufactured by Busu Co., Ltd.), and Kneedex (manufactured by Nippon Coke Industry Co., Ltd.).

Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like, and may be cooled with water or the like in a cooling step.

Next, the cooled resin composition is pulverized to a desired particle size in a pulverization step. In the pulverization process, after coarse pulverization is performed using pulverizers such as crushers, hammer mills, and feather mills, Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), Super Rotor (manufactured by Nissin Engineering Co., Ltd.), Turbo Mill, etc. (manufactured by Turbo Kogyo) or an air jet type pulverizer.

After that, if necessary, use an inertial classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), a centrifugal force classification type Turboplex (manufactured by Hosokawa Micron Co., Ltd.), a TSP separator (manufactured by Hosokawa Micron Co., Ltd.), a faculty (manufactured by Hosokawa Micron Co., Ltd.), The toner base particles are obtained by classification using a classifier or sieve machine (manufactured by Co., Ltd.).

After going through a mixing step in which organosilicon polymer particles are attached to the surface of the toner base particles obtained in this way, the surface is treated with hot air, and if necessary, it is classified using a classifier or sieve machine. Toner particles can be obtained.

The method of attaching the organosilicon polymer particles to the surface of the toner base particles in the attachment step is not particularly limited, and a predetermined amount of toner base particles and organosilicon polymer particles are weighed, blended, and mixed.

Further, other inorganic fine particles, a charge control agent, a fluidity imparting agent, etc. may be added at the same time as long as the effects of the present invention are not impaired.

Examples of the mixing device include a double con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauta mixer, each of which is preferably used.

It is more preferable to use a Henschel mixer as the mixing device since the organosilicon polymer particles can be more uniformly adhered to the surface of the toner base particles.

As for the mixing conditions, the higher the rotational speed of the mixing blade and the longer the mixing time, the more preferable it is because it becomes easier to uniformly adhere the boron nitride particles to the surface of the toner base particles.

However, if the rotational speed of the mixing blade is too high or the mixing time is too long, the frictional heat between the toner and the mixing blade increases, and the temperature of the toner may rise and fuse.

Therefore, it is preferable to actively cool the mixer by providing a mixing blade or a water cooling jacket to the mixer.

It is preferable to adjust the rotation speed of the mixing blade and the mixing time to a range where the temperature inside the mixer is 45° C. or less. Specifically, the maximum circumferential speed of the mixing blade is preferably 10.0 m/sec or more and 150.0 m/sec or less, and the mixing time is preferably adjusted within the range of 0.5 minutes or more and 60 minutes or less.

Further, the adhesion process may be performed in one step or in multiple steps of two or more, and the mixing device, mixing conditions, and toner base particle formulation used in each step may be the same or different. You can leave it there.

Next, the apparatus used for surface treatment of toner base particles has a means for melting the surface of toner particles before treatment using hot air, and has a means for melting the surface of toner particles before treatment using hot air. Any type of device may be used as long as it has a means for cooling with cold air.

An example of such a device is Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Kogyo Co., Ltd.).

One embodiment of the surface treatment method using hot air will be described with reference to FIG. 1, but the present invention is not limited thereto.

FIG. 1 is an example of a cross-sectional view of a surface treatment apparatus used in the present invention. Specifically, in the surface treatment method, organic silicon polymer particles are attached to the surface of toner base particles in advance as a raw material, and the raw material is supplied to the surface treatment apparatus.

The toner particles 114 supplied from the toner particle supply port 100 are accelerated by the injection air jetted from the high-pressure air supply nozzle 115, and head toward the air jetting member 102 located below.

Diffusion air is ejected from the air jetting member 102, and the toner particles 114 are diffused outward by this diffusion air. At this time, the state of diffusion of toner particles can be controlled by adjusting the flow rate of injection air and the flow rate of diffusion air.

Furthermore, cooling jackets 106 are provided around the outer periphery of the toner particle supply port 100, the outer periphery of the surface treatment device, and the outer periphery of the transfer pipe 116 for the purpose of preventing toner particles from fusing.

Note that it is preferable that cooling water (preferably an antifreeze solution such as ethylene glycol) be passed through the cooling jacket.

On the other hand, the surface of the toner particles diffused by the diffusion air is treated by the hot air supplied from the hot air supply port 101.

At this time, the hot air discharge temperature is higher than the softening point of the toner, preferably 130° C. or higher and 300° C. or lower, and more preferably 150° C. or higher and 250° C. or lower.

When the temperature of the hot air is equal to or higher than the softening point of the toner, the binder resin is dissolved, and as a result, the organosilicon polymer particles are fixed to the toner base particles.

If the hot air discharge temperature exceeds 300°C, the melting state of the toner particles will progress too much, and toner particles will tend to coalesce with each other during the manufacturing process, causing the toner particles to become coarse and causing the toner to adhere to the inner wall surface of the device. Particle fusion may become severe.

The toner particles whose surfaces have been treated with hot air are cooled by cold air supplied from a cold air supply port 103 provided on the outer periphery of the upper part of the apparatus. At this time, in order to control the temperature distribution within the apparatus and the surface condition of the toner particles, it is preferable to introduce cold air from a second cold air supply port 104 provided on the side surface of the main body of the apparatus. The outlet of the second cold air supply port 104 can have a slit shape, a louver shape, a perforated plate shape, a mesh shape, etc., and the introduction direction can be selected horizontally toward the center or along the device wall depending on the purpose. It is.

At this time, it is preferable to adjust the amount of hot air and cold air to a small value so that the crosslinking reaction time can be extended.

Further, it is preferable that the cold air is dehumidified air because water molecules generated during the crosslinking reaction can be discharged out of the system. Specifically, it is preferable that the absolute moisture content in the cold air is 5 g/m ³ or less. More preferably, it is 3 g/m ³ or less.

Thereafter, the cooled toner particles are sucked by a blower, passed through a transfer pipe 116, and collected by a cyclone or the like.

Hereinafter, methods for measuring various physical properties of toner and materials in the present invention will be explained.

<Intention hardness of organosilicon polymer particles>
Microhardness tester: Triboindenter TI950 (manufactured by Bruker Japan Co., Ltd.)
Measurement mode: Quasi-static indentation test (load control mode)
Indenter: Berkovich indenter

(Scanning image acquisition conditions)
First, in order to specify the position of the organosilicon polymer particles on the toner, a scanning image was obtained under the following conditions.
Setpoint: 1μN
Scan rate: 1Hz
Tip velocity: 10μm/sec

(Measurement conditions for microhardness test of organosilicon polymer particles on toner)
Next, the position of the convex structure was identified from the obtained scanning image, and an indentation test was conducted under the following conditions.
Maximum pushing load: 2μN
Pushing time: 5 seconds Holding time: 2 seconds Unloading time: 5 seconds Indentation hardness was calculated using the load displacement curve obtained under the above conditions. Note that calculations were performed using dedicated software for the device.

<Identification method of organosilicon polymer particles>
The organosilicon polymer particles contained in the toner can be identified by a combination of shape observation using SEM and elemental analysis using EDS.

Using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.), the toner is observed in a field of view magnified up to 50,000 times. Focus on the toner particle surface and observe the external additive. EDS analysis is performed on each particle of the external additive, and it is determined from the presence or absence of a Si element peak whether the analyzed particle is an organosilicon polymer particle.

If the toner contains both organosilicon polymer particles and silica fine particles, the ratio of Si and O element contents (atomic%) (Si/O ratio) can be compared with the standard product. Identification of organosilicon polymers. Samples of organosilicon polymer particles and fine silica particles are subjected to EDS analysis under the same conditions to obtain the elemental contents (atomic %) of Si and O. Let A be the Si/O ratio of the organosilicon polymer particles, and B be the Si/O ratio of the silica fine particles. Select measurement conditions under which A is significantly larger than B. Specifically, the standard specimen is measured 10 times under the same conditions, and the arithmetic average values of each of A and B are obtained. Measurement conditions are selected such that the obtained average value is A/B>1.1.

When the Si/O ratio of the fine particles to be determined is on the A side rather than [(A+B)/2], the fine particles are determined to be organosilicon polymer particles.

Tospearl 120 (Momentive Performance Materials Japan LLC) is used as a sample of organosilicon polymer particles, and HDK V15 (Asahi Kasei) is used as a sample of silica fine particles.

<Method for identifying composition and ratio of constituent compounds of organosilicon polymer>
NMR is used to identify the composition and ratio of constituent compounds of the organosilicon polymer contained in the toner.

When the toner contains fine silica particles in addition to the organosilicon polymer, 1 g of the toner is placed in a vial, dissolved in 31 g of chloroform, and dispersed. For dispersion, an ultrasonic homogenizer is used for 30 minutes to prepare a dispersion.
Ultrasonic processing device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.)
Microchip: Stepped microchip, tip diameter φ2mm
Microchip tip position: center of glass vial and 5 mm height from the bottom of the vial Ultrasonic conditions: intensity 30%, 30 minutes. At this time, ultrasonic waves are applied while cooling the vial with ice water to prevent the temperature of the dispersion from rising.

The dispersion liquid is transferred to a swing rotor glass tube (50 mL), and centrifuged at 58.33 s ^-1 for 30 minutes using a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.). In the glass tube after centrifugation, the lower layer contains fine silica particles with a heavy specific gravity. A chloroform solution containing the organosilicon polymer in the upper layer is collected, and the chloroform is removed by vacuum drying (40° C./24 hours) to prepare a sample.

Using the above sample or organosilicon polymer, the abundance ratio of the constituent compounds of the organosilicon polymer and the ratio of T unit structure in the organosilicon polymer are measured and calculated by solid state ²⁹ Si-NMR.

In solid state ²⁹ Si-NMR, peaks are detected in different shift regions depending on the number of functional groups bonded to Si constituting the organosilicon polymer.

The number of functional groups in each peak can be determined using standard samples. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of the T unit structure to the total peak area can be determined by calculation.

The measurement conditions for solid state ²⁹ Si-NMR are, for example, as follows.
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method 29Si 45°
Sample tube: Zirconia 3.2mmφ
Sample: Filled in test tube in powder state Sample rotation speed: 10kHz
relaxation delay: 180s
Scan:2000

First, the hydrocarbon group represented by R ^a above is confirmed by ¹³ C-NMR.

^≪13C -NMR (solid) measurement conditions≫
Equipment: JNM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2mmφ
Sample: 150 mg of tetrahydrofuran insoluble content of toner particles for NMR measurement
Measurement temperature: room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25MHz ( ^13C )
Reference substance: Adamantane (external standard: 29.5ppm)
Sample rotation speed: 20kHz
Contact time: 2ms
Delay time: 2s
Accumulated number of times: 1024 times

In the above method, methyl group (Si-CH ₃ ), ethyl group (Si-C ₂ H ₅ ), propyl group (Si-C ₃ H ₇ ), butyl group (Si-C ₄ H ₉ ), pentyl group (Si-C ₅ H ₁₁ ), hexyl group (Si-C ₆ H ₁₃ ), or phenyl group (Si-C ₆ H ₅ -), ^etc. Check the hydrocarbon groups represented.

On the other hand, in solid ²⁹ Si-NMR, peaks are detected in different shift regions depending on the number of functional groups bonded to Si in the constituent compounds of the organosilicon polymer.

The number of functional groups in each peak can be determined using standard samples. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area.

The specific measurement conditions for solid state ²⁹ Si-NMR are as follows.
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method ²⁹ Si 45°
Sample tube: Zirconia 3.2mmφ
Sample: Filled in test tube in powder state Sample rotation speed: 10kHz
relaxation delay: 180s
Scan:2000

After the above measurement, peaks of multiple silane components with different substituents and bonding groups of the organosilicon polymer are separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting, and the peak area of each is calculated. calculate.

Note that the following X3 structure is the T unit structure in the present invention.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (A1)
X2 structure: (Rg) (Rh)Si(O _1/2 ) ₂ (A2)
X3 structure: RmSi(O _1/2 ) ₃ (A3)
X4 structure: Si(O _1/2 ) ₄ (A4)

前記式（Ａ１）、（Ａ２）及び（Ａ３）中のＲｉ、Ｒｊ、Ｒｋ、Ｒｇ、Ｒｈ、Ｒｍはケイ素に結合している、炭素数１以上６以下の炭化水素基などの有機基、ハロゲン原子、ヒドロキシ基、アセトキシ基又はアルコキシ基を示す。）

Ri, Rj, Rk, Rg, Rh, and Rm in the formulas (A1), (A2), and (A3) are organic groups such as hydrocarbon groups having 1 or more and 6 or less carbon atoms, and halogens, which are bonded to silicon. Indicates an atom, hydroxy group, acetoxy group or alkoxy group. )

In addition, if it is necessary to confirm the structure in more detail, it may be identified based on the measurement results of ¹ H-NMR together with the measurement results of ¹³ C-NMR and ²⁹ Si-NMR.

<Number average particle diameter of organosilicon polymer particles>
The number average particle size of the primary particles of the external additive is measured using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.). The toner to which the external additive has been externally added is observed, and the length diameter of 100 primary particles of the external additive is randomly measured in a field of view magnified up to 50,000 times to determine the number average particle diameter. The observation magnification is appropriately adjusted depending on the size of the organosilicon polymer particles.

<Quantification of organosilicon polymer particles contained in toner>
The content of the external additive made of organosilicon polymer particles contained in the toner can be determined by the following method.

If the toner contains silicon-containing substances other than the organosilicon polymer particles, the toner is dispersed in a solvent such as chloroform, and then centrifugation is performed to remove the silicon-containing substances other than the organosilicon polymer particles. After removal, the content of organosilicon polymer particles is determined.

First, the pressed toner is measured using fluorescent X-rays, and the silicon content in the toner is determined by performing analytical processing such as the calibration curve method or the FP method.

Next, the mass ratio of silicon is determined from the molecular weight of the constituent compounds of the organosilicon polymer particles whose structures have been identified using solid-state 29Si NMR, pyrolysis GC/MS, and the like.

The amount of organosilicon polymer particles in the toner can be determined by calculation from the relationship between the silicon content in the toner determined by fluorescent X-rays and the silicon content ratio in the constituent compounds.

<Fixing rate of organosilicon polymer>
Weigh out 20 g of "Contaminon N" (a 30% by mass aqueous solution of pH 7 neutral detergent for cleaning precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder) into a 50 mL vial, and add 1 g of toner and Mix.

Set in "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., set the speed to 50, and shake for 120 seconds. As a result, depending on the state of adhesion of the organosilicon polymer particles, the particles move from the toner particle surface to the dispersion liquid side.

After that, in the case of non-magnetic toner, the organosilicon polymer transferred to the toner and supernatant liquid is separated using a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) (16.67 s ^-1 for 5 minutes). . The separated toner is vacuum dried (40° C./24 hours) to dryness and used as a sample.

In the case of magnetic toner, use a neodymium magnet to restrain the toner particles, separate the external additives that have migrated to the supernatant liquid, and vacuum-dry the precipitated toner (40°C/24 hours). Dry it and use it as a sample.

The toner is pelletized by press molding as described below and used as a sample. With respect to the toner samples before and after the above treatment, the amount of silicon to be analyzed is determined by wavelength dispersive X-ray fluorescence analysis (XRF) as described below. Then, the fixation rate of the organosilicon polymer particles is calculated from the ratio to the amount of silicon remaining on the surface of the toner particles without transferring to the supernatant side through the above treatment, and from the quantitative determination of the organosilicon polymer particles in the toner. I can do it. The arithmetic mean value of 100 samples is adopted.
(i) Example of equipment used Fluorescent X-ray analyzer 3080 (Rigaku Denki Co., Ltd.)
(ii) Sample Preparation A sample press molding machine MAEKAWA Testing Machine (manufactured by MFG Co, Ltd.) is used for sample preparation. Put 0.5 g of toner into an aluminum ring (model number: 3481E1), set the load to 5.0 tons, and press for 1 minute to pelletize.
(iii) Measurement conditions Measurement diameter: 10φ
Measurement potential, voltage 50kV, 50-70mA
2θ angle 25.12°
Crystal plate LiF
Measurement time: 60 seconds (iv) About the method for calculating the fixation rate of organosilicon polymer particles [Formula] Fixation rate of organosilicon polymer (%) = (Quantitative value of organosilicon polymer particles in toner after treatment / Before treatment Quantitative value of organosilicon polymer particles in toner) x 100

In the present invention, "organosilicon polymer is fixed" is defined as a fixation rate of 90% or more in the above measurement.

<Method for measuring relative permittivity of organosilicon polymer particles>
To measure the dielectric constant of organosilicon polymer particles, SI 1260 electrochemical interface (manufactured by Toyo Technica) is used as a power source and ammeter, and 1296 dielectric interface (manufactured by Toyo Technica) is used as a current amplifier.

As the measurement sample, a sample obtained by heating and molding the sample into a disk shape with a thickness of 3.0±0.5 mm is used using a tablet molding machine. Gold electrodes are produced in a circular shape with a diameter of 10 mm on the upper and lower surfaces of the sample using mask evaporation.

A measurement electrode is attached to the prepared measurement sample, and an AC voltage of 100 mVp-p is applied at a frequency of 0.1 MHz to measure the capacitance. Calculate the dielectric constant ε of the measurement sample from the following formula.
ε=dC/ε ₀ S
d: Thickness of measurement sample (m)
C: Capacitance (F)
ε ₀ : Dielectric constant of vacuum (F/m)
S: Electrode area (m ² )

<Shape factor SF-1 of organosilicon polymer particles>
The shape factor SF-1 of the organosilicon polymer particles was calculated as follows by observing the toner using a scanning electron microscope (SEM) "S-4800" (manufactured by Hitachi, Ltd.).

In a field of view magnified 100,000 to 200,000 times, the perimeter and area of the primary particles of 100 organosilicon polymer particles were calculated using image processing software "Image-Pro Plus 5.1J" (manufactured by MediaCybernetics). Calculated.

SF-1 was calculated using the following formula, and the average value was defined as SF-1.
SF-1 = (maximum length of particle) ² / area of particle x π/4 x 100

<Method of measuring toner softening point (1/2 method)>
The softening point (1/2 method) of the toner is measured using a constant-load extrusion type capillary rheometer "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. . In this device, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature.

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D" is the softening point (1/2 method). Note that the melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time the outflow starts, and set the calculated value to X (X = (Smax - Smin) /2). The temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

As for the measurement sample, about 1.0 g of sample was heated at about 10.0 MPa using a tablet molding and compression machine (for example, "NT-100H", manufactured by NP System Co., Ltd.) in an environment at a temperature of 25 ° C. A cylindrical piece with a diameter of about 8 mm is used by compression molding for about 60 seconds.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 50℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

<How to calculate average circularity of toner>
The average circularity of the toner is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under measurement and analysis conditions during calibration work.

The measurement principle of the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to capture a still image of flowing particles and perform image analysis. A sample added to the sample chamber is delivered to a flat sheath flow cell by a sample suction syringe. The sample sent into the flat sheath flow is sandwiched between the sheath liquid and forms a flat flow.

The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, making it possible to capture still images of flowing particles. Furthermore, since the flow is flat, the image is captured in a focused state. Particle images are captured by a CCD camera, and the captured images are processed at an image processing resolution of 512 x 512 pixels (0.37 x 0.37 μm per pixel) to extract the outline of each particle image and create a particle image. The projected area S, perimeter L, etc. of are measured.

Next, the equivalent circle diameter and circularity are determined using the area S and the perimeter L. The equivalent circle diameter is the diameter of a circle that has the same area as the projected area of the particle image, and the circularity C is the value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the particle projection image. It is defined as and calculated using the following formula.
Circularity C=2×(π×S) ^1/2 /L

When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness on the outer periphery of the particle image, the smaller the circularity becomes. After calculating the circularity of each particle, the range of circularity from 0.200 to 1.000 is divided into 800 parts, the arithmetic mean value of the obtained circularity is calculated, and this value is taken as the average circularity.

The specific measurement method is as follows. First, 20 mL of ion-exchanged water from which impure solid matter has been removed is placed in a glass container. This contains "Contaminon N" as a dispersant (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. Add 0.2 mL of a diluted solution prepared by diluting (manufactured by )) with ion-exchanged water to 3 times the mass.

Furthermore, 0.02 g of the measurement sample is added, and a dispersion process is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. At that time, the temperature of the dispersion liquid is appropriately cooled to a temperature of 10° C. or higher and 40° C. or lower. As the ultrasonic disperser, a table-top ultrasonic cleaner disperser (for example, "VS-150" (manufactured by Vervo Crea Co., Ltd.)) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used. A predetermined amount of ion-exchanged water is placed in the water tank, and 2 mL of the contaminon N is added to the water tank.

For the measurement, the aforementioned flow type particle image analyzer equipped with a standard objective lens (10x magnification) is used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in HPF measurement mode and total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analyzed particle diameter is limited to an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is determined.

Before starting the measurement, automatic focus adjustment is performed using standard latex particles. For example, "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific is used after being diluted with ion exchange water. Thereafter, it is preferable to perform focus adjustment every two hours from the start of the measurement.

In the embodiment of the present application, a flow type particle image analyzer that has been calibrated by Sysmex Corporation and has a calibration certificate issued by Sysmex Corporation is used. The measurement is carried out under the measurement and analysis conditions under which the calibration certificate was received, except that the particle diameter for analysis was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Method for measuring weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is calculated as follows.

As a measuring device, a precise particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method and equipped with a 100 μm aperture tube is used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used to set the measurement conditions and analyze the measurement data. Note that the measurement is performed using 25,000 effective measurement channels.

The electrolytic aqueous solution used in the measurement can be one in which special grade sodium chloride is dissolved in ion-exchanged water to have a concentration of 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter, Inc.).

In addition, before performing measurement and analysis, configure the dedicated software as follows.

On the "Change standard measurement method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter). Set the value obtained using By pressing the "Threshold/Noise Level Measurement Button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement".

On the "Pulse to Particle Size Conversion Settings" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker exclusively for Multisizer 3, set it on a sample stand, and stir with a stirrer rod counterclockwise at 24 rotations/second. Then, use the special software's ``aperture flush'' function to remove dirt and air bubbles from inside the aperture tube.
(2) Put 30 mL of the electrolytic aqueous solution into a 100 mL glass flat bottom beaker. This contains "Contaminon N" as a dispersant (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. Add 0.3 mL of a diluted solution prepared by diluting (manufactured by )) with ion-exchanged water to 3 times the mass.
(3) Prepare an ultrasonic dispersion system "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with two built-in oscillators with an oscillation frequency of 50 kHz with their phases shifted by 180 degrees and an electrical output of 120 W. do. Put 3.3 liters of ion-exchanged water into the water tank of the ultrasonic disperser, and add 2 mL of contaminon N into the water tank.
(4) Set the beaker of (2) above in the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, the height position of the beaker is adjusted so that the resonance state of the electrolyte aqueous solution level in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In addition, in the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10° C. or more and 40° C. or less.
(6) Using a pipette, drop the aqueous electrolyte solution of (5) in which toner is dispersed into the round-bottomed beaker of (1) placed in the sample stand, and adjust the measured concentration to 5%. Then, the measurement is continued until the number of particles to be measured reaches 50,000.
(7) Analyze the measurement data using the dedicated software attached to the device and calculate the weight average particle diameter (D4). Note that when the graph/volume % is set in the dedicated software, the "average diameter" on the "analysis/volume statistics (arithmetic mean)" screen is the weight average particle diameter (D4).

The present invention can be particularly suitably used with toners having a weight average particle diameter of 5.0 μm or more and 8.0 μm or less.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Note that all copies of Examples and Comparative Examples are based on mass unless otherwise specified.

<Production example of organosilicon polymer particles 1>
(First step)
360.0 parts of water was placed in a reaction vessel equipped with a thermometer and a stirrer, and 15.0 parts of hydrochloric acid having a concentration of 5.0% by mass was added to form a homogeneous solution. To this was added 133.0 parts of methyltrimethoxysilane with stirring at a temperature of 25°C, and after stirring for 5 hours, it was filtered to obtain a transparent reaction liquid containing a silanol compound or a partial condensate thereof.

(Second process)
540.0 parts of water was placed in a reaction vessel equipped with a thermometer, a stirrer, and a dropping device, and 17.0 parts of ammonia water having a concentration of 10.0% by mass was added to form a homogeneous solution. While stirring this at a temperature of 35° C., 100 parts of the reaction solution obtained in the first step was added dropwise over 0.5 hours, and the mixture was stirred for 6 hours to obtain a suspension. The obtained suspension was centrifuged to precipitate fine particles, which were taken out and dried in a dryer at a temperature of 200° C. for 24 hours to obtain organosilicon polymer particles 1 made of polyalkylsilsesquioxane.

The obtained organosilicon polymer particles 1 had a number average particle diameter of 100 nm when observed using a scanning electron microscope, and a peak of formula (2) was observed when measured by solid state ²⁹ Si-NMR. R ¹ was a methyl group, and X=1.00. Table 2 shows the physical properties of organosilicon polymer particles 1.

<Production examples of organosilicon polymer particles 2 to 14>
Organosilicon polymer particles 2 to 14 were obtained in the same manner as in the production example of organosilicon polymer particles 1, except that the silane compound, reaction initiation temperature, catalyst addition amount, and dropping time were changed as shown in Table 1. Ta. Table 1 shows the physical properties of the organosilicon polymer particles 2 to 14 obtained.

[Production example of binder resin 1]
The following materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
Terephthalic acid: 22.5 parts Trimellitic anhydride: 2.7 parts Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 74.8 parts Titanium dihydroxybis(triethanolaminate) :0.3 part

Thereafter, the mixture was heated to 200° C. and reacted for 8 hours while introducing nitrogen and removing generated water. Thereafter, 3.0 parts of trimellitic anhydride was added, heated to 180° C., and reacted for 2.5 hours to synthesize Binder Resin 1.

Binder Resin 1 had an acid value (AV) of 19 mgKOH/g, a glass transition temperature (Tg) of 62°C, and a softening point (1/2 method) of 122°C.

[Example 1 of manufacturing toner base particles]
Binder resin 1: 100.0 parts Paraffin wax (HNP-9 Nippon Seiro): 5.0 parts C.I. I. Pigment Blue 15: 3: 5.0 parts 3.5-di-t-butylsalicylic acid aluminum compound: 0.5 parts The above materials were mixed in a Henschel mixer ("FM-75 model", manufactured by Mitsui Miike Kakoki Co., Ltd.). After thorough mixing, the mixture was kneaded using a twin-screw kneader ("PCM-30", manufactured by Ikegai Tekko Co., Ltd.) set at a temperature of 140°C. The obtained kneaded product was cooled and coarsely ground to 1 mm or less using a hammer mill to obtain a coarsely ground product. The obtained coarse material was pulverized using a collision-type air flow pulverizer using high-pressure gas. Next, the toner base particles 1 were obtained by classifying them using a wind classifier using the Coanda effect ("Elbow Jet Lab EJ-L3", manufactured by Nippon Steel Mining Co., Ltd.) to remove fine powder and coarse powder at the same time. .

[Example 2 of manufacturing toner base particles]
<Preparation of binder resin particle dispersion>
89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 150 parts of ion-exchanged water was added to this solution and dispersed. While stirring slowly for an additional 10 minutes, an aqueous solution of 0.3 parts of potassium persulfate and 10 parts of ion-exchanged water was added. After purging with nitrogen, emulsion polymerization was carried out at 70°C for 6 hours. After the polymerization was completed, the reaction solution was cooled to room temperature and ion-exchanged water was added to obtain a resin particle dispersion having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

<Preparation of wax dispersion>
100 parts of wax (behenyl behenate, melting point: 72.1°C) and 15 parts of Neogen RK were mixed with 385 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Joko Co., Ltd.) to form a wax. A dispersion was obtained. The concentration of the wax dispersion was 20% by mass.

<Preparation of colorant dispersion>
As a colorant, 100 parts of carbon black "Nipex 35 (manufactured by Orion Engineered Carbons)" and 15 parts of Neogen RK were mixed with 885 parts of ion-exchanged water and dispersed for about 1 hour using a wet jet mill JN100 to form a colorant dispersion. I got it.

<Example of production of toner base particle 2>
265 parts of the resin particle dispersion, 10 parts of the wax dispersion, and 10 parts of the colorant dispersion are dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). The temperature inside the container was adjusted to 30° C. while stirring, and a 1 mol/L aqueous sodium hydroxide solution was added to adjust the pH to 8.0. As a flocculant, an aqueous solution prepared by dissolving 0.3 parts of magnesium sulfate in 10 parts of ion-exchanged water was added over 10 minutes with stirring at 30°C. After leaving it for 3 minutes, heating was started and the temperature was raised to 50°C to generate associated particles. In this state, the particle size of the associated particles is measured using "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). When the weight average particle diameter reached 6.5 μm, 3.0 parts of sodium chloride and 8.0 parts of Neogen RK were added to stop particle growth.

Thereafter, the temperature was raised to 95° C. to fuse and spheroidize the associated particles. When the average circularity reached 0.980, the temperature was started to decrease to 30° C. to obtain toner particle dispersion 1.

Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was stirred for 1 hour and then separated into solid and liquid using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separation was performed using the aforementioned filter. After repeating the reslurry and solid-liquid separation until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner cake. The obtained toner cake was dried using a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were a blowing temperature of 90.degree. C., a dryer outlet temperature of 40.degree. C., and a supply rate of the toner cake so that the outlet temperature did not deviate from 40.degree. C. in accordance with the moisture content of the toner cake. Furthermore, fine and coarse powder was cut using a multi-division classifier utilizing the Coanda effect to obtain toner base particles 2.

[Toner production example 1]
Toner base particles 1: 100.0 parts Organosilicon polymer particles 1: 2.0 parts The above materials were put into a Henschel mixer ("FM-75 model", manufactured by Mitsui Miike Kakoki Co., Ltd.), and the The organosilicon polymer particles 1 were attached to the surface of the toner base particles 1 by mixing at a speed of 35 m/sec for a mixing time of 5 minutes.

Next, treatment was performed using a surface treatment apparatus using hot air shown in FIG.

The conditions during surface modification were as follows: raw material supply rate 1.0 kg/hr, hot air flow rate 1.4 m ³ /min, hot air discharge temperature 180°C, cold air temperature 3°C, cold air flow rate 1.2 m ³ /min. Surface treatment was performed at an absolute moisture content of 3.0 g/m ³ .

Next, fine powder and coarse powder were simultaneously classified and removed using a wind classifier ("Elbow Jet Lab EJ-L3", manufactured by Nippon Steel Mining Co., Ltd.) utilizing the Coanda effect to obtain toner particles 1.

Next, 100.0 parts of toner particles and 1.0 parts of hydrophobic silica fine particles (surface treated with 15% by mass of hexamethyldisilazane, number average diameter of primary particles 50 nm) were mixed in a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.). FM-75 model manufactured by )) at a temperature of 30° C., the circumferential speed of the rotary blade was set to 35 m/sec, and the mixing time was set to 8 minutes, and the mixture was passed through a sieve with an opening of 45 μm to obtain Toner 1.

[Toner production examples 2 to 16 and toner production examples 18 to 22]
Toner production example 1 except that the toner base particles, the particle types of the organosilicon polymer particles, the number of parts added of the organosilicon polymer particles, the mixing before hot air treatment, and the hot air discharge temperature were changed as shown in Table 3. Toners 2 to 16 and toners 18 to 22 were prepared in the same manner as in the above.

[Toner production example 17]
Toner base particles: 1: 100.0 parts Organosilicon polymer particles: 1: 2.0 parts Weigh each of the above materials so that the total weight is 10.0 kg at the above mixing ratio, and put them into a 900 mm x 700 mm plastic bag. . Seal the bag to prevent the contents from leaking, lift it with both hands and shake it 5 times. After the subsequent surface modification step, Toner 17 was produced in the same manner as in Toner Production Example 1.

[Toner production example 23]
Toner 23 was produced without using a surface treatment process using hot air.

Specifically, 1:100.0 parts of toner mother particles and 1:2.0 parts of organosilicon polymer particles were put into a Henschel mixer ("FM-75 model", manufactured by Mitsui Miike Kakoki Co., Ltd.), By mixing at a circumferential speed of the rotating blade of 35 m/sec and a mixing time of 20 minutes, the organosilicon polymer particles 1 were adhered to the surface of the toner base particles 1 to obtain toner particles 23.

Next, 100.0 parts of toner particles 23 and 1.0 part of hydrophobic silica fine particles (surface treated with 15% by mass of hexamethyldisilazane, number average diameter of primary particles 50 nm) were mixed in a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.). FM-75 model manufactured by )) at a temperature of 30° C., the circumferential speed of the rotary blade was set to 35 m/sec, and the mixing time was set to 8 minutes, and the toner 23 was obtained through a sieve with an opening of 45 μm.

The material composition and physical properties of toners 1 to 23 are summarized in Table 3.

[Examples 1 to 16, Comparative Examples 1 to 7]
<Measurement of adhesion rate of organosilicon polymer particles>
In the above measurements, the fixation rates of toners 1 to 23 were measured and are listed in Table 4.

<Evaluation method>
Evaluations were made using the following evaluation methods and criteria (1) to (3) from the viewpoint of member contamination and durability. Various evaluations were conducted by modifying the Canon laser beam printer LBP652C so that the fixing temperature and process speed could be adjusted, and by expanding the container capacity of the cartridge and increasing the toner filling amount to fill each toner. .

For evaluation, 24,000 1% printed images were output using A4 CS-680 (basis weight 68 g/cm ² ).

[Evaluation (1): Evaluation of photoreceptor drum scratches]
In an environment of 15° C./10% RH, scratches on the surface of the photoreceptor were observed using a magnifying glass when 24,000 sheets were output for the above-mentioned durable development evaluation. The evaluation criteria are as follows.

(Evaluation criteria)
A: There are no scratches on the surface of the photoreceptor drum.
B: Fine scratches with a width of less than 1.0 μm are present on the surface of the photoreceptor drum.
C: A scratch with a width of 1.0 μm or more and less than 5.0 μm is present on the photoreceptor drum surface.
D: A scratch with a width of 5.0 μm or more is present on the surface of the photoreceptor drum. (Unpractical level)

The evaluation results are shown in Table 4.

[Evaluation (2): Charging roller contamination evaluation (durability evaluation)]
In an environment of 30° C./80% RH, the staining property of the charging roller (“roller-shaped charging member”) was evaluated when 24,000 sheets were output in the above-mentioned durable development evaluation. Measure the charging AC current value of the charging roller by applying a constant AC voltage before and after durability (if the charging roller is contaminated, the resistance will increase and the charging current will decrease), and the amount of decrease in current is considered as contamination and is determined as follows. It was evaluated based on the criteria.
Amount of current decrease (mA) = (Initial current value) - (Current value after durability)

(Evaluation criteria)
A: The amount of decrease in current is less than 0.10 mA B: The amount of decrease in current is 0.10 mA or more and less than 0.30 mA C: The amount of decrease in current is 0.30 mA or more and less than 0.50 mA D: The amount of decrease in current is 0.10 mA or more and less than 0.50 mA. 50mA or more (unpractical level)

The evaluation results are shown in Table 4.

[Evaluation (3): Fog]
In an environment of 15° C./10% RH, the fog density at the initial stage and after 24,000 sheets were output, and the reflectance (%) of the non-image area were measured using “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using the numerical value (%) subtracted from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. The smaller the value, the more suppressed image fogging is.

(Evaluation criteria)
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 5.0% D: 5.0% or more (practically unacceptable level)

The evaluation results are shown in Table 4.

100: Toner particle supply port, 101: Hot air supply port, 102: Air jetting member, 103: Cold air supply port, 104: Second cold air supply port, 106: Cooling jacket, 114: Toner particles, 115: High pressure air supply nozzle , 116: Transfer piping

Claims (5)

A method for producing a toner comprising toner particles having toner base particles containing a binder resin, wax, and a colorant, and organosilicon polymer particles, the method comprising:
a step of mixing the toner base particles and the organosilicon polymer particles, and then subjecting the toner base particles to surface treatment with hot air;
The organosilicon polymer particles adhere to the surface of the toner base particles,
The adhesion rate of the organosilicon polymer particles to the toner base particles is 90% or more,
The organosilicon polymer particles have an intention hardness of 0.10 GPa or more and 1.50 GPa or less at a load of 2 μN, a number average diameter of primary particles of 35 nm or more and 300 nm or less, and a relative dielectric constant εra measured at 10 Hz. 3.5 or less. 2. The toner manufacturing method according to claim 1 , wherein the temperature of the hot air is equal to or higher than the softening point of the toner. 3. The method for producing a toner according to claim 1 , wherein a blending ratio of the organosilicon polymer particles is 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the toner base particles. 4. The method for producing a toner according to claim 1 , wherein the organosilicon polymer particles have a shape factor SF-1 of 114 or less. The organosilicon polymer particles have a structure in which silicon atoms and oxygen atoms are alternately bonded, and a part of the organosilicon polymer particles have a T unit structure represented by R ^a SiO _3/2 . ,
The R ^a represents an alkyl group or a phenyl group having 1 to 6 carbon atoms,
In the ²⁹ Si-NMR measurement using the chloroform-insoluble content of the organosilicon polymer particles, the peak derived from silicon having a T unit structure relative to the total area of the peaks derived from all silicon elements contained in the chloroform-insoluble content 5. The method for producing a toner according to claim 1 , wherein the area ratio of is 0.50 or more and 1.00 or less.

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