JP2003103187A - Method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner by which toner of a long life having excellent developing property, excellent transfer character and stable electrostatic chargeability even under circumstances of high temperature and high humidity can be obtained by controlling a surface shape of the toner in a mechanical pulverizer. SOLUTION: The mechanical pulverizer is provided with a ring-shaped pulverizing rotor 2 which is supported by a rotary axis and has a pulverizing blade constituted of a plurality of projecting and recessing parts provided on an outside surface and a liner 3 which is fixedly arranged facing the pulverizing rotor with some space and has a plurality of projecting and recessing parts. Further the mechanical pulverizer incorporates a rotary blade type classifying rotor 4 which discharges pulverized raw material of below prescribed grain size to an exit side, is provided with a circulating passage of the raw material not discharged to the exit side below the pulverizing blade and is characterized by that length L of a pulverizing section of the pulverizing rotor and an outside diameter D of the pulverizing rotor satisfies the relation: 0.06<=L/D<=0.20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing a toner formed from a binder resin used for image formation by electrophotography and a method for producing a toner using the apparatus.

[0002]

2. Description of the Related Art In image forming methods such as electrophotography, electrostatic photography and electrostatic printing, a toner is used for developing an electrostatic image.

Generally, as a method for producing a toner for developing an electrostatic image, a binder resin for fixing it on a transfer material, various colorants for producing a tint as a toner, and charge control for imparting an electric charge to particles are used. Agent as raw material, or JP-A-54
In the so-called one-component developing method as disclosed in JP-A-42141 and JP-A-55-18656, in addition to these, various magnetic materials for imparting transportability and the like to the toner itself are used and further required. Depending on, for example, other additives such as a release agent and a fluidity-imparting agent are added and dry-mixed, followed by melt-kneading with a general-purpose kneading device such as a roll mill and an extruder, followed by cooling and solidification, Particle size required for toner is obtained by refining the kneaded product with various crushing devices such as jet airflow crusher and mechanical collision crusher, and introducing the obtained coarse crushed product into various wind classifiers for classification. The obtained classified product is further added, and if necessary, a fluidizing agent, a lubricant and the like are externally added and dry mixed to obtain a toner for image formation. Further, in the case of the toner used in the two-component developing method, various magnetic carriers are mixed with the above-mentioned toner and then used for image formation.

Various crushing devices are used as the crushing means. Among them, for crushing the toner coarsely crushed products mainly composed of a binder resin, a jet air flow type crusher using a jet air flow as shown in FIG. 2, particularly, A collision type airflow crusher is used.

A collision type air flow crusher using a high pressure gas such as a jet air stream conveys a powder raw material by a jet air stream and jets the powder raw material from an outlet of an accelerating pipe to face the opening surface of the outlet of the accelerating pipe. The colliding member is collided with the colliding surface of the colliding member, and the powder material is crushed by the impact force.

For example, in the collision type air flow pulverizer shown in FIG. 2, a collision member 17 is provided so as to face the outlet 19 of the acceleration tube 20 to which the high pressure gas supply nozzle 21 is connected, and the high pressure gas supplied to the acceleration tube 20 causes The powder material is sucked into the accelerating tube 20 through the powder material supply port 14 communicating with the middle of the accelerating tube 20, and the powder material is ejected together with the high-pressure gas to collide with the collision member 17.
It collides with the collision surface 15 and is crushed by the impact, and the crushed material is discharged from the crushed material discharge port 16.

However, since the above-mentioned collision type air flow pulverizer is constructed so that the powder raw material is ejected together with the high-pressure gas to collide with the collision surface of the collision member and is crushed by the impact, a toner having a small particle size is produced. To do so requires a large amount of air. Therefore, it consumes an extremely large amount of electricity and has a problem in terms of energy cost. Further, when the toner is pulverized by a collision type air flow pulverizer, the amount of fine powder generated increases, which leads to a reduction in the classification yield in the subsequent classification process, which is not preferable in terms of toner productivity.

Particularly in recent years, in order to cope with environmental problems, energy saving of the apparatus has been required, and instead of the conventional collision type airflow crusher, a mechanical collision type crusher which does not require a large amount of air and consumes less electric power. Is being noticed.

The mechanical crusher is different from a collision type air flow crusher in which a powder raw material is collided with a high pressure gas on a collision surface of a collision member and crushed, and a stator called a liner and a stator are included in the stator. The powder raw material is crushed by a shock wave generated at a distance from a rotor called a rotor that can rotate at high speed.

Since such a mechanical crusher consumes less electric power than the conventional collision type airflow crusher, it is possible to cope with the energy saving of the device which has been sought in recent years. Further, the toner pulverized by the mechanical pulverizer has a smaller amount of fine powder than the toner pulverized by the collision type air flow pulverizer, and a toner having a sharp particle size distribution can be obtained.

However, in recent years, as the image quality and definition of copying machines and printers have become higher, the performance required for toner as a toner has become more severe, and the particle size of the toner has become smaller, resulting in a particle size distribution of the toner. Is increasingly demanded to have sharp particles which do not contain coarse particles and have a small amount of ultrafine powder. Further, regarding the toner surface shape, further control of the toner surface shape is required along with the demand for environmental stability at a high level.

[0012]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, to efficiently pulverize a powder raw material, to obtain a sharp particle size distribution, and to control the surface shape of a toner arbitrarily. An object of the present invention is to provide a mechanical crusher suitable for use in the production of toner.

A further object of the present invention is to provide a method for producing a toner which can solve the above problems.

The object of the present invention is to control the surface shape of the toner in a mechanical grinder so that even in a high temperature and high humidity environment, it has good developability, transferability, and stable chargeability from the beginning, and has a long life. Another object of the present invention is to provide a method for producing a toner capable of obtaining a different toner.

Further, an object of the present invention is to obtain a toner having a high image density even in a high temperature and high humidity environment, from the initial stage and after standing by controlling the surface shape of the toner in a mechanical grinder. It is to provide a method for manufacturing a toner.

A further object of the present invention is to provide a method for producing a toner which can obtain a toner having excellent durability on a large number of sheets.

[0017]

According to the present invention, a mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled, the cooled product is roughly pulverized, and the coarsely pulverized product is pulverized. In the method for producing a toner, wherein the finely pulverized product is finely pulverized by a means, and a toner having a weight average particle diameter of 4 to 12 μm is produced from the finely pulverized product, the pulverizing means is a mechanical pulverizer, The mechanical crusher has a ring-shaped crushing rotor having a crushing blade which is supported by at least a rotating shaft and has a plurality of irregularities provided on the outer surface substantially all around, and a space between the crushing rotor. And a liner having a plurality of irregularities on the surface facing the crushing rotor and fixed, and having a predetermined particle size or less of the raw material crushed between the crushing rotor and the liner and brought upward Discharge things to the exit side A mechanical crusher having a rotary-blade type classification rotor built therein, and a circulation passage provided below the crushing blade for introducing a raw material that is not discharged to the outlet side to the lower side of the interval, which is a mechanical crusher. Length L (m
m) and the outer diameter D (mm) of the crushing rotor satisfy the following conditions. 0.06 ≦ L / D ≦ 0.20

As a result of earnest studies to solve the above-mentioned problems of the prior art, the present inventor found out whether or not there is a classification mechanism in the mechanical crusher, the length of the crushing rotor crushing section, and the crushing by the mechanical crusher. The present invention having the above structure was derived by finding that there is a relationship between the particle size distribution and surface shape of the toner.

That is, the mechanical crusher used in the crushing process is crushed in the crushing zone between the crushing rotor and the liner, and the material having a predetermined particle size or less introduced above is discharged from the discharge port. And a built-in rotary-blade-type classification rotor for returning the raw material that is not discharged to the discharge port side to the crushing zone,
And, a mechanical crusher characterized in that a circulation passage for introducing a raw material not discharged to the outlet side to the lower side of the interval is provided below the crushing blade, and the mechanical crusher is put in an appropriate state. Controlled operation prevents excessive pulverization of the toner, and toner with a sharp particle size distribution with less generation of fine powder can be obtained. Moreover, the surface shape of the toner can be controlled arbitrarily, and it can be used under high temperature and high humidity environment. However, it is possible to obtain a long-life toner having good developability, transferability, and stable chargeability from the initial stage, and further, to obtain a toner having a high image density from the initial stage and even after standing. Found that a toner having excellent durability on a large number of sheets can be obtained, and arrived at the present invention.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to preferred embodiments.

First, a raw material for toner particles containing at least a binder resin and a colorant used in the present invention will be described.

[Resin] As the binder resin used in the present invention, various resin compounds conventionally known as binder resins can be used. For example, a vinyl resin,
Phenol resin, natural resin modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene Examples thereof include resins, coumaroindene resins, petroleum-based resins and the like. Of these, vinyl-based resins and polyester-based resins are preferable in terms of charging property and fixing property.

Examples of vinyl resins include styrene;
o-methylstyrene, m-methylstyrene, p-methylenestyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene,
such as pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene. Styrene derivative;
Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate , Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate , Acrylic acid esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone ,
Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes:
Acrylic or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; α, β
-Esters of unsaturated acids, diesters of dibasic acids; acrylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinylacetic acid, isocrotonic acid, angelic acid and the like α- or β -Alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, alkenylsuccinic acid, itaconic acid, mesaconic acid, dimethylmaleic acid and dimethylfumaric acid, and vinyl-based monomers such as monoester derivatives or anhydrides thereof. The polymer used may be mentioned.

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

Further, the binder resin used in the present invention may be a polymer or a copolymer which is cross-linked with a cross-linking monomer as exemplified below, if necessary.

As the crosslinkable monomer, a monomer having two or more unsaturated bonds capable of crosslinking can be used. As such a crosslinkable monomer, various monomers as shown below have been conventionally known and can be suitably used for the toner of the present invention.

Examples of the crosslinkable monomer include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 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 the acrylates of the above compounds with methacrylates; ether bonds Examples of the diacrylate compounds linked by an alkyl chain containing: include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol. Diacrylates and the above compounds in which acrylates are replaced by methacrylates; diacrylates linked by chains containing aromatic groups and ether bonds Examples of the compound include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) provandiacrylate and The acrylates of the above compounds may be replaced by methacrylates; polyester-type diacrylates, for example, trade name MANDA
(Nippon Kayaku) and the like.

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compounds with methacrylate; Triallyl cyanurate, triallyl trimellitate and the like can be mentioned.

The following polyester resins are also preferable as the binder resin used in the present invention. 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.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, the following (B)
A bisphenol derivative represented by the formula:

[0031]

[Chemical 1] (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.) (C) A diol represented by the formula;

[0032]

[Chemical 2]

Further, polyhydric alcohols such as glycerin, sorbit, sorbitan and the like can be mentioned.

The acid component is preferably a carboxylic acid, and the divalent carboxylic acid is a benzendicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid or phthalic anhydride or an anhydride thereof; Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or their anhydrides, and the like, and 3 Examples of the carboxylic acid having a valence of 3 or more include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

The alcohol component of the particularly preferred polyester resin is a bisphenol derivative represented by the above formula (B), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-
Dicarboxylic acids such as dodecenyl succinic acid or its anhydride, fumaric acid, maleic acid, and maleic anhydride; and tricarboxylic acid of trimellitic acid or its anhydride. This is because the heat roller fixing toner using the polyester resin obtained from the acid component and the alcohol component 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 magnetic material contained in the magnetic toner is not particularly limited as long as it is a commonly used magnetic material, and examples thereof include magnetite, maghemite, and ferrite. Such as iron oxides, and iron oxides containing other metal oxides; F
Metals such as e, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, S
b, Be, Bi, Cd, Ca, Mn, Se, Ti, W,
Examples thereof include alloys with metals such as V, and mixtures thereof.

Specifically, as the magnetic material, iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), iron oxide Cadmium (C
dFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe
₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), iron oxide lead (Pb)
Fe ₁₂ O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron niobium oxide (NdFe ₂ O ₃ ), iron oxide barium (BaF)
e ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni), and the like. The above magnetic materials are used alone or in combination of two or more. Particularly suitable magnetic materials are iron trioxide or γ-
It is a fine powder of iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic characteristics under application of 795.8 kA / m are coercive force of 1.6 to 12.0 kA / m and saturation magnetization of 50 to 200 A.
Those having m ² / kg (preferably 50 to 100 Am ² / kg) and remanent magnetization of ^{2 to 20} Am ² / kg are particularly preferable for use in the electrophotographic image forming method.

Further, these magnetic materials are based on the binder resin 100.
It is preferable to contain 60 to 200 parts by mass, more preferably 80 to 150 parts by mass with respect to parts by mass.

[Colorant] As described above, in the toner of the present invention, a magnetic substance may be used as a colorant, 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 pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, red bean, phthalocyanine blue, and indanthrene blue. These are added in an amount of 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, relative to 100 parts by mass of the binder resin. Further, a dye is used in the same manner, and the binder resin 10
0.1 to 20 parts by weight, preferably 0.3
The addition amount of 10 to 10 parts by mass is good.

As the colorant used in the present invention, carbon black, a magnetic substance, or a yellow / magenta / cyan colorant shown below is used as a black colorant, which is toned in black.

As the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound and an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

As the magenta colorant, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacdrine compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound and a perylene compound are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5,202,206,220,221,254 are particularly preferred.

As the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound 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, 66 can be used particularly preferably.

[Wax] As the wax used in the present invention, various wax components conventionally known as a releasing agent can be used, and there are the following ones. Examples of the hydrocarbon wax include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, and aliphatic hydrocarbon wax such as Fischer-Tropsch wax.

Examples of the wax having a functional group include oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; plants such as candelilla wax, carnauba wax, wood wax and jojoba wax. -Based waxes; animal-based waxes such as beeswax, lanolin and whale wax; mineral-based waxes such as ozokerite, ceresin and petrolactam; waxes containing aliphatic esters such as montanic acid ester wax and castor wax as the main component: deoxidized carnauba Examples thereof include those obtained by partially or completely deoxidizing an aliphatic ester such as wax.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid. ; Stearyl alcohol, eicosyl alcohol,
Saturated alcohols such as behenyl alcohol, kaunavir alcohol, ceryl alcohol, melysyl alcohol, or alkyl alcohols having longer chain alkyl groups; polyhydric alcohols such as sorbitol; fats such as linoleic acid amide, oleic acid amide, and lauric acid amide. Group amides; saturated aliphatic bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N Unsaturated fatty acid amides such as'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; aroma such as m-xylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide Bisamides; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metallic soap); partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; vegetable Examples thereof include a methyl ester compound having a hydroxyl group obtained by hydrogenating fats and oils.

As the wax grafted with a vinyl monomer, there is a wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid.

The wax preferably used is a polyolefin obtained by radically polymerizing an olefin under high pressure;
Polyolefins obtained by purifying low molecular weight by-products obtained during the polymerization of high molecular weight polyolefins; polyolefins polymerized under low pressure by using catalysts such as Ziegler catalysts and metallocene catalysts; polyolefins polymerized by utilizing radiation, electromagnetic waves or light; paraffin wax , Microcrystalline wax, Fischer-Tropsch wax; Synthetic hydrocarbon wax synthesized by the Zintol method, Hydrochol method, Arge method, etc .; Synthetic wax having a compound having one carbon atom as a monomer; Hydroxyl group, carboxyl group or ester group Hydrocarbon wax having functional group; Mixture of hydrocarbon wax and hydrocarbon wax having functional group; styrene, maleic acid ester, acrylate, methacrylate, maleic anhydride using these waxes as a base material Waxes obtained by graft-modified with such vinyl monomers.

These waxes are those having a sharp molecular weight distribution obtained by a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal precipitation method, or a low molecular weight solid fatty acid. Low molecular weight solid alcohol,
A low molecular weight solid compound and a compound from which other impurities are removed are also preferably used.

[Charge Control Agent] In the toner of the present invention, a charge control agent can be used, if necessary, in order to further stabilize the chargeability thereof. The charge control agent is the binder resin 10
0.1-10 parts by weight per 0 parts by weight, preferably 1-5
It is preferable to use parts by mass in order to control the charging property 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 which makes the toner negatively chargeable, for example, an organometallic complex or a chelate compound is effective. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, their anhydrides,
Alternatively, esters thereof, phenol derivatives of bisphenol and the like can be mentioned. Preferred is a monoazo metal compound, which has an alkyl group as a substituent,
C of a monoazo dye synthesized from phenol and naphthol having halogen, nitro group, carbamoyl group, etc.
Examples thereof include metal complex compounds of r, Co and Fe. A metal compound of an aromatic carboxylic acid is also preferably used, which has an alkyl group, a halogen, a nitro group or the like, a carboxylic acid of benzene, naphthalene, anthracene or phenanthrene,
Examples thereof include metal compounds of hydroxycarboxylic acid and dicarboxylic acid.

Examples of the positive charge control agent that makes the toner positively charge include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts. For example, modified products of nigrosine and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate,
And onium salts such as phosphonium salts and the like, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxide such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate. Such as diorgano tin borate; these can be used alone or in combination of two or more kinds.

[External Additive] As described above, the toner of the present invention generally contains, in addition to the toner particles, an external additive for adjusting the fluidity and chargeability of the toner. As such an external additive, a fluidity improver may be added to the toner of the present invention. The fluidity improver can be added externally to the toner particles to increase the fluidity before and after the addition. For example, fluorine-based resin powder such as fine powder of vinylidene fluoride; fine powder silica such as wet process silica, dry process silica, fine powder titanium oxide, fine powder alumina, silane compound, titanium coupling agent, silicone oil on the surface There are treated fine powders which have been treated.

As a method of hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs to the fine powder.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethydimethylchlorosilane,
α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and Si having 2 to 12 siloxane units per molecule, one for each terminally located unit There is dimethylpolysiloxane containing a hydroxyl group bonded to the like. Further, a silicone oil such as dimethyl silicone oil may be mentioned. These are used in one kind or a mixture of two or more kinds.

As the particles of 0.1 to 5.0 μm used in the present invention, inorganic fine particles, organic fine particles, and mixtures and composites thereof can be used. Specifically, strontium titanate, cerium oxide, aluminum oxide,
Examples thereof include metal oxides such as magnesium oxide, fluororesin powder, resin fine particles and the like. Strontium titanate and cerium oxide are particularly preferable in terms of charging characteristics.

[Charge Control Agent II] The toner of the present invention preferably contains a charge control agent.

The following compounds can be used to control the toner to be negatively charged.

Organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol.

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

[0063]

[Chemical 3] [In the formula, M represents a coordination center metal, and Sc, Ti, V, C
Examples thereof include r, Co, Ni, Mn, and Fe. Ar
Is an aryl group, an aryl group such as a phenyl group and a naphthyl group, and may have a substituent. Examples of the substituent in this case 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. ]

Particularly, Fe or Cr is preferable as the central metal, halogen, an alkyl group or an anilide group is preferable as the substituent, and hydrogen is the counter ion.
Alkali metals, ammonium or aliphatic ammonium are preferred. A mixture of complex salts having different counter ions is also preferably used.

The basic organometallic complex represented by the following formula (2) is also preferable as the charge control agent which imparts negative chargeability.

[0066]

[Chemical 4]

The following compounds are available for controlling the toner to have a positive charge property.

Nigrosine modified with nigrosine and fatty acid metal salts; tributylbenzylammonium-1-
Hydroxy-4-naphthosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (As lakers, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin Diorgano tin oxides such as oxides and dicyclohexyl tin oxides; Diorgano tin borates such as dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate; Guanidine compounds; Imidazole Compounds, and the like. These may be used alone or in combination of two or more.

Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. Formula (3) below

[0070]

[Chemical 5] [In the formula, 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 homopolymer of a monomer represented by the following; a copolymer with a polymerizable monomer such as styrene, acrylic acid ester, and 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 (all or part of) a binder resin.

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

[0072]

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

As a method of incorporating the charge control agent into the toner, there are a method of adding the charge control agent inside the toner particles and a method of adding it externally. The amount of these charge control agents used is determined according to the type of binder resin, the presence or absence of other additives, and the toner manufacturing method including the dispersion method, and is not uniquely limited. It is preferably used in an amount 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.

Next, the procedure for producing a toner by the method for producing a toner of the present invention using the above-mentioned materials for forming toner particles and external additives will be described.

First, in the raw material mixing step, as a toner internal additive, at least a predetermined amount of resin and colorant are weighed and mixed, and mixed. As an example of a mixing device,
There are mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers and the like.

Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch-type 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 because of their advantages such as continuous production. For example, KTK twin-screw extruder manufactured by Kobe Steel, Ltd., TEM twin-screw extruder manufactured by Toshiba Machine Co., Ltd. Generally, a twin-screw extruder manufactured by CAC Corporation, a co-kneader manufactured by Bus Co., and the like are used. Further, the colored resin composition obtained by melt-kneading the toner raw material is melt-kneaded, rolled by a two-roll mill or the like, and cooled through a cooling step of cooling with water or the like.

The cooled product of the colored resin composition obtained above is then crushed to a desired particle size in a crushing step.
In the pulverizing step, first, coarse pulverization is performed by a crusher, hammer mill, feather mill, etc., and then fine pulverization is performed by a mechanical pulverizer. In the pulverizing step, the toner particles are pulverized stepwise as described above. Further, after pulverization, the toner is classified by using a classifier such as an inertial classification type elbow jet, a centrifugal force classification type Microplex, a DS separator, etc. to obtain a toner having an average particle size of 4 to 12 μm.

Incidentally, the toner coarse powder generated by the classification in the classification step is returned to the pulverization step and pulverized. Further, the fine powder generated in the classification step may be returned to the blending step of the toner raw material and reused.

Further, in the method for producing a toner of the present invention, inorganic fine particles having an average particle size of 50 nm or less are externally added to the toner obtained as described above as an external additive. As a method of externally adding an external additive to the toner, the classified toner and various known external additives are mixed in a predetermined amount, and a high-speed stirrer such as a Henschel mixer or a super mixer that gives a shearing force to the powder is removed. It is preferable to use as an adder and stir and mix. At this time, heat is generated inside the external additive machine, and aggregates are easily generated. Therefore, it is preferable to adjust the temperature by means such as cooling the periphery of the container part of the external additive machine with water.

Next, the mechanical crusher used in the toner crushing step of the present invention and the toner manufacturing method using the mechanical crusher will be specifically described with reference to the drawings.

FIG. 1 shows a schematic sectional view of a mechanical crusher used in the present invention.

In the mechanical crusher shown in FIG. 1, a casing 1, a jacket (not shown) through which cooling water or an antifreeze liquid can pass, and a rotating body attached to the central rotating shaft in the casing 1 rotate at high speed. The crushing rotor 2 having a large number of grooves on the surface, the liner 3 having a large number of grooves on the surface of the crushing rotor 2 arranged at a constant distance on the outer periphery, and the crushed raw material A classification rotor 4 for classifying to a predetermined particle size, a cold air inlet 5 for introducing cold air, a raw material supply inlet 6 for introducing a raw material to be treated, and a powder discharge outlet for discharging powder after treatment. 7 and 7. Grinding rotor 2 and liner 3
The space between and is the crushing zone, and the classification rotor 4 and the peripheral area of the rotor are the classification zones.

In the mechanical crusher configured as described above, the raw material introduced into the pulverizing chamber from the raw material supply port 6 is introduced into the circulating flow 8 generated by the pulverizing rotor 2 to the pulverizing section and the pulverizing rotor. Impact between the liner 2 and the liner 3,
Be crushed. The crushed raw material is guided to the classification zone by the cool air passing through the inside of the machine, and the classification rotor 4 discharges the fine powder to the outside of the machine as a crushed product. The coarse powder returns to the crushing rotor 2 again by being circulated, and is repeatedly crushed.

The installation direction of the classification rotor 4 may be vertical as shown in FIG. 1 or horizontal. Further, the number of classification rotors 4 may be a single unit as shown in FIG. 1 or a plurality thereof.

An example of the mechanical crusher of this type is an inomizer manufactured by Hosokawa Micron.

The feature of the toner manufacturing method of the present invention is that FIG.
Crush the toner using the mechanical crusher shown in, and
The relationship between the length L (mm) of the crushing rotor crushing portion and the outer diameter D (mm) of the crushing rotor is 0.06 ≦ L / D ≦
It is to be 0.20.

That is, as a result of the study by the present inventor, the mechanical crusher used in the crushing step is a mechanical crusher having a classification rotor for classifying the crushed raw material into a predetermined particle size as shown in FIG. Machine is preferred. When the toner is further crushed, the length L of the crushing rotor crushing portion of the mechanical crusher is L
(Mm) and the outer diameter D (mm) of the crushing rotor are preferably 0.06 ≦ L / D ≦ 0.20, and further 0.08 ≦ L / D ≦ 0.18. It is preferable that

That is, as a result of examination by the present inventor, the mechanical crusher is of a type having a built-in classifying rotor for classifying the crushed raw material into a predetermined particle size as shown in FIG. , The length L (mm) of the crushing rotor crushing part of the mechanical crusher and the outer diameter D (mm) of the crushing rotor
By setting the relationship of 0.06 ≦ L / D ≦ 0.20 (more preferably 0.08 ≦ L / D ≦ 0.18),
Prevents excessive pulverization of the toner, sharpens the particle size distribution of the toner, reduces the amount of coarse powder generated, and can control the surface shape of the toner arbitrarily, and has good developability from the beginning even in a high temperature and high humidity environment. A long-life toner having transferability and stable chargeability can be obtained. Further, a toner having a high image density can be obtained from the initial stage and after standing, and further, it is excellent in durability of many sheets. Toner can be obtained.

For the above reason, the particle size distribution of the toner is
It depends on the grinding efficiency of the toner in the mechanical grinder.
That is, in order to sharpen the particle size distribution of the toner, it is important to prevent the increase of fine powder due to over-pulverization and not to generate coarse powder. Originally, the mechanical crusher is less likely to be over-crushed when crushing the toner as compared with the collision type airflow crusher, so that the amount of fine powder generated is small. However, as a result of the study by the present inventor, as the length of the crushing portion of the crushing rotor becomes longer, that is, the length L (m of the crushing rotor crushing portion is increased.
It was found that the larger the value of m) / outer diameter D (mm) of the crushing rotor, the greater the amount of fine powder generated, even for the toner crushed by the mechanical crusher. Further, by reducing the amount of coarse powder generated, the particle size distribution of the toner can be made sharper. Further, it is considered that the surface shape of the toner depends on the residence time of the toner in the mechanical grinder. That is, in order to control the surface shape of the toner, it is important to control the residence time of the toner in the mechanical grinder. In the present invention, the mechanical crusher used in the crushing step is of a type having a built-in classifying rotor for classifying the crushed raw material into a predetermined particle size as shown in FIG. By adjusting the rotation speed of the classifying rotor in a timely manner,
The residence time of the toner in the mechanical pulverizer can be controlled, and the surface shape of the toner can be arbitrarily controlled. In addition, a classification rotor for classifying the crushed raw material into a predetermined particle size is incorporated, and the length L of the crushing rotor crushing section is L.
(Mm) and the outer diameter D (mm) of the crushing rotor are controlled in an appropriate state to prevent excessive crushing in the mechanical crusher and re-crush coarse powder. The distribution can be sharpened.

The circularity (average circularity) of the toner can be arbitrarily set within the range of 0.940 to 1.000. This is because the surface shape of the toner can be arbitrarily controlled by the mechanical pulverizer as described above.

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, it is measured by using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics. The circularity of the measured particles is determined by the following formula, and the value obtained by dividing the total sum of the measured circularity of all particles by the total number of particles is defined as the average circularity.

[0092]

[Equation 1]

As a measuring method, about 5 m of the toner is dissolved in 10 ml of water in which about 0.1 mg of the nonionic surfactant is dissolved.
g to disperse to prepare a dispersion liquid, and ultrasonic waves (20 kHz, 5
(0 W) is irradiated to the dispersion for 5 minutes to adjust the dispersion concentration to 5000
The circularity of the toner is measured by the above apparatus at 20,000 particles / μl.

The "average circularity" in the present invention is an index of the degree of unevenness of the toner particles, and shows 1.000 when the toner is a perfect sphere, and the average circularity becomes smaller as the toner shape becomes more complicated. Becomes

Further, in the toner manufacturing method of the present invention, it is preferable that the temperature T1 of the cold air introduced into the mechanical pulverizer is 5 ° C. or lower. The temperature T1 of the cold air introduced into the mechanical pulverizer is 5 ° C. or lower (more preferably 0 ° C. or lower,
More preferably, it is -5 ° C or less), so that the particle size distribution of the toner can be sharpened, and the surface shape of the toner can be arbitrarily controlled. If the temperature T1 of the cold air introduced into the mechanical pulverizer is 6 ° C. or higher, the surface of the toner is likely to be deteriorated by heat generated during pulverization and fusion in the machine is likely to occur, which is not preferable from the viewpoint of toner productivity.

Further, as the refrigerant used in the cool air generator introduced into the mechanical crusher, alternative CFCs are preferable from the viewpoint of environmental problems of the whole earth.

Alternative CFCs are R134a and R40.
4A, R407c, R410A, R507A, R717
Among them, R404A is particularly preferable from the viewpoint of energy saving and safety.

Further, in the method for producing a toner of the present invention, as a cooling means for cooling the inside of the mechanical pulverizer,
It is preferable to use a jacket structure and pass cooling water (preferably an antifreeze liquid such as ethylene glycol). With the jacket structure, it is possible to prevent fusion in the machine when the toner is pulverized.

Further, in the toner manufacturing method of the present invention, it is preferable that the room temperature T2 of the rear chamber of the classifying rotor in the mechanical pulverizer is 45 ° C. or lower. By setting the room temperature T2 of the rear chamber of the classification rotor in the mechanical pulverizer to 45 ° C. or lower (more preferably 40 ° C. or lower, further preferably 35 ° C. or lower), the particle size distribution of the toner can be sharpened, and
The surface shape of the toner can be controlled arbitrarily. If the room temperature T2 of the rear chamber of the classifying rotor in the mechanical pulverizer is 46 ° C. or higher, the surface of the toner is likely to be deteriorated by heat generated during pulverization and fusion in the machine is likely to occur, which is not preferable from the viewpoint of toner productivity.

Further, in the method for producing a toner of the present invention, the room temperature T2 in the rear chamber of the classifying rotor in the mechanical pulverizer is used.
And the temperature difference ΔT (T2-T1) between the cold air temperature T1 introduced into the mechanical crusher and the temperature T1 is preferably 60 ° C. or less. Room temperature T2 in the rear chamber of the classification rotor in the mechanical crusher
And the temperature difference ΔT (T2-T1) between the cold air temperature T1 introduced into the mechanical pulverizer and 60 ° C. or less (more preferably 50
C. or less, more preferably 40.degree. C. or less), the particle size distribution of the toner can be sharpened, and the surface shape of the toner can be arbitrarily controlled. Temperature difference ΔT (T2-T1) between the room temperature T2 of the rear chamber of the classifying rotor in the mechanical crusher and the temperature T1 of the cold air introduced into the mechanical crusher.
Of 61 ° C. or more is not preferable from the viewpoint of toner productivity, because surface modification of the toner due to heat generated during pulverization and in-machine fusion are likely to occur.

Further, in the method for producing a toner of the present invention, the minimum distance between the crushing rotor and the liner in the mechanical crusher is preferably 0.5 mm to 2.0 mm, and further, The thickness is preferably 1.0 mm to 1.8 mm. The minimum distance between the grinding rotor and the liner in the mechanical grinder is 0.5 mm to 2.0 m.
By setting m (preferably 1.0 mm to 1.8 m), the particle size distribution of the toner can be sharpened and the surface shape of the toner can be arbitrarily controlled. When the minimum distance between the crushing rotor and the liner is less than 0.5 mm, the load on the apparatus itself increases, and at the same time, the toner is over-crushed during crushing, and the surface of the toner is likely to be deteriorated or fused inside the machine. It is not preferable from the viewpoint of toner productivity. On the other hand, if the minimum distance between the crushing rotor and the liner is 2.1 mm or more, the processing capacity must be reduced in order to obtain a predetermined particle size, which is also not preferable in terms of toner productivity.

Further, in the method for producing a toner of the present invention, the peripheral speed of rotation of the crushing rotor is 120 to 175 m /
It is preferably sec. When the peripheral speed of rotation of the crushing rotor is 120 m / sec or less, the processing capacity must be reduced in order to obtain a predetermined particle size, which is not preferable in terms of toner productivity. Further, since the circulation amount of the toner becomes too large, it is unpreferable from the viewpoint of toner productivity because it is excessively pulverized at the time of pulverization and the surface of the toner is likely to be deteriorated by heat and fused in the machine. On the contrary, the rotation speed of the crushing rotor is 17
If it is 5 m / sec or more, the load on the apparatus itself becomes large, and at the same time, the toner is over-pulverized during pulverization and the surface of the toner is likely to be deteriorated by heat and fused inside the machine.

Further, in the toner manufacturing method of the present invention, the relationship between the outer diameter D of the crushing rotor and the number of crushing blades n provided on the outer surface of the crushing rotor is n / D ≧
0.8 is preferable, and 0.8 ≦ n / D is further preferable.
It is preferable that ≦ 1.3. If n / D is less than 0.8, the processing capacity must be reduced to obtain a predetermined particle size, which is not preferable in terms of toner productivity. Further, since the circulation amount of the toner becomes too large, the toner is excessively pulverized at the time of pulverization and the surface of the toner is likely to be deteriorated by heat and fused inside the machine, which is not preferable from the viewpoint of toner productivity. On the other hand, when n / D is 1.4 or more, the toner is excessively pulverized at the time of pulverization and the surface of the toner is likely to be deteriorated by heat and fused inside the machine, which is not preferable from the viewpoint of toner productivity.

Further, in the method for producing a toner of the present invention, the relation between the inner diameter D'of the liner and the number of crushing blades n'provided on the inner surface of the liner is n '/ D'≥
0.8 is preferable, and 0.8 ≦ n ′ /
It is preferable that D ′ ≦ 1.3. n '/ D' is 0.
If it is less than 8, the processing ability must be reduced in order to obtain a predetermined particle size, which is not preferable in terms of toner productivity. Further, since the circulation amount of the toner becomes too large, it is unpreferable from the viewpoint of toner productivity because it is excessively pulverized at the time of pulverization and the surface of the toner is likely to be deteriorated by heat and fused in the machine. On the other hand, when n '/ D' is 1.4 or more, it is excessively pulverized at the time of pulverization and the surface of the toner is likely to be deteriorated by heat and fused in the machine, which is also not preferable from the viewpoint of toner productivity.

In the present invention, it is preferable in terms of toner productivity that the crushing surface of the crushing rotor and the liner in the mechanical crusher is subjected to abrasion resistance. Incidentally, the antiwear treatment method is not limited at all. Further, the blade shapes of the crushing rotor and the liner in the mechanical crusher are not limited at all.

[0106]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Reference Examples of the present invention.

Example 1 Binder resin 100 parts by mass (styrene-butyl acrylate-butyl maleate half ester copolymer) (Tg 62 ° C., molecular weight: Mp13000, Mn6400, Mw240000) ・ Magnetic iron oxide 90 parts by mass (average particle diameter 0.22 [mu] m, 795.8 kA / m characteristic Hc5.1kA / m in a magnetic ^{field, σs85.1Am 2 /kg,σr5.1Am 2 / kg)} · monoazo metal complex (negative charge control agent) 2 parts by weight -Low molecular weight ethylene-propylene copolymer 3 parts by mass The materials having the above-mentioned formulation were well mixed by a Henschel mixer, and then kneaded by a biaxial kneader set to a temperature of 130 ° C. Cool the obtained kneaded product and use a hammer mill for 1 mm
Coarse pulverization was performed below to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.

The obtained powder raw material was finely pulverized by a mechanical pulverizer shown in FIG. 1 (a modified machine obtained by modifying Hosokawa Micron's INOMIZER INM30 type as follows). At that time, in this embodiment, the length L of the crushing portion of the crushing rotor 2 is L.
(Mm) / outer diameter D (mm) of the crushing rotor 2 is 0.13
And the cold air temperature T1 was set to 5 ° C. The distance between the crushing rotor 2 and the liner 3 is 1.0 mm, the peripheral speed of the crushing rotor 2 is 150 m / s, the number of crushing rotor blades n / the crushing rotor outer diameter D is 1.0, the number of liner blades n ′ / the inner diameter of the liner. D'was set to 0.8, the raw material supply amount was set to 40 kg / Hr, and the powder was crushed.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 34 ° C. Therefore, ΔT (T2-T1) was 29 ° C.

At this time, the target particle size of the finely pulverized product obtained was set to have a weight average diameter of 6.5 ± 0.5 μm. In this embodiment, by setting the peripheral speed of the classification rotor 4 to 60 m / s,
The finely pulverized product obtained by the mechanical pulverizer had a weight average diameter of 6.7 μm and a particle diameter of 4.00 μm as shown in Table 1.
The following particles had a sharp particle size distribution containing 40% by number.

For the average particle size and particle size distribution of the toner, a Coulter counter TA-II type or a Coulter Multisizer (manufactured by Coulter Co.) is used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting number distribution and volume distribution and P
C9801 personal computer (manufactured by NEC) is connected, and electrolyte is 1% NaC using primary sodium chloride.
l Prepare an aqueous solution. As the electrolytic solution, for example, ISO
TON R-II (made by Coulter Scientific Japan) can be used. As a measuring method, a surfactant (preferably alkylbenzene sulfonate) as a dispersant was added to 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1.
Add 1 to 5 ml, and further add 2 to 20 mg of the measurement sample.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles of 2 μm or more are measured using the Coulter Counter TA-II type with an aperture of 100 μm as an aperture. Then, the volume distribution and the number distribution were calculated. Then, the volume-based weight average particle diameter (D4:
(The median value of each channel is the representative value of the channel.)
Then, the cumulative number of toner particles of 4.00 μm or less obtained from the number distribution was obtained. Here, the fine powder is defined as 4.00 μm or less. That is, a smaller value of 4.00 μm or less indicates a sharper particle size distribution, and a larger value indicates a broader particle size distribution.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.954. Further, the surface shape of the toner was observed with a field emission scanning electron microscope (FE-SEM: Hitachi S-800) at a magnification of 10,000 times.
It was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ◎: Circular silhouette ○: Slightly elliptical silhouette △: Curved but irregular ×: Square silhouette

Next, to 100 parts by mass of the classified toner, 1.0 part by mass of dry silica having a primary particle size of 12 nm which has been hydrophobized with hexamethyldisilazane and silicone oil is added, and externally added with a Henschel mixer. The toner for evaluation was mixed.

Using this toner, LBP made by Canon
-930 modified machine (1.5 equivalent to 235 mm / sec)
Image quality was evaluated by the following items.

(Evaluation-1) The evaluation toner is put in a developing device and left overnight (12 hours or more) in a room temperature and normal humidity chamber (23 ° C., 60%). After outputting 1000 sheets, the image density is measured. Take out the developing device and put it in a high temperature and high humidity chamber
%) Overnight (12 hours). After returning the developing device to the room temperature and humidity room, 20 sheets of images are immediately output and the image density is measured in the same manner as the previous day. The last day image density is compared with the first image density. The evaluation level is confirmed by the difference between the density of the 1000th sheet (last day before) and the density after standing. (The smaller the value, the better) In this example, as shown in Table 2, the density difference was less than 0.05. ◎: Less than 0.05 ○: 0.05 or more, less than 0.10 △: 0.10 or more, less than 0.30 ×: 0.30 or more

(Evaluation-2) The evaluation toner is put in a developing device and left in a high temperature and high humidity chamber (32.5 ° C., 85%) overnight (12 hours). After measuring the mass of the developing device, the developing device was installed and the developing sleeve was rotated for 3 minutes. At this time, the cleaner section and the waste toner collecting section in the main body are once removed in advance and the mass is measured. Using a test chart with a printing ratio of 6%, 500 sheets were printed and the transfer rate was evaluated. In this example, as shown in Table 2, the transfer efficiency was 93%.

The transfer rate was calculated by the following calculation formula. Transfer rate = {developing device decrease amount− (cleaner part increase amount + waste toner collecting part increase amount)} / developing device decrease amount × 100

After the operation was completed, the fusion in the machine was 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 was found on the crushing rotor and the liner. ◎: No in-flight fusion ○: In-flight fusion is slightly visible but can be used △: Some in-flight fusion is visible, but practical ×: In-flight fusion is noticeable and not practical

Example 2 The powder raw material used in Example 1 was finely pulverized by the mechanical pulverizer shown in FIG. At that time, in this example, grinding was performed in the same manner as in Example 1 except that the cold air temperature T1 was set to -15 ° C.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 29 ° C. Therefore, ΔT (T2-T1) was 44 ° C.

At this time, the peripheral speed of the classification rotor 4 is 55 m /
By setting s, the finely pulverized product obtained by pulverizing with the mechanical pulverizer has a weight average diameter of 6.7 μm as shown in Table 1.
m, and had a sharp particle size distribution in which 45% by number of particles having a particle size of 4.00 μm or less were contained.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an airflow classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.952. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 1.

Next, the classified toner was subjected to external additive mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. as a result,
As shown in Table 2, good results were obtained. In addition, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the crushing rotor and the liner.

Example 3 The powder raw material used in Example 1 was finely pulverized by the mechanical pulverizer shown in FIG. At that time, in this embodiment, the length L of the crushing portion of the crushing rotor 2 is L.
(Mm) / outer diameter D (mm) of the crushing rotor 2 is 0.07
And the cold air temperature T1 was set to 5 ° C. Further, the distance between the crushing rotor 2 and the liner 3 is 1.0 mm, the peripheral speed of the crushing rotor 2 is 135 m / s, the number of crushing rotor blades n / the crushing rotor outer diameter D is 1.0, the number of liner blades n ′ / the inner diameter of the liner. D'was set to 0.8, the raw material supply amount was set to 22 kg / Hr, and the powder was pulverized.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 30 ° C. Therefore, ΔT (T2-T1) was 25 ° C.

At this time, the peripheral speed of the classification rotor 4 is set to 65 m /
By setting s, the finely pulverized product obtained by pulverizing with the mechanical pulverizer has a weight average diameter of 6.5 μm as shown in Table 1.
m, and had a sharp particle size distribution containing 38% by number of particles having a particle size of 4.00 μm or less.

However, the feed amount was lower than that in Example 1. It is considered that this is because the crushing capacity was lowered because the L / D value was small.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.952. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 1.

Next, the classified toner was subjected to external mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. The results are shown in Table 2.
Shown in. In addition, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the crushing rotor and the liner.

Example 4 The powder raw material used in Example 1 was finely pulverized by the mechanical pulverizer shown in FIG. At that time, in this example, grinding was performed in the same manner as in Example 3 except that the cold air temperature T1 was −15 ° C. and the raw material supply amount was 27 kg / Hr.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 23 ° C. Therefore, ΔT (T2-T1) was 38 ° C.

At this time, the peripheral speed of the classification rotor 4 is 60 m /
By setting s, the finely pulverized product obtained by pulverizing with the mechanical pulverizer has a weight average diameter of 6.8 μm as shown in Table 1.
m, and had a sharp particle size distribution containing 40% by number of particles having a particle size of 4.00 μm or less.

However, the feed amount was lower than that in Example 2. It is considered that this is because the crushing capacity was lowered because the L / D value was small.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.948. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 1.

Next, the classified toner was subjected to external mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. The results are shown in Table 2.
Shown in. In addition, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the crushing rotor and the liner.

Example 5 The powder raw material used in Example 1 was finely pulverized by the mechanical pulverizer shown in FIG. At that time, in this embodiment, the length L of the crushing portion of the crushing rotor 2 is L.
(Mm) / outer diameter D (mm) of the crushing rotor 2 is 0.19
And the cold air temperature T1 was set to 5 ° C. Further, the distance between the crushing rotor 2 and the liner 3 is 1.0 mm, the peripheral speed of the crushing rotor 2 is 165 m / s, the number of crushing rotor blades n / the crushing rotor outer diameter D is 1.0, the number of liner blades n ′ / the inner diameter of the liner. D'was set to 0.8, the raw material supply amount was set to 58 kg / Hr, and the powder was crushed.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 43 ° C. Therefore, ΔT (T2-T1) was 38 ° C.

At this time, the peripheral speed of the classification rotor 4 is 55 m /
By setting s, the finely pulverized product obtained by pulverizing with the mechanical pulverizer has a weight average diameter of 6.9 μm as shown in Table 1.
m, and had a particle size distribution in which 52% by number of particles having a particle size of 4.00 μm or less were contained.

However, the number% of particles having a particle size of 4.00 μm or less was higher than that in Example 1. It is considered that this is because the value of L / D was large, so that the powder was overcrushed.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.956. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 1.

Next, the classified toner was subjected to external mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. The results are shown in Table 2.
Shown in. In addition, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the crushing rotor and the liner.

Example 6 The powder raw material used in Example 1 was finely pulverized by the mechanical pulverizer shown in FIG. At that time, in this example, grinding was performed in the same manner as in Example 5 except that the cold air temperature T1 was −15 ° C. and the raw material supply amount was 72 kg / Hr.

As a result of operating for 30 minutes in this state, the room temperature T2 of the rear chamber of the classification rotor 4 was stable at 37 ° C. Therefore, ΔT (T2-T1) was 52 ° C.

At this time, the peripheral speed of the classification rotor 4 is 50 m /
By setting s, the finely pulverized product obtained by pulverizing with the mechanical pulverizer has a weight average diameter of 6.6 μm as shown in Table 1.
m, and had a particle size distribution in which 54% by number of particles having a particle size of 4.00 μm or less were contained.

However, the number% of particles having a particle size of 4.00 μm or less was higher than that in Example 2. It is considered that this is because the value of L / D was large, so that the powder was overcrushed.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream type classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.953. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 1.

Next, the classified toner was subjected to external additive mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. The results are shown in Table 2.
Shown in. In addition, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the crushing rotor and the liner.

[0148]

[Table 1]

[0149]

[Table 2]

Comparative Example 1 The powder raw material used in Example 1 was finely pulverized by a collision type air flow pulverizer (IDS-5 type: manufactured by Nippon Pneumatic Mfg. Co., Ltd.) shown in FIG. In FIG.
The crusher 31 has the same specifications as those described in FIG.

In this comparative example, the compressed air pressure used in the collision type airflow crusher was 6.0 kg / cm ² G. Further, the target particle size of the obtained finely pulverized product was set to be 6.5 ± 0.5 μm in weight average diameter as in the example, and the raw material supply amount was 46 kg / Hr in order to obtain the target particle size.

At this time, as shown in Table 3, the finely pulverized product obtained by pulverizing with the collision type airflow pulverizer had a weight average diameter of 6.9 μm and a particle diameter of 4.00 μm or less. 62
It had a particle size distribution of containing a few percent. Compared with the examples, the value of fine powder was large and the particle size distribution was broad.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.932. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 3.

Then, the obtained toner was subjected to external additive mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. as a result,
As shown in Table 4, the result was inferior to that of the example, and a satisfactory result was not obtained.

After the completion of the operation, when the inside of the collision type air flow crusher was inspected, no fusion was found in the crushing chamber and the collision plate.

[Comparative Example 2] The powder raw material used in Example 1 was finely pulverized by a collision type air flow pulverizer (IDS-5 type: manufactured by Nippon Pneumatic Mfg. Co., Ltd.) shown in FIG.

In this comparative example, the compressed air pressure used was 4.5 kg / cm ² G for the purpose of increasing the amount of toner circulation in the collision type airflow pulverizer. Further, in order to obtain the target particle size, the raw material supply rate was set to 28 kg / Hr.

At this time, as shown in Table 3, the finely pulverized product obtained by pulverizing with the collision type air flow pulverizer had a weight average diameter of 6.8 μm and a particle diameter of 4.00 μm or less. 58
It had a particle size distribution containing a few percent. Compared with the examples, the value of fine powder was large and the particle size distribution was broad.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an airflow classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.933. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 3. In this comparative example, the compressed air pressure was decreased and the raw material supply amount was decreased to increase the toner circulation amount inside the apparatus, but the toner shape was not different from that in Comparative example 1.

Next, the obtained toner was subjected to external mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. as a result,
As shown in Table 4, the result was inferior to that of the example, and a satisfactory result was not obtained.

After the completion of the operation, when the inside of the collision type airflow crusher was inspected, no fusion was found in the crushing chamber and the collision plate.

[Comparative Example 3] The powder raw material used in Example 1 was finely pulverized by a collision type air flow pulverizer (IDS-5 type: manufactured by Nippon Pneumatic Mfg. Co., Ltd.) shown in FIG.

In this comparative example, the compressed air pressure used was 3.0 kg / cm ² G for the purpose of further increasing the amount of toner circulation in the collision type airflow pulverizer. Further, in order to obtain the target particle size, the raw material supply amount was set to 16 kg / Hr.

At this time, as shown in Table 3, the finely pulverized product obtained by pulverizing with the collision type air flow pulverizer had a weight average diameter of 6.9 μm and a particle diameter of 4.00 μm or less. 58
It had a particle size distribution containing a few percent. Compared with the examples, the value of fine powder was large and the particle size distribution was broad.

Next, the finely pulverized product obtained by pulverizing with the above mechanical pulverizer was introduced into an air stream classifier and classified to obtain a classified toner. The circularity of the obtained toner was measured and found to be 0.933. Further, the surface shape of this toner was observed by an SEM photograph. The results are shown in Table 3. In this comparative example, the compressed air pressure was further reduced and the raw material supply amount was reduced to increase the toner circulation amount in the apparatus, but the toner shape was not different from that of Comparative example 1.

Next, the obtained toner was subjected to external additive mixing treatment in the same manner as in Example 1 to obtain a toner for evaluation. as a result,
As shown in Table 4, the results were inferior to those of the examples, although they were at a practical level, and satisfactory results were not obtained.

After the completion of the operation, the inside of the collision type airflow crusher was inspected, and it was found that fusion did not occur in the crushing chamber and the collision plate.

[0168]

[Table 3]

[0169]

[Table 4]

[0170]

As described above, according to the present invention, the mechanical crusher is of a type having a built-in classifying rotor for classifying the crushed raw material to a predetermined particle size, and when further crushing the toner, The length L (mm) of the crushing rotor crushing part of the mechanical crusher and the outer diameter D (m of the crushing rotor
By making the relationship m) appropriate, excessive crushing of the toner can be prevented, the particle size distribution of the toner can be sharpened, the amount of coarse particles generated can be reduced, and the surface shape of the toner can be controlled arbitrarily, and high temperature Provided are a mechanical pulverizer and a method for producing a toner, which can obtain a long-life toner having good developability, transferability, and stable chargeability from the initial stage even in a high humidity environment.

Further, by controlling the surface shape of the toner in the mechanical pulverizer, a method for producing a toner in which a toner having a high image density can be obtained from the beginning in a high temperature and high humidity environment and also after standing Will be provided.

Further, there is provided a method for producing a toner capable of obtaining a toner having excellent durability on a large number of sheets.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a mechanical pulverizer used in a toner pulverizing step of the present invention.

FIG. 2 is a schematic sectional view of a conventional collision type airflow crusher.

FIG. 3 is a schematic cross-sectional view of an example collision-type airflow crusher used in a comparative example of the present invention.

[Explanation of symbols]

1 casing 2 crushing rotor 3 liner 4-class rotor 5 Cold air inlet 6 Raw material supply port 7 Powder outlet 8 circulating flow 14 Raw material supply port 15 collision surface 17 Collision member 18 Grinding chamber 19 Accelerator tube exit 20 Accelerator 21 High pressure gas supply nozzle 31 crusher 32 classifier 33 Raw material feeder 34 Conveyor tube 35 nozzles 36 collision plate 37 Grinding chamber 38 collectors 39 Body hopper 40 center core 41 Separate core 42 Discharge pipe 43 Secondary air supply port

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/087 G03G 9/08 381 (72) Inventor Tetsuya Ida 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. In-house (72) Inventor Kazuhiko Hayami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AB04 EA05 EA10 4D065 AA12 AA18 BB20 EB20 ED24 ED32 EE02 EE19

Claims (12)

[Claims] 1. A mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled, the cooled product is roughly pulverized, and the coarsely pulverized product is finely pulverized by a pulverizing means. A finely pulverized product, and a weight average particle diameter of 4 to 12
In the method for producing a toner for producing a toner having a particle size of μm, the pulverizing means is a mechanical pulverizer, and the mechanical pulverizer is supported by at least a rotating shaft and is provided on the outer surface substantially all around. A ring-shaped crushing rotor having a crushing blade composed of a plurality of irregularities, and a liner having a plurality of irregularities on a surface facing the crushing rotor and fixedly arranged with a space between the crushing rotor. , Incorporating a rotary blade type classification rotor for discharging to the outlet side those having a predetermined particle size or less of the raw material crushed between the crushing rotor and the liner, and the raw material not discharged to the outlet side A mechanical crusher having a circulation passage provided below the crushing blade for bringing the crushing blade to the lower part of the interval, the length L (mm) of the crushing rotor crushing portion, and the outer diameter D (mm) of the crushing rotor. of Method for producing a toner, wherein the engagement satisfies the following conditions. 0.06 ≦ L / D ≦ 0.20 2. The method for producing a toner according to claim 1, wherein the toner produced by the mechanical pulverizer has an average circularity of 0.940 to 1.00. 3. A cold air temperature T1 introduced into the mechanical crusher.
Is 5 ° C. or lower, and the method for producing a toner according to claim 1, wherein 4. The method for producing a toner according to claim 1, wherein the mechanical crusher is provided with a cooling means for cooling the inside of the machine. 5. The mechanical crusher is equipped with a jacket for cooling the inside of the machine, and the powder raw material is crushed while passing cooling water through the jacket. The method for producing a toner according to claim 1. 6. The method for producing a toner according to claim 1, wherein the room temperature T2 of the rear chamber of the classifying rotor of the mechanical pulverizer is 45 ° C. or lower. 7. A temperature difference ΔT (T) between the temperature T2 and the temperature T1.
7. The method for producing a toner according to claim 1, wherein 2-T1) is 60 ° C. or lower. 8. The minimum distance between the crushing rotor and the liner is 0.5 mm to 2.0 mm, and the rotating peripheral speed of the crushing rotor is 120 to 175 m / sec. 8. The method for producing a toner according to any one of 1 to 7. 9. The relationship between the outer diameter D (mm) of the crushing rotor and the number of crushing blades n provided on the outer surface of the crushing rotor has the following relationship. 5. The method for producing a toner according to any one of 1. n / D ≧ 0.8 10. The toner according to claim 9, wherein the outer diameter D of the crushing rotor and the number n of crushing blades provided on the outer surface of the crushing rotor have the following relationship. Method. 0.8 ≦ n / D ≦ 1.3 11. The liner inner diameter D ′ (mm) and the number of crushing blades n ′ provided on the inner surface of the liner have the following relationship: The method for producing a toner according to claim 1. n '/ D' ≧ 0.8 12. The method for producing a toner according to claim 11, wherein the inner diameter D ′ of the liner and the number n ′ of crushing blades provided on the inner surface of the liner have the following relationship. . 0.8 ≦ n ′ / D ′ ≦ 1.3