JP4208693B2 - Toner production method and toner particle surface modification device - Google Patents

Description

  The present invention relates to a method for producing a toner for developing an electrostatic charge image in an image forming method such as electronic printing, or a method for producing a toner for forming a toner-fixed image in a toner jet image forming method, and The present invention relates to a surface modification apparatus suitably used in a production method. The production method and the surface modification apparatus of the present invention are particularly suitable for use in a production method of toner used for a fixing method in which a toner image is heat-fixed on a print sheet such as a transfer material.

  Generally, as a method for producing a toner, a method of producing a toner by mixing raw materials and heating, melting, and dispersing with a kneader or the like to obtain a uniform composition, and then cooling and pulverizing and classifying the mixture. It is the current mainstream from the viewpoint of mass productivity and cost.

  However, since the toner particles produced by such a kneading and pulverizing method have irregular shapes, the toner characteristics tend to vary. For this reason, in the technical trends such as miniaturization, simplification, and high image quality of electrophotographic apparatuses, the performance required for toner is very advanced today, and the present situation is not fully satisfied. In recent years, in order to improve the transferability of toner in order to introduce a cleanerless system and reduce the amount of waste toner, it is necessary to modify the surface shape of the toner (= sphericalization etc.). It is coming.

  As a method for modifying the surface shape of the toner, for example, a method of making the toner spherical by applying a mechanical impact force has been proposed (for example, see Patent Document 1). In addition to the method using the mechanical impact force described above, a method of melting the toner surface with hot air, a method of using heat, and the like are known (for example, see Patent Document 2). However, there is a problem that the surface composition of the toner changes due to heat. In particular, since the presence state of the wax component added as a release agent changes, the method of melting the surface by heat is not preferable from the viewpoint of maintaining the quality of the toner. . Further, in the method using mechanical impact force, in the case of toner that is easily over-pulverized during spheroidization, the toner is pulverized due to the impact accompanying spheronization and the amount of fine powder increases. There are still unfavorable aspects from the viewpoint of toner productivity.

Thus, since the toner requires many different properties, the properties of the toner are often influenced by the method of producing the toner in addition to the raw materials used. Further, in the toner surface modification process, it is required to produce a high-quality toner stably and efficiently at low cost without generating fine powder during the spheronization process.
Japanese Patent Laid-Open No. 9-85741 JP 2000-29241 A

  The present invention eliminates the above-mentioned problems of the prior art, and produces toner that can more efficiently obtain surface-modified particles having a sharp particle size distribution that is less affected by heat at the time of surface modification and has less fine powder. It is an object of the present invention to provide a method and a surface modifying apparatus that enables the production of such a toner.

In addition, the present invention can control the surface shape of the surface-modified particles to a desired one, and by controlling the surface shape of the surface-modified particles, good developability, transferability, cleaning properties, and stability can be achieved. It is an object of the present invention to provide a production method capable of obtaining a long-life toner having the above-described charging property, and a surface modifying apparatus capable of producing such a toner.

  As a result of intensive studies to solve the above-described problems of the prior art, the inventor of the present invention is a batch type surface reforming apparatus that classifies particles and performs spheroidization, and the structure of members and the structure and positional relationship between members. By operating the product in an appropriate state, it is possible to prevent excessive pulverization of the particles accompanying the surface modification, and the surface modified particles having a sharp particle size distribution with less influence of heat and less fine powder are more efficient. By knowing that the surface shape of the obtained surface modified particles can be arbitrarily controlled, and by performing surface modification treatment using such a surface modification device, good developability, transferability and cleaning can be achieved. The present inventors have found that a long-life toner having excellent chargeability and stable chargeability can be obtained.

The present invention also provides a step of producing toner raw material particles containing at least a binder resin and a colorant, and obtaining toner particles by subjecting the toner raw material particles to a surface modification treatment using a toner particle surface modifying device. A process for producing a toner comprising the steps of:
The toner particle surface modifying device includes a main body casing, a top plate installed in the main body casing so as to be openable and closable, a charging unit for charging toner raw material particles into the main casing, and a predetermined amount of toner raw particles charged in the main casing. Classifying means for continuously removing fine powder having a particle size or less to obtain processed toner particles, fine powder discharging section for discharging fine powder removed by the classification means to the outside of the main body casing, processed toner particles from which the fine powder has been removed A surface treatment means for performing a surface modification treatment using a mechanical impact force, a cylindrical guide means for partitioning a space between the classification means and the surface treatment means into a first space and a second space, and the Fine particles having a predetermined particle diameter or less are removed by the classifying means, and the toner particles to be treated, which have been subjected to the surface modification treatment by the surface treatment means, are discharged out of the casing as toner particles. The toner raw material particles introduced into the main body casing from the charging unit are introduced into the first space, and the fine particles having a predetermined particle diameter or less are removed by the classifying means to continuously out of the apparatus. It is discharged through the second space, introduced into the surface treatment means, subjected to surface modification treatment, and circulated to the first space again to repeat classification and surface modification treatment, whereby predetermined particles are obtained. To obtain toner particles from which fine powder of a diameter or less has been removed and subjected to surface modification treatment,
The input part is provided with an input port having an openable / closable raw material particle supply valve, and the discharge part for discharging the surface modified particles from which fine powder having a predetermined particle size or less is discharged has an openable / removable surface modification. A discharge port having a particulate discharge valve is provided, the discharge port has a cylindrical shape, the surface-modified particle discharge valve has a packing member on a surface that contacts the discharge port, and the center line of the discharge port at a position that is surface modified particles valve located in the surface modified particles discharge valve is closed, the outlet and the surface in a state in which the surface modified particles discharge valve is closed method for producing a toner, characterized in that said packing member modified particles discharge valve has is an angle θ is 85 to 95 ° between the contact surfaces about.

Furthermore, the present invention is a batch-type surface modification device for classifying toner raw material particles and performing spheronization treatment,
Main body casing, top plate installed in the main body casing so as to be openable and closable, a charging part for charging raw material particles into the main body casing, and fine particles having a predetermined particle size or less are continuously removed from the raw material particles charged into the main body casing. Classifying means for obtaining treated particles, a fine powder discharging unit for discharging fine powder removed by the classifying means to the outside of the main body casing, and surface modifying treatment for the treated particles from which the fine powder has been removed using mechanical impact force Surface treatment means, cylindrical guide means that partitions the classification means and the surface treatment means into a first space and a second space, and fine powder having a predetermined particle size or less are removed by the classification means, And a discharge section for discharging the particles to be treated, which have been subjected to the surface modification treatment by the surface treatment means, to the outside of the main casing as the surface modification particles,
The raw material particles introduced into the main body casing from the introduction part are introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classification means, and the second space is discharged continuously from the apparatus. The surface is introduced through the surface treatment means and subjected to surface modification treatment, and is again circulated to the first space to repeat classification and surface modification treatment, thereby removing the fine powder having a predetermined particle size or less. To obtain modified particles,
The input part is provided with an input port having an openable / closable raw material particle supply valve, and the discharge part for discharging the surface modified particles from which fine powder having a predetermined particle size or less is discharged has an openable / removable surface modification. A discharge port having a particulate discharge valve is provided, the discharge port has a cylindrical shape, the surface-modified particle discharge valve has a packing member on a surface that contacts the discharge port, and the center line of the discharge port at a position that is surface modified particles valve located in the surface modified particles discharge valve is closed, the outlet and the surface in a state in which the surface modified particles discharge valve is closed The modified particle discharge valve has
A toner particle surface modification apparatus characterized by the packing member is an angle θ is 85 to 95 ° between the contact surfaces.

  According to the present invention, excessive pulverization associated with the surface modification of toner particles is prevented, surface-modified particles having a sharp particle size distribution with less influence of heat and less fine powder can be obtained more efficiently, and surface modification can be achieved. A toner particle surface modifying apparatus capable of arbitrarily controlling the surface shape of the particle is obtained. In addition, according to the present invention, a long-life toner having good developability, transferability, cleanability, and stable chargeability can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

  <Method for Producing Toner of the Present Invention>

The method for producing a toner of the present invention comprises a step of producing toner raw material particles containing at least a binder resin and a colorant, and subjecting the toner raw material particles to a surface modification treatment using a toner particle surface modifying device. A method of producing a toner comprising a step of obtaining particles,
The toner particle surface modifying device includes a main body casing, a top plate installed in the main body casing so as to be openable and closable, a charging unit for charging toner raw material particles into the main body casing, and a predetermined particle size from the toner raw material particles charged into the main body casing. Classifying means for continuously removing the following fine powder to obtain treated toner particles, fine powder discharging section for discharging the fine powder removed by the classification means to the outside of the main body casing, processed toner particles from which fine powder has been removed, Surface treatment means for surface modification treatment using an impact force, cylindrical guide means for partitioning the first space and the second space between the classification means and the surface treatment means, and the predetermined particle size by the classification means A discharge unit that discharges the toner particles to be processed, from which the following fine powder has been removed and the surface modification processing by the surface treatment means, to the outside of the main body casing as toner particles; The toner raw material particles put into the main body casing are introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classifying means and continuously discharged out of the apparatus through the second space, Introduced into the surface treatment means, the surface modification treatment is performed, and the classification and the surface modification treatment are repeated by circulating again to the first space, whereby fine particles having a predetermined particle diameter or less are removed and the surface modification treatment is performed. To obtain toner particles made,
At least a part of the classification means is covered by the guide means, and the vertical length l of the portion of the classification means covered by the guide means and the overall length L of the classification means in the vertical direction are expressed by the following formula: It satisfies the relationship (1).
l / L ≦ 0.7 (1)

  Further, another aspect of the toner production method of the present invention includes a main body casing, a charging unit, a classification unit, a fine powder discharging unit, a surface treatment unit, a guiding unit, and a discharging unit as described above. The toner raw material particles introduced into the main body casing are introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classifying means and continuously discharged out of the apparatus through the second space, Introduced into the surface treatment means, the surface modification treatment is performed, and the classification and the surface modification treatment are repeated by circulating again to the first space, whereby fine particles having a predetermined particle diameter or less are removed and the surface modification treatment is performed. In the toner surface reforming apparatus for obtaining the toner particles made, the charging unit is provided with a charging port having a raw material particle supply valve that can be opened and closed, and the surface modifying particles from which fine powder having a predetermined particle size or less is removed are provided. Open and close the discharge section A discharge port having an effective surface-modified particle discharge valve is provided, and an angle θ between the center line of the discharge port and a surface of the discharge port facing the surface-modified particle discharge valve is 85 to 95 °. It is characterized by being.

  The toner produced by the production method of the present invention has toner particles containing at least a binder resin and a colorant, and an external additive added to and mixed with the toner particles as necessary. First, raw materials for toner particles will be described. The toner particles used in the present invention contain at least a binder resin and a colorant, and if necessary, further contain other materials contained in conventional toners such as wax and charge control agent.

[Binder resin]
As the binder resin used in the present invention, various resin compounds known as binder resins for conventional toners can be used. For example, vinyl resins, phenol resins, natural resin-modified phenol resins, natural resins 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, coumaroindene resin, petroleum resin, etc. It is done. Of these, vinyl resins and polyester resins are preferred in terms of chargeability and fixability.

  Examples of vinyl resins include styrene; o-methylstyrene, m-methylstyrene, p-methylenestyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethyl. Styrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene Styrene derivatives such as pn-dodecylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as: vinyl acetate, vinyl propionate, benzo Vinyl esters such as vinyl acid; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, Α-methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acrylic acid esters such as n-octyl acid, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinylmethyl Vinyl ethers such as ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone N-vinyl compounds such as: vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; esters of α, β-unsaturated acids, diesters of dibasic acids; acrylic acid, methacrylic acid, Acrylic acid such as α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid and α- or β-alkyl derivatives thereof; fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid And polymers using vinyl monomers such as unsaturated dicarboxylic acids such as mesaconic acid, dimethylmaleic acid and dimethylfumaric acid, and monoester derivatives or anhydrides thereof.

  In the vinyl resin, the vinyl monomers as described above are used alone or in combination of two or more. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  In addition, the binder resin used in the present invention may be a polymer or copolymer cross-linked with a cross-linkable monomer as exemplified below if necessary.

  As the crosslinkable monomer, a monomer having at least two crosslinkable unsaturated bonds can be used. As such a crosslinkable monomer, various monomers as shown below are known and can be suitably used for the toner used in the present invention.

Examples of monofunctional monomers among the crosslinkable monomers include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate, 1,3- Butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylate Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, and tetraethylene glycol diacrylate. , Polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and acrylates of the above compounds are replaced by methacrylate; linked by a chain containing an aromatic group and an ether bond Examples of the diacrylate compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propande Examples of the polyester-type diacrylates include trade name MANDA (Nippon Kayaku Co., Ltd.) and the like.

  Polyfunctional crosslinkable monomers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; Examples thereof include lucyanurate and triallyl trimellitate.

  As binder resin used for this invention, the polyester resin shown below is also preferable. It is preferable that 45 to 55 mol% of the polyester resin is an alcohol component and 55 to 45 mol% is an acid component in all components.

  Examples of alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1,6- Xanthdiol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (B);

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

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

又はグリセリン、ソルビット、ソルビタン等の多価アルコール類等が挙げられる。 Diols represented by the following formula (C);

Or polyhydric alcohols, such as glycerin, sorbit, sorbitan, etc. are mentioned.

  As the acid component, a carboxylic acid can be preferably exemplified, and as the divalent carboxylic acid, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride, or anhydrides thereof; succinic acid, adipine Alkyl dicarboxylic acids such as acid, sebacic acid and azelaic acid or their anhydrides; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or their anhydrides; Examples of the acid include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and its anhydride.

  A particularly preferable alcohol component of the polyester resin is a bisphenol derivative represented by the formula (B), and examples of the acid component include phthalic acid, terephthalic acid, isophthalic acid or anhydride thereof, succinic acid, n-dodecenyl succinic acid, or the like. Examples thereof include dicarboxylic acids such as anhydride, fumaric acid, maleic acid and maleic anhydride; trimellitic acid or tricarboxylic acid of anhydride thereof. This is because the heat roller fixing toner using a polyester resin obtained from these acid components and alcohol components as a binder resin has good fixability and excellent offset resistance.

[Magnetic material]
When the toner of the present invention is used as a magnetic toner, the toner is used by containing a magnetic material. The magnetic substance contained in the magnetic toner is not particularly limited as long as it is normally used. For example, iron oxide containing magnetite, maghemite, ferrite, and other metal oxides; Fe, Co, Ni Or such metals and metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V And alloys thereof, and mixtures thereof.

Specifically, examples of the magnetic substance include triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), and iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder ( Ni) and the like. The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.

These magnetic materials have an average particle diameter of 0.05 to 2 μm, magnetic characteristics of 795.8 kA / m applied, coercive force of 1.6 to 12.0 kA / m, saturation magnetization of 50 to ²⁰⁰ Am ² / kg (preferably 50 to 100 Am ² / kg) and a residual magnetization of ^{2 to 20} Am ² / kg are particularly preferable for use in an electrophotographic image forming method. In addition, these magnetic materials are preferably contained in an amount of 60 to 200 parts by mass, more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

[Colorant]
In the present invention, the magnetic material may be used as a colorant for toner, but a nonmagnetic colorant or the like may be used as another colorant. Such non-magnetic colorants include any suitable pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, bengara, phthalocyanine blue, and indanthrene blue. These are added in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Similarly, a dye is used, and an addition amount of 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass is good with respect to 100 parts by mass of the binder resin.

  As the colorant used in the present invention, as a black colorant, carbon black, a magnetic material, and a yellow / magenta / cyan colorant shown below are used, and a black colorant is used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacdrine compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66 can be particularly preferably used.

〔wax〕
The toner in the present invention may further contain a wax. As the wax used in the present invention, various waxes conventionally known as mold release agents can be used, and there are the following. Examples of hydrocarbon waxes include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin wax, microcrystalline wax, paraffin wax, and aliphatic hydrocarbon wax such as Fischer-Tropsch wax.

  As the wax having a functional group, an oxide of an aliphatic hydrocarbon wax such as oxidized polyethylene wax; or a block copolymer thereof; a plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; Animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolactam; waxes based on aliphatic esters such as montanate wax and castor wax: deacidified carnauba wax The thing which partly or entirely deoxidized aliphatic ester is mentioned.

In addition, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid; stearyl alcohol Saturated alcohol such as eicosyl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or alkyl alcohol having a long chain alkyl group; polyhydric alcohol such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bis-stearic acid amide, ethylene bis-capric acid amide, ethylene bis-lauric acid amide, hexamethylene bis-stearic acid amide; ethylene bis-olei Unsaturated fatty acid amides such as acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N Aromatic bisamides such as'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); fatty acids such as behenic acid monoglyceride And a partially esterified product of polyhydric alcohol; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  Wax grafted with a vinyl monomer can also be used in the toner of the present invention. As such a wax, there is a wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid.

  Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures Polyolefins; polyolefins polymerized using radiation, electromagnetic waves, or light; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon waxes synthesized by the Gintor method, Hydrocol method, Age method, etc. Synthetic waxes using compounds as monomers; hydrocarbon waxes having functional groups such as hydroxyl groups, carboxyl groups or ester groups; mixtures of hydrocarbon waxes and hydrocarbon waxes having functional groups; these waxes Styrene as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

[Charge control agent]
In the toner used in the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. The charge control agent is preferably used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the binder resin, from the viewpoint of controlling the chargeability of the toner.

As the charge control agent, various conventionally known charge control agents can be used, and examples thereof include the following. As a negative charge control agent for controlling the toner to be negative charge, for example, an organometallic complex or a chelate compound is effective. Examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, or phenol derivatives of bisphenol. Preferable examples include metal complexes of Cr, Co, and Fe, which are monoazo dyes synthesized from phenol or naphthol, which is a monoazo metal compound having an alkyl group, halogen, nitro group, carbamoyl group or the like as a substituent. A metal compound of an aromatic carboxylic acid is also preferably used, and examples thereof include benzene, naphthalene, anthracene, phenanthrene carboxylic acid, hydroxycarboxylic acid, and dicarboxylic acid metal compounds having an alkyl group, a halogen, a nitro group, and the like.

  Among these, an azo metal complex represented by the following formula (1) is preferable.

〔式中、Ｍは配位中心金属を表し、Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｃｏ，Ｎｉ，Ｍｎ又はＦｅ
等が挙げられる。Ａｒはアリール基であり、フェニル基、ナフチル基の如きアリール基であり、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン基、カルボキシル基、アニリド基及び炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基がある。Ｘ，Ｘ’，Ｙ及びＹ’は−Ｏ−，−ＣＯ−，−ＮＨ−，−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ｃ^＋はカウンターイオンを示し、水素、ナトリウム、カリウム、アンモニウム、脂肪族アンモニウム或いはそれらの混合イオンを示す。〕

[Wherein M represents a coordination center metal, Sc, Ti, V, Cr, Co, Ni, Mn or Fe
Etc. Ar is an aryl group, which is an aryl group such as a phenyl group or a naphthyl group, and may have a substituent. In this case, examples of the substituent include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. X, X ′, Y and Y ′ are —O—, —CO—, —NH—, —NR— (R is an alkyl group having 1 to 4 carbon atoms). C ⁺ represents a counter ion and represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium, or a mixed ion thereof. ]

  In the above formula (1), Fe or Cr is particularly preferable as the central metal, halogen, alkyl group or anilide group is preferable as the substituent, and hydrogen, alkali metal, ammonium or aliphatic ammonium is preferable as the counter ion. A mixture of complex salts having different counter ions is also preferably used.

  A basic organometallic complex represented by the following formula (2) is also preferable as a charge control agent imparting negative chargeability.

Examples of the positive charge control agent that controls the toner to be positively charged include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts. For example, modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide) , Ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicycline Diorgano tin borate such as hexyl tin borate; they can be used alone or in combination of two or more kinds.

〔式中、Ｒ_１はＨ又はＣＨ_３を示し、Ｒ_２及びＲ_３は置換又は未置換のアルキル基（好ましくは、Ｃ_１〜Ｃ_４）を示す。〕
で表されるモノマーの単重合体；前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合、この単重合体及び共重合体は荷電制御剤としての機能と、結着樹脂（の全部又は一部）としての機能を有する。 Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used. Moreover, following formula (3)

[Wherein, R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ ). ]
A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, the homopolymer and the copolymer have a function as a charge control agent and a function as a binder resin (all or a part thereof).

In particular, a compound represented by the following formula (4) is preferable as the toner positive charge control agent of the present invention.

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different from each other, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. Represents an aryl group. R ₇ , R ₈ and R ₉ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. A ^- is such sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxyl ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, a tetrafluoroborate Indicates an anion. ]

As a method for adding the charge control agent to the toner, there are a method of adding the charge control agent inside the toner particles and a method of adding the toner to the toner particles. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

(External additive)
As described above, the toner of the present invention generally contains, in addition to toner particles, external additives for adjusting the fluidity and chargeability of the toner as necessary. As such an external additive, a fluidity improver may be added to the toner. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder; fine powder silica such as wet process silica and dry process silica; fine powder titanium oxide; fine powder alumina; surface of them with silane compound, titanium coupling agent, silicone oil There are treated fine powders.

  The hydrophobizing method is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with fine powder.

  Examples of organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane, and α-chloro. Ethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3 -Diphenyltetramethyldisiloxane and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing a hydroxyl group bonded to one Si at each terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used in one kind or a mixture of two or more kinds.

  In the present invention, particles having a particle size of 0.1 to 5.0 μm may be further externally added to the toner particles in order to provide a polishing effect and / or a spacer effect. As such particles, inorganic fine particles, organic fine particles, and mixtures and composites thereof can be used. Specifically, metal oxides such as strontium titanate, cerium oxide, aluminum oxide, and magnesium oxide, fluorine resin powder, resin fine particles, and the like can be given. Particularly in terms of charging characteristics, strontium titanate and cerium oxide are preferable.

  Next, the method for producing the toner of the present invention will be described by taking as an example the case of producing the toner using the toner constituent materials and external additives described above. As described above, the toner production method of the present invention includes a step of producing toner raw material particles containing at least a binder resin and a colorant, and a surface modification treatment of the toner raw material particles using a surface modifying device. Thereby obtaining toner particles. In the present invention, “toner raw material particles” means toner particles (surface modified particles) that have been subjected to surface modification treatment by the surface modification device of the present invention before the surface modification treatment is performed. It shows untreated toner particles (raw material particles). Further, in the present invention, “toner particles to be treated (treated particles)” indicate toner raw material particles (raw material particles) subjected to classification and surface modification treatment in the surface modifying apparatus of the present invention. . That is, toner particles to be processed (processed particles) that have been subjected to a predetermined process in the surface modifying apparatus are discharged out of the apparatus as toner particles (surface modified particles).

  The process for producing the toner raw material particles can be a process for producing toner particles using a conventionally known method such as a pulverization method or a polymerization method, and is not particularly limited. However, from the viewpoint that the effect of the surface modification treatment by the surface modification apparatus of the present invention is maximized, a step of obtaining a kneaded product by melt-kneading a composition containing at least a binder resin and a colorant; A step of cooling and solidifying the obtained kneaded product and obtaining a finely pulverized product as toner raw material particles by pulverizing the cooled and solidified product using a collision-type airflow pulverizer or a mechanical pulverizer. It is preferable that it is the process manufactured by a method.

  A method for producing toner raw material particles by the pulverization method will be described. First, at least a resin and a colorant are weighed and mixed as toner particle internal additives and mixed (this is referred to as a “raw material mixing step”). Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw material (composition) blended and mixed as described above is melt-kneaded to melt the resins and disperse the colorant and the like therein (this is referred to as “melt-kneading step”). In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Further, the colored resin composition as a kneaded product obtained by melt-kneading the toner raw material is rolled by a two-roll or the like after the melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization process, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill, etc., and further, a counter jet mill (manufactured by Hosokawa Micron), a micron jet T type (manufactured by Hosokawa Micron), a cross jet mill (manufactured by Kurimoto Steel Works) ), Collision type airflow crushers such as IDS type and PJM jet mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd.), or innomizer (manufactured by Hosokawa Micron), kryptron (manufactured by Kawasaki Heavy Industries, Ltd.), super rotor (manufactured by Nisshin Engineering Co., Ltd.) ), A turbo mill (manufactured by Turbo Kogyo Co., Ltd.), a tornado mill (manufactured by Nikkiso Co., Ltd.) and the like. In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step.

  Further, the pulverized product as the toner raw material particles obtained in the pulverization step is subjected to surface modification, that is, spheroidization treatment, in the surface modification step to obtain surface modified particles. In the present invention, the surface modified particles thus obtained may be used as toner particles. In addition, after passing through the above surface modification step, the surface-modified particles are optionally classified into inertial class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), TSP separator ( Toner particles having a weight average particle diameter of 3 to 11 μm through a classification step using a classifier such as an airflow classifier such as Hosokawa Micron Co., Ltd., or a sieving machine such as a wind voltaic high volter (manufactured by Shin Tokyo Machinery Co., Ltd.). You may get. Further, the classification step may be performed before the surface modification step.

  The toner coarse powder generated in the classification step is returned to the pulverization step and pulverized. Further, it is preferable in terms of toner productivity that the toner fine powder generated in the classification process is returned to the toner raw material blending process and reused.

The toner in the present invention may be composed only of the toner particles obtained as described above, and an external additive as described above may be further added to the obtained toner particles as necessary. It may be a mixture. As a method of externally adding an external additive to the toner, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives shearing force to powder such as a Henschel mixer or a super mixer is removed. It is preferable to use it as an accessory and stir and mix. At this time, since heat is generated inside the external adder and it becomes easy to generate aggregates, it is preferable in terms of toner productivity to adjust the temperature by means such as cooling the periphery of the container of the external adder with water.

  Next, the surface modification step in the toner production method of the present invention and the batch type surface modification apparatus of the present invention used in the surface modification step will be specifically described with reference to the drawings.

  FIG. 1 is a schematic sectional view showing an example of a toner particle batch type surface reforming apparatus used in the present invention, and FIG. 2 is a top view of a rotor (dispersing rotor 32) that rotates at a high speed in FIG. 3 is a schematic diagram of a toner particle batch type surface modifying apparatus used in the present invention, and FIG. 4 is a schematic diagram of a surface modified particle discharge mechanism of the toner particle batch type surface modifying apparatus used in the present invention. is there.

  The toner particle batch type surface modification apparatus shown in FIG. 1 includes a main body casing 30; a top plate 43 installed to be openable and closable at the top of the main body casing; a fine powder discharge casing 44 as a fine powder discharge section; Cooling jacket 31 that can be formed: a disk that rotates in a high speed and has a plurality of square disks or cylindrical pins 33 on its upper surface, which is attached to the central rotating shaft in the main body casing 30 as surface treatment means A distributed rotor 32 as a rotating body; a liner 34 (a groove on the liner surface) which is fixedly arranged around the distributed rotor 32 at a constant interval and has a large number of grooves on the surface. The classification rotor 35 as a classifying means for classifying the surface-modified raw material particles into a predetermined particle size and continuously removing fine particles having a predetermined particle size or less. A fine powder discharge port 45 as a fine powder discharge portion for discharging fine powder removed by the classification rotor 35 to the outside of the apparatus (that is, outside the main body casing 30); and a cold air introduction port 46 for introducing cold air into the main body casing 30 A raw material input port 37 and a raw material supply port 39 as input portions for introducing the raw material particles; a discharge portion for discharging the powder after the surface modification treatment (that is, the surface modified particles) to the outside of the main body casing 30; A product discharge port 40 and a product extraction port 42; and an openable and closable raw material supply valve 38 installed between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be freely adjusted. And a product discharge valve 41 as a surface modified particle discharge valve installed between the product discharge port 40 and the product extraction port 42.

  The surface modifying apparatus further includes a guide ring 36 as a cylindrical guide means in the main body casing 30. The upper end of the guide ring 36 is provided at a predetermined distance from the top plate, and is installed in a state where at least a part of the classification rotor 36 is covered with the cylinder. Further, the lower end of the guide ring 36 is provided at a predetermined distance from the disk portion of the dispersion rotor 32 or the pin 33. By this guide ring 36, the space between the classification rotor 35 and the dispersion rotor 32-liner 34 in the apparatus is divided into a first space 47 outside the cylinder and a second space 48 inside the cylinder. . Here, the first space 47 is a space for introducing the particles to be processed into the classification rotor 35, and the second space is a space for introducing the particles to be processed into the dispersion rotor. Further, a gap portion between the liner 34 and the square disk or cylindrical pin 33 installed on the dispersion rotor 32 is a surface modification zone 49, and the classification rotor 35 and the periphery of the rotor are classification zones. 50.

  The classifying means used in the present invention is not particularly limited as long as it can remove fine powder having a predetermined particle size or less from the particles to be treated, but is preferably a means for classifying by rotation of an impeller type classification rotor. At this time, the classifying rotor may be installed vertically or horizontally as shown in FIG. Further, the number of classification rotors may be single as shown in FIG. 1 or plural. Moreover, it is preferable that the rotation direction of a dispersion | distribution rotor and a classification rotor is the same direction. If the rotation directions of the dispersion rotor and the classification rotor are reversed, the load on the classification rotor increases, and normal operation cannot be performed, which is not satisfactory from the viewpoint of toner productivity.

Further, in the toner particle batch type surface reforming apparatus, it is preferable in terms of the apparatus configuration that the contacting surface portion of the classification rotor 35 with respect to the top plate 43 is not brought into close contact with the top plate 43 and an appropriate gap is provided. At this time, the distance between the contact surface portion of the classification rotor 35 and the top plate is preferably 1.0 mm or less. Further, it is more preferable that air is blown out from the interval. When the interval exceeds 1.0 mm, there is a short path in which the surface-modified particles enter the fine powder casing without passing through the classification rotor from the interval even if air is blown out from the interval. The toner productivity may not be sufficiently satisfied. In addition, the air flow rate which blows off from this space | interval has preferable 0.5 m < ³ > / min or more, and 1.0 m < ³ > / min or more is more preferable. The air pressure is preferably 0.05 MPa or more, and more preferably 0.1 MPa or more.

  In the toner particle batch surface reforming apparatus of the present invention configured as described above, the raw material supply valve 38 is opened with the product discharge valve 41 closed, and the raw material particles (toner raw material) are supplied from the raw material inlet 37. Particles) and the raw material supply valve 38 is closed after a predetermined time. The raw material particles introduced into the apparatus from the raw material supply port 39 are first sucked by a blower (not shown), classified by the classification rotor 35, and become processed particles. At that time, the classified fine powder having a predetermined particle size or less is continuously discharged and removed through the fine powder discharge casing 44 and the fine powder discharge port 45 to the outside of the apparatus. Coarse powder having a predetermined particle size or more is guided along the inner periphery (second space 48) of the guide ring 36 by centrifugal force and is swirled along the circulating flow generated by the dispersion rotor 32 to the surface modification zone 49. The particles to be treated guided to the surface modification zone 49 are subjected to a mechanical impact force between the liner 34 and the square disk or cylindrical pin 33 installed on the dispersion rotor 32, Modified (ie, spheronized). The surface-treated particles whose surface has been modified are guided to the classification zone 50 while swirling along the outer periphery (first space 47) of the guide ring 36 along the cold air and blower suction flow passing through the machine. By the rotor 35, the fine powder is again discharged out of the machine through the fine powder discharge casing 44 and the fine powder discharge port 45, and the coarse powder is returned to the surface reforming zone 49 again through the circulation flow and subjected to surface modification treatment repeatedly. The After a certain period of time, the product discharge valve 41 is opened, and the surface-modified particles from which fine powder having a predetermined particle size or less has been removed from the product extraction port 42 are recovered.

  In addition, it is preferable in terms of toner productivity that the fine powder generated by the batch-type surface reforming apparatus is collected by a collecting device such as a cyclone or a bag and returned to the toner raw material mixing step and reused.

  The feature of the toner production method of the present invention is that the surface shape of the toner particles is controlled to a desired one by using a batch type surface modification device as shown in FIG. 1, and further, fine powder cut classification is performed. Thus, toner particles as surface modified particles having a sharp particle size distribution can be obtained more efficiently.

  That is, as a result of the study by the present inventors, the surface modifying apparatus used in the step of performing the surface modifying process in the toner production method is a batch type surface modifying apparatus as shown in FIG. It is a type with a built-in classification rotor that classifies into particle size, and further sets the configuration of the members in the batch type surface reforming apparatus and the structure and positional relationship between the members, and sets the operating conditions in the surface reforming zone. By controlling to an appropriate state, it is possible to prevent an increase in the amount of fine powder during the surface modification process and sharply classify the particle size distribution of the toner even when the surface of the toner that is easily overmilled is modified. it can. Furthermore, by arbitrarily setting the time to open and close the material supply valve and the time to open the product discharge valve, the toner residence time in the device can be adjusted, the toner surface shape can be arbitrarily controlled, and good development is achieved. A long-life toner having excellent properties, transferability and cleaning properties, and stable chargeability can be obtained.

The reason why the above effects can be obtained is as follows. The surface modified particles, that is, the surface shape of the surface modified particles depends on the residence time of the particles to be treated in the surface modifying apparatus. That is, in order to control the surface shape of the surface modified particles, it is important to control the residence time of the particles to be treated in the surface modifying apparatus. In the present invention, the surface modification device used in the surface modification treatment step is a batch type surface modification device as shown in FIG. 1, so that the product discharge valve 41 is closed after the raw material supply valve 38 is closed. (Surface modification) processing time to release the wheel, tooth shape and rotational peripheral speed of the disk upper surface of the dispersion rotor 32, distance between the dispersion rotor 32 and the liner 34, distance between the guide ring 36 and the dispersion rotor 32, etc. By controlling to a proper state, it is possible to prevent an increase in fine powder during the surface modification treatment, control the residence time of the particles to be treated in the surface modification device, and arbitrarily control the surface shape of the surface modified particles. Can do. In addition, a classification rotor 35 that classifies the particles to be processed into a predetermined particle size is further incorporated, and by controlling the rotational peripheral speed of the classification rotor 35 to an appropriate state, fine particles below the predetermined particles are continuously discharged out of the apparatus. Since the coarse powder can be surface-modified again, surface-modified particles having a sharp particle size distribution from which fine powder having a predetermined particle diameter or less are removed can be obtained.

Further, the feature of the toner particle surface modifying apparatus of the present invention used in the toner production method of the present invention is that the length of the portion of the classification rotor 35 covered with the guide ring 36 in the vertical direction is l, and the classification rotor 35 When the overall length in the vertical direction is L, the relationship of the following equation (1) is satisfied, and preferably the relationship of the following equation (2) is satisfied (see FIG. 3).
l / L ≦ 0.7 (1)
0.05 ≦ l / L ≦ 0.67 (2)

  As a result of studies by the present inventors, when l / L exceeds 0.7, the particle size distribution of the surface modified particles becomes broad, and the surface modified particles having a desired sharp particle size distribution may not be obtained. . On the other hand, when 1 / L is less than 0.05, the product yield may decrease. The reason for this is that when l / L exceeds 0.7, the classifying rotor enters too deeply into the guide ring, so that the classifying rotor and the surrounding classifying zone become narrower, and thereby the particle size distribution of the surface modified particles. Is considered to be broad. In addition, when l / L is less than 0.05, the distance between the classification rotor and the guide ring becomes too wide, so that the retention of particles in the classification zone around the lower portion of the classification rotor increases, and the classification efficiency is considered to decrease. It is done.

Accordingly, the vertical length l of the portion of the classification rotor 35 covered by the guide ring 36
When the overall length L in the vertical direction of the classifying rotor 35 is set to a value that satisfies the relationship of the above formula (1), preferably a value that satisfies the relationship of the above formula (2), Surface modified particles having a distribution can be obtained with higher product recovery.

Furthermore, in the present invention, when the outer diameter of the classification rotor 35 of the batch type surface reforming apparatus in FIG. 3 is R and the inner diameter of the guide ring 36 is d, these R and d are represented by the following formula (3). It is preferable to satisfy the relationship, and it is more preferable to satisfy the relationship of the following formula (4).
53.0 × 10 ⁻² ≦ R / d ≦ 85.0 × 10 ⁻² (3)
59.0 × 10 ⁻² ≦ R / d ≦ 80.0 × 10 ⁻² (4)

As a result of investigation by the present inventors, when R / d is less than 53.0 × 10 ⁻² , the product yield may be lowered. On the other hand, when R / d exceeds 85.0 × 10 ⁻² , the particle size distribution of the surface modified particles becomes broad, and the surface modified particles having a desired sharp particle size distribution may not be obtained.

The reason for this is considered as follows. When the outer diameter of the classification rotor 35 is constant, if R / d is less than 53.0 × 10 ⁻² , the first space that is the gap between the outer peripheral surface of the guide ring and the main body casing is narrowed. The passing speed of the particles to be processed in the first space becomes too fast. For this reason, the amount of particles to be processed to jump into the classification rotor 35 increases, and the particles to be processed that are supposed to be classified by the classification rotor 35 and led to the surface modification zone are excessively attracted to the classification rotor 35. Product yield will be reduced. R / d is 85.0 × 1
If it exceeds 0 ^-2 , conversely, the second space becomes narrow, the classification rotor 35 and the surrounding classification zone become narrow, the load on the classification rotor increases, the classification efficiency decreases, and the surface The particle size distribution of the modified particles becomes broad.

  Accordingly, the outer diameter R of the classification rotor 35 and the inner diameter d of the guide ring 36 of the batch type surface reforming apparatus satisfy the relationship of the above formula (3), and more preferably the relationship of the above formula (4). By satisfying the above, surface modified particles having a sharp particle size distribution can be obtained at a higher product recovery rate.

  Furthermore, in the present invention, the angle θ formed by the center line a of the product discharge port 40 and the surface of the product discharge port 40 facing the product discharge valve 41 is preferably 85 to 95 °. The product discharge port 40 has a cylindrical shape, and the product discharge valve 41 has a packing member 51 on a surface 53 facing the product discharge port 40 and is sealed by the packing member 51 and the product discharge port 40. There is preferably (see FIG. 4).

  In FIG. 4, the product discharge port 40 has a cylindrical shape, and a packing member 51 is installed on a surface 53 of the product discharge valve 41 facing the product discharge port. When the product discharge valve is closed, The packing member 51 and the product discharge portion 54 are in flat contact with each other to prevent an air leak phenomenon.

  As a result of the study by the present inventor, for example, as shown in FIG. 8, the angle θ formed by the center line a of the product discharge port 40 and the surface of the product discharge port 40 facing the product discharge valve 41 is less than 85 °, and When the product discharge valve 41 is closed and sealed with the product discharge portion and the tapered surface 81 of the product discharge valve, the product discharge port 40 and the product discharge valve 41 are sealed by contact with the tapered surface. For this reason, when surface-modified particles adhere to the product discharge valve 41 or the product discharge port 40, an air leak phenomenon in which outside air enters into the apparatus from the leak portion is likely to occur, and toner productivity may be reduced. . For the packing member 51, a known material such as silicone, nylon, fluororesin, or rubber can be used.

  In the present invention, when the product discharge valve 41 is opened and closed in order to discharge the surface modified particles out of the casing, it is preferable that compressed air is injected into the product discharge valve 41 and the product discharge port 40. . Without such a configuration, during long run operation, an air leak phenomenon in which outside air enters the apparatus from the leak location is likely to occur, which is not fully satisfactory from the viewpoint of toner productivity.

  Therefore, in the toner particle batch surface reforming apparatus, an angle θ formed by the center line a of the product discharge port 40 and the surface 53 of the product discharge port 40 facing the product discharge valve 41 is set to 85 to 95 °. Thus, the product discharge port 40 has a cylindrical shape, the packing member 51 is provided on the product discharge valve 41, and further, the product discharge valve 41 is provided to discharge the surface modified particles out of the main body casing 30. When opening and closing, the product discharge valve 41 and the product discharge port 40 are configured to inject compressed air so that the air particle phenomenon can be prevented from occurring even when the toner particle surface modification device is operated for a long time. It is preferable in terms of productivity.

  As a method for injecting compressed air to the product discharge valve and the product discharge port, a known method such as installation of an injection ring or an injection nozzle can be used.

Furthermore, in the present invention, as shown in FIG. 3, a guide plate 52 for sending the surface modified particles out of the main body casing 30 is installed at the product discharge port 40 of the toner particle surface modifying apparatus. Is preferred. At this time, when the width of the guide plate 52 viewed from the direction perpendicular to the center line of the product discharge port 40 is w and the distance between the inner wall of the main body casing 30 and the guide ring 36 is W, these w and W are expressed by the following formulae. It is preferable to satisfy the relationship (5), and it is more preferable to satisfy the relationship of the following formula (6).
w / W ≦ 0.9 (5)
0.3 ≦ w / W ≦ 0.9 (6)

  As a result of the study by the present inventor, as described above, by installing the guide plate 52 for sending the surface modified particles out of the casing at the product discharge port 40 of the surface modifying apparatus of the present invention, the surface modification is performed. The quality particles can be discharged out of the main casing more efficiently. Without this guide plate, the surface-modified particles may not be efficiently discharged outside the main body casing, which may be undesirable from the viewpoint of toner productivity.

  Further, as a result of examination by the present inventors, the width w of the guide plate and the distance W from the inner wall of the main body casing to the guide ring are w / W ≦ 0.9, more preferably 0.3 ≦ w / W ≦ 0.9. By adjusting the value to satisfy the relationship, the surface modified particles can be obtained at a higher product recovery rate.

  The reason for this is considered as follows. When the value of w / W exceeds 0.9, the distance between the guide plate and the guide ring becomes too narrow, and it is considered that turbulent flow occurs in this portion. It is considered that the surface modified particles jump into the classification rotor due to this influence, and the product recovery rate is lowered. Further, when the value of w / W is less than 0.3, the distance between the guide plate and the guide ring becomes too wide, so that when the discharge valve is opened, the surface modified particles cannot be collected and the product recovery rate is high. It is thought to decline.

  Therefore, the width w of the guide plate installed at the product discharge port and the distance W between the inner wall of the main body casing and the guide ring satisfy the relationship of the above formula (5), and more preferably the formula (6). By satisfying the relationship, the surface modified particles can be obtained with a higher product yield.

  FIG. 5 is a schematic cross-sectional view when the vicinity of the product discharge port 40 is viewed from the right hand direction of FIG. 3 in order to explain the configuration of the guide plate 52. As shown in FIG. 5, the guide plate 52 is preferably located at the center of the product discharge port 40. Moreover, it is preferable to adjust the length of the guide plate 52 so as to exist from the top plate 43 to the lower end of the product discharge port 40.

  As a result of the study by the present inventors, by setting the configuration of the members in the toner particle surface modification device and the structure and positional relationship between the members within the above range, the generation of fine powder during the surface modification treatment is suppressed, Surface modified particles having a sharp particle size distribution with less fine powder can be obtained at a higher product recovery rate.

  Furthermore, in the toner production method of the present invention, the surface modification time in the toner particle batch surface modification device is preferably 5 seconds or more and 180 seconds or less, and more preferably 15 seconds or more and 120 seconds or less. preferable. When the surface modification time is less than 5 seconds, since the surface modification time is too short, surface modified particles may not be obtained, which is not preferable in terms of toner quality. In addition, if the surface modification time exceeds 180 seconds, the surface modification time is too long, which may cause surface deterioration due to heat generated during surface modification, occurrence of in-machine fusion, and reduction in processing capacity. However, it is not satisfactory from the viewpoint of toner productivity.

Furthermore, in the present invention, the minimum distance between the dispersion rotor and the liner in the toner particle batch type surface modification device is preferably 0.5 to 15.0 mm, and more preferably 2.0 to 10.0 mm. More preferred. Further, the rotational peripheral speed of the dispersion rotor is preferably 30 to 175 m / sec, and more preferably 40 to 160 m / sec. Further, the minimum distance between the upper end of the rectangular disk or cylindrical pin 33 installed on the upper surface of the dispersion rotor in the batch type surface reforming apparatus and the lower end of the cylindrical guide ring 36 is set to 2.0 to. It is preferable to set it as 50.0 mm, and it is more preferable to set it as 5.0-45.0 mm.

  As a result of the study by the present inventors, when the minimum distance between the dispersion rotor 32 and the liner in the toner particle batch type surface modification device is less than 0.5 mm, the load on the device itself is increased, and at the same time, the surface modification is performed. Sometimes the particles to be treated are excessively pulverized and are liable to cause surface alteration or in-machine fusion due to heat, so that the toner productivity may not be sufficiently satisfied. Further, if the minimum distance between the dispersion rotor and the liner exceeds 15.0 mm, the processing capacity must be lowered to obtain surface-modified particles, which may not be sufficiently satisfactory in terms of toner productivity. .

  Further, if the rotational peripheral speed of the dispersion rotor in the toner particle batch type surface modification device is less than 30 m / sec, the processing capability must be reduced in order to obtain surface modified particles having a predetermined circularity, The toner productivity may not be fully satisfied. Further, if the rotational speed of the dispersion rotor exceeds 175 m / sec, the load on the apparatus itself increases, and at the same time, the surface-modified particles are excessively pulverized during the surface modification, and at the same time, the surface is altered by heat. And in-machine fusion, it may become unsatisfactory in terms of toner productivity.

  Further, the minimum distance between the upper end of the square disk or cylindrical pin installed on the upper surface of the disk of the dispersion rotor in the toner particle batch surface reforming apparatus and the lower end of the cylindrical guide ring is set to 2. If it is less than 0.0 mm, the load on the apparatus itself increases, and at the same time, the residence time of the particles to be treated in the first space inside the guide ring becomes long, and the surface is modified by the heat during the surface modification, Since fusing is likely to occur, the toner productivity may not be satisfactory. Further, if the minimum distance between the upper end of the rectangular disk or cylindrical pin installed on the upper surface of the dispersion rotor and the lower end of the cylindrical guide ring exceeds 50.0 mm, the particles to be processed are sufficient. This may cause a short path of flowing out into the second space outside the guide ring in a state where the surface is not modified, which is also not preferable in terms of toner productivity.

  Furthermore, in the toner production method of the present invention, it is preferable that the cold air temperature T1 introduced into the toner particle batch type surface modification device is 5 ° C. or less. By setting the cold air temperature T1 introduced into the toner particle batch type surface reforming apparatus to 5 ° C. or less (more preferably 0 ° C. or less, more preferably −5 ° C. or less), the heat generated by the surface modification is reduced. It is possible to prevent surface modification of the treated particles and in-machine fusion. When the cold air temperature T1 introduced into the toner particle batch type surface reforming apparatus exceeds 5 ° C. or more, the surface is easily deteriorated due to heat generated during the surface reforming or in-machine fusion, so toner productivity From the point of view, it is not preferable.

  Further, as the refrigerant used in the cool air generating device introduced into the toner particle batch type surface reforming device, an alternative chlorofluorocarbon is preferable from the viewpoint of environmental problems of the entire earth. Alternative CFCs include R134a, R404A, R407c, R410A, R507A, R717, etc. Among them, R404A is particularly preferable from the viewpoint of energy saving and safety.

  The cold air introduced into the toner particle batch type surface modification device is preferably dehumidified from the viewpoint of preventing condensation in the device from the viewpoint of toner productivity. As the cold air dehumidifying device, a known device can be used. The supply air dew point temperature is preferably −15 ° C. or lower, and more preferably −20 ° C. or lower.

  Furthermore, in the toner production method of the present invention, the inside of the toner particle batch type surface modification apparatus further includes a jacket for cooling the inside of the apparatus, and a refrigerant (preferably cooling water, more preferably, inside the jacket). It is preferable that the particles to be treated are surface-modified while passing through an antifreeze such as ethylene glycol). In-machine cooling by the jacket can prevent surface alteration and in-machine fusion due to heat during surface modification.

  The temperature of the refrigerant passed through the jacket of the toner particle batch type surface reforming apparatus is preferably 5 ° C. or less. Generated during surface modification by setting the temperature of the refrigerant passed through the jacket in the toner particle batch type surface modification device to 5 ° C. or lower (more preferably 0 ° C. or lower, more preferably −5 ° C. or lower). It is possible to prevent the surface modification of the particles to be treated and the in-machine fusion caused by heat. If the temperature of the refrigerant introduced into the cooling jacket exceeds 5 ° C., surface modification of the particles to be processed and in-machine fusion are liable to occur due to heat generated during surface modification, which is sufficient from the viewpoint of toner productivity. It is not satisfactory.

  In the toner production method of the present invention, it is preferable that the temperature T2 in the fine powder outlet 45 located behind the classification rotor 35 in the toner particle batch type surface modification device is 60 ° C. or less. By setting the temperature T2 to 60 ° C. or less (more preferably 50 ° C. or less), it is possible to prevent surface modification and in-machine fusion of the particles to be treated due to heat generated during surface modification. Assuming that the temperature T2 in the fine powder outlet 45 exceeds 60 ° C., it is presumed that a temperature higher than that in the surface modification zone has an influence, and the particles to be treated due to the heat generated during the surface modification. Since surface alteration and in-machine fusion are likely to occur, it is not preferable from the viewpoint of toner productivity.

  Further, in the toner manufacturing method of the present invention, the temperature difference ΔT (T2−T1) between the temperature T2 in the fine powder outlet and the cold air temperature T1 introduced into the batch type surface reforming apparatus is set to 80 ° C. or less. It is preferable. By setting the temperature difference ΔT (T2−T1) to 80 ° C. or less (more preferably 70 ° C. or less), it is possible to prevent surface modification and in-machine fusion of the particles to be treated due to heat generated during surface modification. . If the temperature difference ΔT (T2−T1) exceeds 80 ° C., it is assumed that a temperature higher than that in the surface modification zone has an influence, and the particles to be treated due to heat generated during the surface modification are affected. Surface alteration and in-machine fusion are likely to occur, and the toner productivity is not satisfactory.

  As a result of the study by the present inventor, by controlling the operating conditions of the toner particle batch surface modification device within the above range, the influence of heat during the surface modification can be reduced, and the surface shape of the surface modified particles can be reduced. It is possible to obtain a long-life toner that can be controlled as desired and has good developability, transferability and cleaning properties, and stable chargeability.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.
[Example 1]
・ Binder resin 100 parts by mass (styrene-butyl acrylate-maleic acid butyl half ester copolymer; Tg 65 ° C.)
Magnetic iron oxide 90 parts by mass (average particle diameter 0.22 [mu] m, the characteristics in 795.8 kA / m magnetic field: Hc = 5.1kA / m, σs = 85.1Am 2 /kg,σr=5.1Am 2 / kg )
・ Monoazo metal complex 2 parts by mass (negative charge control agent, T-77, manufactured by Hodogaya Chemical Co., Ltd.)
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer

  The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) for toner production.

The obtained powder raw material is finely pulverized by a mechanical pulverizer shown in FIG. 6 and classified by an inertia classification elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) shown in FIG. 0.0 μm,
Toner raw material particles having an abundance of particles having a particle diameter of 4.00 μm or less of 40% by number were obtained. Thereafter, the toner material particles were subjected to surface modification using a batch type surface modification apparatus shown in FIG. In addition, the structure of the surface modification process particle | grain discharge valve of the batch type surface treatment apparatus used at this time shall be what was shown to FIG.

  FIG. 6 is a schematic sectional view showing an example of a toner particle pulverizing apparatus system incorporating a mechanical pulverizer used in the present invention. In FIG. 6, the mechanical pulverizer includes a casing 313, a jacket 316 in the casing 313 that allows cooling water to pass, and a rotating body in the casing 313 that is attached to the central rotating shaft 312. In order to introduce a raw material to be processed, and further, a rotor 310 that is rotated at a high speed, a stator 310 that is arranged on the outer periphery of the rotor 314 at a constant interval and has a number of grooves on its surface, and The raw material inlet 311 and the raw material outlet 302 for discharging the processed powder. A gap portion between the rotor 314 and the stator 310 is a grinding zone.

  In the mechanical pulverizer configured as described above, when a predetermined amount of powder raw material is charged into the raw material charging port 311 of the mechanical pulverizer shown in FIG. Between a rotor 314 that is introduced into a processing chamber and rotates at a high speed in the crushing processing chamber and has a large number of corrugated grooves on the surface, and a stator 310 that has a large number of corrugated grooves on the surface Are instantaneously pulverized by the impact generated in the slab, a large number of ultra-high speed vortices generated behind this, and high-frequency pressure vibrations generated thereby. Thereafter, the finely pulverized material passes through the material discharge port 302 and is discharged out of the apparatus. The air carrying the toner particles passes through the pulverization chamber and is discharged out of the apparatus system through the material discharge port 302, the pipe 219, the collecting cyclone 229, the bag filter 222, and the suction filter 224. Is done.

  FIG. 7 shows an example of a multi-division classifier used in the present invention. In the multi-division classifier shown in FIG. 7, the classification chamber having a classification area mainly includes side walls 141 and 142, lower walls 143 and 144, and a Coanda block 145 having a shape as shown in FIG. The lower walls 143 and 144 have knife edge type classification edges 146 and 147, respectively, and the classification zones 146 and 147 divide the classification zone into three. Under the side wall 141, raw material supply pipes 148 and 149 that open to the classification chamber are provided, and a Coanda block 145 that is bent downward with respect to the extending direction of the bottom tangent of the supply pipe to draw a long elliptical arc is provided. Yes. Further, the upper wall 150 of the classification chamber includes a knife-edge type inlet edge 151 directed toward the lower portion of the classification chamber, and inlet tubes 152 and 153 that open to the classification chamber are provided at the upper portion of the classification chamber. Yes. The inlet pipes 152 and 153 are provided with gas introduction adjusting means 154 and 155 such as dampers, and static pressure meters 156 and 157, respectively. The positions of the classification edges 146 and 147 and the intake air edge 151 vary depending on the type of raw material to be classified and the desired particle size. Further, discharge ports 158, 159 and 160 that open into the classification chamber are provided on the bottom surface of the classification chamber so as to correspond to the respective classification areas.

The raw material supply pipe is preferably composed of a cylindrical raw material supply pipe 148 and a pyramidal cylindrical raw material supply pipe 149, but the ratio of the inner diameter of the raw material supply pipe 148 to the inner diameter of the narrowest portion of the raw material supply pipe 149 Is set to 20: 1 to 1: 1, preferably 10: 1 to 2: 1, a good insertion speed is obtained. In addition, as a means of feeding the powder raw material to be classified into the supply pipe together with the air flow, a method of sending by applying a pressure of 0.1 to 3 kg / cm ² , a fan on the downstream side of the classification zone is enlarged, and the negative of the classification zone is used. Method of naturally sucking outside air and powder raw material by increasing pressure, or method of attaching an injection feeder to the raw material powder inlet and sucking raw material powder and outside air and sending them to the classification zone through the supply pipe Etc.

The classification operation in the multi-division classification area having the above configuration is performed, for example, as follows. That is, the classification area is depressurized through at least one of the discharge ports 158, 159 and 160,
The raw material powder is supplied to the classification region through the raw material supply pipes 148 and 149 by the air flow flowing by the reduced pressure at a flow rate of 50 to 300 m / second. If the raw material is supplied to the classification region at a flow rate of less than 50 m / sec, it is difficult to sufficiently loosen the raw materials, and it is easy to cause a reduction in classification yield and classification accuracy. In addition, when the raw material is supplied to the classification region at a speed exceeding 300 m / sec, the particles are likely to be pulverized due to collision between the particles, and it is easy to produce ultrafine particles. Absent.

  By the above means, the supplied powder raw material moves along a curved line due to the Coanda effect by the action of the Coanda block 145 and the action of a gas such as air flowing at that time. Accordingly, large particles (particles having a particle size exceeding the standard particle size) are classified outside the air stream, that is, the first fraction area outside the classification edge 147, and intermediate particles (particles having a standard particle size) are classified. In the second fraction area between edges 146 and 147, small particles (particles less than the standard particle size) are divided into third fraction areas inside classification edge 146, respectively, and large particles (coarse powder) are discharged. From the outlet 158, intermediate particles (medium powder) are discharged from the outlet 159, and smaller particles (fine powder) are discharged from the outlet 160, respectively.

In the present embodiment, in the batch type surface reforming apparatus shown in FIG. 1, the length in the vertical direction of the portion covered with the guide ring 36 of the classifying means is l, and the length in the vertical direction of the entire classifying rotor 35 is L / L when L is 0.67, the outer diameter of the classification rotor 35 is R, and R / d when the inner diameter of the guide ring 36 is d is 63.9 × 10 ⁻² . In addition, the angle θ formed by the center line of the product discharge port 40 and the surface 53 of the product discharge valve 41 was 90 °. The width of the guide plate for sending the surface modified particles installed in the product discharge port 40 to the outside of the apparatus is w, and w / W is 0 when the distance between the inner wall of the main body casing and the guide ring is W. .7.

Further, eight square disks were installed on the upper surface of the disk of the dispersion rotor 32, the distance between the lower end of the guide ring 36 and the square disk 33 was 10 mm, and the distance between the square disk 33 and the liner 34 was 5 mm. Moreover, the rotational peripheral speed of the dispersion | distribution rotor 32 was 125 m / sec, and the blower air volume was 15 m < ³ > / min. The feed amount of the toner raw material particles was 80 kg / hr, and the surface modification time was 45 sec. The temperature of the refrigerant passed through the jacket was −10 ° C., and the cold air temperature T1 was −15 ° C. As a result of operating for 60 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 29 ° C. Therefore, ΔT (T2−T1) was 39 ° C.

  At this time, the target particle size of the obtained toner particles (surface modified particles) is set to a weight average particle size of 7.2 ± 0.3 μm and an abundance of particles having a particle size of 4.00 μm or less: 20% by number or less (more specifically, 15 to 18% by number), and the product recovery rate of the surface modified particles when adjusted within this particle size range was evaluated according to the following criteria. (Of course, a higher product recovery rate is preferable for toner productivity.)

A: Product recovery rate is 75% or more B: Product recovery rate is 65% or more and less than 75% C: Product recovery rate is 55% or more and less than 65% D: Product recovery rate is less than 55%

  In this example, by adjusting the peripheral speed of the classification rotor, the surface modification having a sharp particle size distribution having a weight average diameter of 7.2 μm and containing 15% by number of particles having a particle diameter of 4.00 μm or less. Quality particles (toner particles) could be obtained with a product recovery rate of 78%. This achieves a higher product recovery rate than the comparative example described later, the equipment configuration in the batch type surface reforming apparatus, that is, the structure of the members in the surface reforming apparatus and the structure of the members and As a result of setting the positional relationship in an appropriate state, it is assumed that the classification accuracy in the classification zone around the classification rotor has improved.

  The average particle size and particle size distribution of the toner were measured by the following method. A Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co., Ltd.) or the like was used to connect an interface (manufactured by Nikka) and a PC9801 personal computer (manufactured by NEC) that output number distribution and volume distribution. The electrolyte used was a 1% NaCl aqueous solution prepared using primary sodium chloride. As this electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) was added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample was further added. 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. Using the Coulter counter TA-II, a 100 μm aperture is used as an aperture, and the volume and number of toner having a particle diameter of 2 μm or more are determined. The volume distribution and the number distribution were calculated by measurement. Then, a toner having a volume-based weight average particle diameter obtained from the volume distribution according to the present invention (D4: the median value of each channel is a representative value of the channel) and a particle diameter obtained from the number distribution of 4.00 μm or less. The cumulative number of was determined. Here, the fine powder is defined as a particle size of 4.00 μm or less. That is, the smaller the value of the particle size is 4.00 μm or less, the sharper the particle size distribution is, and the larger the value is, the broad particle size distribution is.

  Further, in this example, the evaluation was performed using the average circularity as an index to indicate the degree of surface modification (= sphericalization) of the surface modified particles.

  The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and in the present invention, measurement is performed using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics, The circularity of the measured particles was determined by the following equation, and the value obtained by dividing the total circularity of all the measured particles by the total number of particles was defined as the average circularity.

  As a measuring method, about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved to prepare a dispersion, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 5 minutes. The circularity of the toner was measured with the above apparatus at a density of 5000-20000 / μl.

  The “average circularity” in the present invention is an index of the degree of unevenness of the surface-modified particles, and indicates 1.000 when the toner is a perfect sphere, and the average circularity becomes smaller as the toner shape becomes more complicated. Become. In this example, the average circularity was 0.965.

  Further, the surface shape of the surface modified particles was observed with a field emission scanning electron microscope (FE-SEM: Hitachi S-800) at a magnification of 10000 times, visually observed, and evaluated according to the following criteria. In this example, the surface shape of the surface modified particles had a circular silhouette.

A: Circular silhouette, practical use B: Slightly elliptical silhouette, practical use C: Curved but irregular, somehow practical D: Square silhouette, impractical

  Further, after the operation of the batch type surface reforming apparatus, the presence / absence of the in-machine fusion of the particles to be treated and the degree thereof were visually confirmed and judged according to the following criteria. In this example, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the dispersion rotor and the liner.

A: Practical use is possible without in-machine fusion B: In-machine fusion is slightly observed, but practical use is possible C: In-machine fusion is slightly observed, but practical use is possible D: In-machine fusion is noticeable, impractical

  Tables 1 and 2 show the production conditions and evaluation results of the surface modified particles (toner particles) in this example.

[Example 2]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this example, the same procedure as in Example 1 was performed except that l / L was set to 0.37. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 1 and 2 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 3]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this example, the same procedure as in Example 1 was performed except that l / L was set to 0.04. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 1 and 2 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 4]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At that time, in this example, the same procedure as in Example 1 was performed except that 1 / L was set to 0.73. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 1 and 2 show the production conditions and evaluation results of the surface modified particles (toner particles).

  Also in this example, the surface-modified particles containing 18% by number of particles having a weight average diameter of 7.3 μm and a particle diameter of 4.00 μm or less are adjusted to obtain a target particle size distribution. Got. However, the product recovery rate of the surface-modified particles was as low as 62%, and satisfactory results were not obtained as compared with the above-described examples. This is presumably because an effective classification effect could not be obtained in the classification zone around the classification rotor because the value of l / L exceeded 0.7.

［実施例５］
実施例１で得たトナー原料粒子を図１に示す回分式の表面改質装置で表面改質した。その際、本実施例においては、製品排出口４０中心線ａと、製品排出弁４１の面５３とのなす角度θを８５°とした。得られた表面改質粒子及び処理後の表面改質装置について、実施例１と同様に評価した。表面改質粒子（トナー粒子）の製造条件及び評価結果を表３及び４に示す。

[Example 5]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, the angle θ formed by the product discharge port 40 center line a and the surface 53 of the product discharge valve 41 is set to 85 °. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 3 and 4 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 6]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, the angle θ formed by the center line a of the product discharge port 40 and the surface 53 of the product discharge valve 41 is set to 95 °. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 3 and 4 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 7]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, the configuration of the product discharge portion is as shown in FIG. 8 (the angle θ formed by the product discharge port 40 center line and the surface of the product discharge port 40 where the product discharge valve exists is 30 °) The procedure was the same as in Example 1 except for the change. The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 3 and 4 show the production conditions and evaluation results of the surface modified particles (toner particles).

  In Example 7 as well, the classifying rotation speed was adjusted to obtain the target particle size distribution, and the surface modification contained 18% by number of particles having a weight average diameter of 7.3 μm and a particle diameter of 4.00 μm or less. Particles were obtained. However, the product recovery rate of the surface modified particles was as low as 57%, and satisfactory results were not obtained as compared with Examples 5 and 6 described above. This is because the angle θ formed by the center line of the product discharge port and the surface of the product discharge port where the product discharge valve exists is less than 85 °, and the product discharge when the product discharge valve is closed. Since the contact between the outlet and the product discharge valve is a taper surface contact, surface leakage particles adhere to the product discharge valve or the product discharge port, and an air leak phenomenon occurs in which outside air enters the machine, and the area around the classification rotor This is probably because an effective classification effect was not obtained in the classification zone.

[Example 8]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At that time, in this example, it was the same as Example 1 except that R / d was set to 57.5 × 10 ⁻² . As a result of operating for 60 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 25 ° C. Therefore, ΔT (T2−T1) was 35 ° C.

  At this time, the target particle size of the obtained surface-modified particles was the same as in Example 1. In this example, it is possible to obtain surface-modified particles having a sharp particle size distribution having a weight average diameter of 7.2 μm and containing 14% by number of particles having a particle diameter of 4.00 μm or less at a product recovery rate of 72%. did it. This achieves a higher product recovery rate compared to the comparative example described later, and as a result of setting the equipment configuration in the batch type surface reforming apparatus to an appropriate state, the classification in the classification zone around the classification rotor is achieved. This is probably because classification accuracy has improved. Tables 5 and 6 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 9]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At that time, in this example, the same procedure as in Example 1 was performed except that R / d was set to 82.1 × 10 ⁻² . Tables 5 and 6 show the production conditions and evaluation results of the surface modified particles (toner particles).

[Example 10]
The toner raw material particles obtained in Example 1 were subjected to surface modification using a batch type surface modification apparatus shown in FIG. At that time, in this comparative example, it was the same as Example 1 except that R / d was set to 88.5 × 10 ⁻² . The obtained surface modified particles and the treated surface modification apparatus were evaluated in the same manner as in Example 1. Tables 5 and 6 show the production conditions and evaluation results of the surface modified particles (toner particles).

Also in this example, the surface modification containing 17% by number of particles having a weight average diameter of 7.2 μm and a particle diameter of 4.00 μm or less was adjusted to obtain a target particle size distribution. Particles were obtained. However, the product recovery rate of the surface modified particles was as low as 61%, and satisfactory results were not obtained as compared with Example 1 described above. This is presumably because the value of the classification rotor outer diameter R / guide ring inner diameter d was 85.0 × 10 ⁻² or more, so that an effective classification effect could not be obtained in the classification zone around the classification rotor.

Schematic sectional view showing an example of the surface modification apparatus of the present invention used in the method for producing the toner of the present invention Schematic top view of the dispersion rotor 32 in FIG. Schematic sectional view showing an example of the surface modification apparatus of the present invention used in the method for producing the toner of the present invention Schematic sectional view of the surface modified particle discharge mechanism of the surface modification device of the present invention The schematic sectional drawing for demonstrating the guide plate installed in the surface modification particle | grain discharge port of the surface modification apparatus of this invention Schematic cross-sectional view of a mechanical pulverizer used in the toner pulverization process of the embodiment Schematic sectional view of a classification device used in the toner classification process of the embodiment Schematic cross-sectional view of the surface modified particle discharge mechanism of the surface modification device of the prior art

Explanation of symbols

30 Main body casing 31 Cooling jacket 32 Dispersion rotor 33 Disc or pin 34 Liner 35 Classification rotor 36 Guide ring 37 Raw material inlet 38 Raw material supply valve 39 Raw material supply port 40 Product discharge port 41 Product discharge valve 42 Product extraction port 43 Top plate 44 Fine powder Discharge casing 45 Fine powder discharge port 46 Cold air inlet 47 First space 48 Second space 49 Surface reforming zone 50 Classification zone 51 Packing member 52 Guide plate 53 Seal surface 54 Product discharge part 141, 142 Classification chamber side wall 143, 144 Classification chamber lower wall 145 Coanda block 146, 147 Classification edge 148, 149 Raw material supply pipe 150 Classification chamber upper wall 151 Inlet air edge 152, 153 Inlet pipe 154, 155 Gas introduction control means 156, 157 Static pressure gauge 158, 159, 160 Exhaust Port 212 Spiral chamber 219 Pipe 220 Distributor 222 Bag filter 224 Suction blower 229 Collection cyclone 301 Mechanical pulverizer 302 Powder discharge port 310 Stator 311 Powder input port 312 Rotating shaft 313 Casing 314 Rotor 315 First fixed amount Supply machine 316 Jacket 317 Cooling water supply port 318 Cooling water discharge port 319 Cold air generating means 320 Rear chamber

Claims (17)

A process comprising: producing toner raw material particles containing at least a binder resin and a colorant; and obtaining toner particles by subjecting the toner raw material particles to surface modification treatment using a toner particle surface modifying device. A manufacturing method comprising:
The toner particle surface modifying device includes a main body casing, a top plate installed in the main body casing so as to be openable and closable, a charging unit for charging toner raw material particles into the main casing, and a predetermined amount of toner raw particles charged in the main casing. Classifying means for continuously removing fine powder having a particle size or less to obtain processed toner particles, fine powder discharging section for discharging fine powder removed by the classification means to the outside of the main body casing, processed toner particles from which the fine powder has been removed A surface treatment means for performing a surface modification treatment using a mechanical impact force, a cylindrical guide means for partitioning a space between the classification means and the surface treatment means into a first space and a second space, and the Fine particles having a predetermined particle diameter or less are removed by the classifying means, and the toner particles to be treated, which have been subjected to the surface modification treatment by the surface treatment means, are discharged out of the casing as toner particles. The toner raw material particles introduced into the main body casing from the charging unit are introduced into the first space, and the fine particles having a predetermined particle diameter or less are removed by the classifying means to continuously out of the apparatus. It is discharged through the second space, introduced into the surface treatment means, subjected to surface modification treatment, and circulated to the first space again to repeat classification and surface modification treatment, whereby predetermined particles are obtained. To obtain toner particles from which fine powder of a diameter or less has been removed and subjected to surface modification treatment,
The input part is provided with an input port having an openable / closable raw material particle supply valve, and the discharge part for discharging the surface modified particles from which fine powder having a predetermined particle size or less is discharged has an openable / removable surface modification. A discharge port having a particulate discharge valve is provided, the discharge port has a cylindrical shape, the surface-modified particle discharge valve has a packing member on a surface that contacts the discharge port, and the center line of the discharge port at a position that is surface modified particles valve located in the surface modified particles discharge valve is closed, the outlet and the surface in a state in which the surface modified particles discharge valve is closed method for producing a toner, characterized in that said packing member modified particles discharge valve has is an angle θ is 85 to 95 ° between the contact surfaces.   The toner particle surface modifying device discharges the surface modified particle when the surface modified particle discharge valve is opened and closed to discharge the surface modified particles from which fine powder having a predetermined particle size or less has been removed to the outside of the main body casing. The method for producing toner according to claim 1, wherein compressed air is injected to the valve and the discharge port.   3. The toner manufacturing method according to claim 1, wherein the classification means is a means for performing classification by rotation of an impeller type classification rotor. 4. The toner manufacturing method according to claim 3, wherein an outer diameter R of the classification rotor and an inner diameter d of the guiding means satisfy a relationship of the following formula (3).
53.0 × 10 ⁻² ≦ R / d ≦ 85.0 × 10 ⁻² (3) 5. The toner manufacturing method according to claim 4, wherein an outer diameter R of the classification rotor and an inner diameter d of the guide means satisfy a relationship of the following formula (4).
59.0 × 10 ⁻² ≦ R / d ≦ 80.0 × 10 ⁻² (4)   The said discharge part further has a guide plate installed in the discharge port in order to send the surface modification processed product from which the fine powder of the predetermined particle size or less was removed out of the main body casing. The method for producing a toner according to any one of the above. The toner manufacturing method according to claim 6, wherein the width w of the guide plate and the distance W from the inner wall of the main body casing to the guide means satisfy the relationship of the following formula (5).
w / W ≦ 0.9 (5) 8. The toner manufacturing method according to claim 7, wherein the width w of the guide plate and the distance W from the inner wall of the main body casing to the guide means satisfy the relationship of the following formula (6).
0.3 ≦ w / W ≦ 0.9 (6)   The step of obtaining the toner raw material particles includes a step of obtaining a kneaded product by melt-kneading a composition containing at least a binder resin and a colorant, and cooling and solidifying the obtained kneaded product, and And a step of obtaining a finely pulverized product as toner raw material particles by finely pulverizing using a pulverizer or a mechanical pulverizer. Method. A batch-type surface modification device that classifies toner raw material particles and spheroidizes them,
Main body casing, top plate installed in the main body casing so as to be openable and closable, a charging part for charging raw material particles into the main body casing, and fine particles having a predetermined particle size or less are continuously removed from the raw material particles charged into the main body casing. Classifying means for obtaining treated particles, a fine powder discharging unit for discharging fine powder removed by the classifying means to the outside of the main body casing, and surface modifying treatment for the treated particles from which the fine powder has been removed using mechanical impact force Surface treatment means, cylindrical guide means that partitions the classification means and the surface treatment means into a first space and a second space, and fine powder having a predetermined particle size or less are removed by the classification means, And a discharge section for discharging the particles to be treated, which have been subjected to the surface modification treatment by the surface treatment means, to the outside of the main casing as the surface modification particles,
The raw material particles introduced into the main body casing from the introduction part are introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classification means, and the second space is discharged continuously from the apparatus. The surface is introduced through the surface treatment means and subjected to surface modification treatment, and is again circulated to the first space to repeat classification and surface modification treatment, thereby removing the fine powder having a predetermined particle size or less. To obtain modified particles,
The input part is provided with an input port having an openable / closable raw material particle supply valve, and the discharge part for discharging the surface modified particles from which fine powder having a predetermined particle size or less is discharged has an openable / removable surface modification. A discharge port having a particulate discharge valve is provided, the discharge port has a cylindrical shape, the surface-modified particle discharge valve has a packing member on a surface that contacts the discharge port, and the center line of the discharge port at a position that is surface modified particles valve located in the surface modified particles discharge valve is closed, the outlet and the surface in a state in which the surface modified particles discharge valve is closed The modified particle discharge valve has
Toner particle surface modifying apparatus, characterized in that the packing member is an angle θ is 85 to 95 ° between the contact surfaces.   The surface modifying device, when opening and closing the surface modified particle discharge valve in order to discharge the surface modified particles from which fine powder of the predetermined particle size or less has been removed out of the main body casing, 11. The toner particle surface modifying apparatus according to claim 10, wherein compressed air is jetted to the discharge port.   12. The toner particle surface modifying apparatus according to claim 10, wherein the classification means is a means for performing classification by rotation of an impeller type classification rotor. 13. The toner particle surface modifying apparatus according to claim 12, wherein an outer diameter R of the classification rotor and an inner diameter d of the guiding means satisfy a relationship of the following formula (3).
53.0 × 10 ⁻² ≦ R / d ≦ 85.0 × 10 ⁻² (3) 14. The toner particle surface modifying apparatus according to claim 13, wherein an outer diameter R of the classification rotor and an inner diameter d of the guiding means satisfy a relationship of the following formula (4).
59.0 × 10 ⁻² ≦ R / d ≦ 80.0 × 10 ⁻² (4)   15. The discharge unit according to claim 10, further comprising a guide plate installed at the discharge port for sending the surface-modified product from which fine powder having a predetermined particle size or less has been removed to the outside of the main body casing. The toner particle surface modifying apparatus according to any one of the preceding claims. 16. The toner particle surface modifying apparatus according to claim 15, wherein the width w of the guide plate and the distance W from the inner wall of the main body casing to the guide means satisfy the relationship of the following formula (5).
w / W ≦ 0.9 (5) The toner particle surface modifying apparatus according to claim 16, wherein the width w of the guide plate and the distance W from the inner wall of the main body casing to the guide means satisfy the relationship of the following formula (5). 3 ≦ w / W ≦ 0.9 (6)

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