JP2002287429A - Binary color developer and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binary color developer at a low cost which is excellent in the electrification rising property of the toner and in the environmental stability and which allows the powder not meeting the standard in the manufacture process to be reused. SOLUTION: The method is for manufacturing the binary color developer containing a negative electrification color toner which contains a binder resin, a coloring agent, and compounds expressed by general formula (I). In the method for manufacturing composed of processes of mechanically mixing of the toner, of melting and kneading, of pulverizing and of classifying, the powder particles which do not meet the standard and are produced in the pulverizing and classifying processes are again added to the source material and mechanically mixed. In the formula, each of R1 and R4 represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aromatic ring, each of R2 and R3 represents a substituted or unsubstituted aromatic ring, B is boron and X<+> represents a cation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner manufacturing method, and more particularly to a two-component color developer used in an electrophotographic copying machine or an electrostatic recording apparatus, and a manufacturing method thereof.

[0002]

2. Description of the Related Art As a developing method used in an electronic copying machine or an electrostatic recording apparatus, a developer is transported by a transport member, and an electrostatic latent image formed on a photoreceptor is visualized by the developer. The method is well known.

In this developing method, a one-component developer composed of only a toner or a two-component developer composed of a toner and a carrier is generally used. Generally, a toner is composed of a binder resin, a colorant, a charge control agent, and other additives. Various charge control agents have been proposed to impart desirable charging characteristics, stability over time, and environmental stability. In particular, the charge control agent for full-color toner has a great limitation that a colored material cannot be used. Therefore, colorless, white, or light-colored charge control agents that do not affect the hue have been proposed.

For example, a metal complex salt compound of a salicylic acid derivative (JP-B-55-42752, JP-A-61-6907)
No. 3, JP-A-61-221756, JP-A-9-124
No. 659), a metal salt compound of an aromatic dicarboxylic acid (see JP-A-57-111541), a metal complex salt compound of an anthranilic acid derivative (see JP-A-62-94856).
There is. However, these charge control agents are chromium compounds, which are considered to be considered important in the future and are concerned about environmental safety, lack of charge imparting effect, lack of environmental stability, lack of charge rising property, etc. However, none of them had satisfactory performance as a charge control agent.

Further, a full-color developer often uses expensive dyes and pigments and charge control agents. In addition, there is a tendency that a smaller particle size of the developer is required from the viewpoint of image reproducibility, and the amount of fine particles and coarse particles (hereinafter referred to as nonstandard products) other than products generated mainly in the pulverization and classification processes is also reduced. More
The manufacturing speed and yield tend to decrease, and the cost is very high as compared with the black toner. Therefore, in order to reduce costs, it has been attempted to return these nonstandard products to the original kneading and manufacturing process and adjust them again to the standardized product particle size. Is
Naturally, the component amounts of the standard product and the nonstandard product must be the same. However, the charge control agent mentioned above is poorly dispersed in the binder resin, and the amount contained in the standard product is often different from the nonstandard product (particularly, fine particles). In particular, this phenomenon becomes remarkable when the toner particle size is reduced with the recent increase in image quality, making it difficult to reuse nonstandard products and hindering cost reduction.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a two-component color developer which is excellent in charge rising property and environmental stability of a toner and which can reuse nonstandard powders during a manufacturing process at a low cost. an object of the present invention is to.

[0007]

In order to achieve the above object, the invention of a method for producing a two-component color developer according to claim 1 comprises at least a binder resin, a colorant, and a compound represented by the following general formula (1). The method is characterized in that a negatively chargeable color toner containing the compound represented by I) is mixed with a raw material and melt-kneaded, and then the non-standard powder particles generated during pulverization and classification are mixed with the raw material.

Embedded image [Wherein, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (including a condensed ring) )
Are shown, B represents boron, X + represents a cation. ]

According to a second aspect of the present invention, in the method for producing a two-component color developer according to the first aspect, the nonstandard powder particles are mixed in an amount of 30% by weight or less based on the raw material.

The invention described in claim 3 is the first or second invention.
Wherein the negatively chargeable toner has a volume average particle size of 5 to 9 μm,
It is characterized in that 10% by number or less of particles having a particle size of not more than m exist.

[0010] The two-component color developer according to claim 4 has at least a binder resin, a colorant, and a negatively chargeable color toner containing a compound represented by the following general formula (I). After the raw materials are mixed and kneaded, they are characterized by containing the non-standard powder particles generated during pulverization and classification, and the raw materials.

[0011]

Embedded image

[In the formula, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (condensed ring) B includes boron, and X + represents a cation. ]

According to a fifth aspect of the present invention, in the two-component color developer of the fourth aspect, the negatively chargeable toner has a volume average particle diameter of 5 to 9 μm, and particles having a particle diameter of 4 μm or less are 10 μm or less. It is characterized in that it exists in a number of not more than%.

[0014]

The above object of the present invention is achieved by the following means. According to the present invention, there is provided a two-component color developer having at least a binder resin, a colorant, and a negatively chargeable color toner containing a compound represented by the following general formula (I). The toner is other than particles that are classified and collected as standardized products in a pulverization or classification step in a method for producing a toner having a step of mechanically mixing, a step of melt-kneading, a step of pulverization, and a step of classification. of the most important feature that in addition to raw materials nonstandard powder particles again a toner prepared by mechanically mixing.

[0015]

Embedded image

[In the formula, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (condensed ring) B includes boron, and X + represents a cation. ]

Secondly, in the step of mechanically mixing the particles according to the first aspect, the step of mixing the particle powder, which has not been adopted as a standard product, obtained in the step of pulverizing or classifying into the raw material, comprises 100% by weight of the raw material. On the other hand, the main feature is a two-component color developer in which non-standardized powder particles are added in an amount of 30% by weight or less and mechanically mixed.

Third, in the two-component color developer according to claim 1, the volume average particle diameter of the negatively chargeable toner is 5 to 5.
The main feature is that 10% by number or less of toner particles having a particle size of 9 μm and a particle size of 4 μm or less exist.

Fourthly, in the two-component color developer according to claim 1, a method for producing a toner comprising a step of mechanically mixing, a step of melt-kneading, a step of pulverizing, and a step of classifying. The method according to claim 1, wherein, in the step of mechanically mixing, at least particle powder not obtained as a standard product obtained in the step of pulverizing or classifying is added to the raw material and mechanically mixed. The most main feature is the method for producing a color toner. The details will be described below.

The present applicants have conducted intensive studies to overcome the problems of the prior art, and as a result, have found that the above-mentioned object can be achieved by using a specific charge controlling agent. Was completed.

(Two-Component Full-Color Developer) As the charge control agent used in the present invention, a charge control agent defined by the following formula is used. Of course, it can be used in combination with another charge control agent to reinforce the charge (hereinafter, this charge control agent is referred to as a main charge control agent). The compound represented by formula (I) will be described in detail. The alkyl groups of R ₁ and R ₄ of the anion include:
Methyl group, ethyl group, n-butyl group, iso-amyl group,
n-dodecyl group, n-octadecyl group, cyclohexyl group, etc., and the aromatic ring of R ₁ , R ₂ , R ₃ , R ₄ include a benzene ring and a naphthalene ring, and the substituent is an alkyl group. , An alkoxy group, a halogen atom, an aryl group, an aralkyl group, a nitro group, a cyan group and the like.

As a method for producing the charge control agent, for example, the following general formula (II) can be mentioned for an aqueous solution of boric acid and an amine.

[0023]

Embedded image

(In the formula, R ₁ and R ₂ are the same as in the compound (I)), and can be easily obtained by adding and reacting.

The amount of the main charge control agent can be freely changed by the system.
0.2 to 7 parts by weight are preferred. More preferably,
0.3 to 5 weight is preferred. At this time, if the amount of the main charge control agent is less than 0.2 parts by weight, the effect cannot be exhibited. Further, if the amount is more than 7 parts by weight, the effect is not only limited, but also the cost is increased and the method is not practical. By using this main charge control agent, the rise of charging is sufficient without contaminating the color characteristics as a full-color developer,
A product having a high charge level and being suitable as a full-color developer with little generation of a reversely charged developer can be obtained. Therefore, a high-quality image with high image density and little background stain can be obtained.

It has also been found that the main charge control agent has a strong interaction with the binder resin, is uniformly dispersed in the developer particles, and does not easily transfer to the fixing roller at the time of fixing even at a high temperature, that is, hardly causes so-called hot offset. did. As a result, the service life of the fixing roller is greatly extended, and the amount of the release agent applied to the fixing roller can be extremely reduced, and sometimes it becomes unnecessary. Here, as the toner used in the present invention, any known method can be used for the production method and the material.

As the binder resin, polystyrene,
Polymers of styrene such as poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-
Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Coalescence, styrene-
Styrene-based copolymers such as maleic ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, Polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be used alone or in combination.

As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (1
0G, 5G, G), cadmium yellow, yellow iron oxide, ocher, graphite, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow ( G, G
R), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cad Muum Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phisaed Red, Parachlor Ortho Nitroaniline Red, Risor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine Min BS, Permanent Red (F2R, F4R, FRL, FRL)
L, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F
2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Museum, Eosin Lake,
Rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue , Alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (R
S, BC), indigo, ultramarine, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc White, Lithobon and mixtures thereof can be used. The amount used is generally 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.

The color toner of the present invention may optionally contain a charge control agent for reinforcement. As the charge control agent for reinforcement, any known charge control agents can be used. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium Salts (including fluorinated quaternary ammonium salts), alkylamides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bongron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-3 of a metal-containing azo dye
4, E-82 of oxynaphthoic acid-based metal complex, E-84 of salicylic acid-based metal complex, E-8 of phenol-based condensate
9, TP-302 and TP-415 of quaternary ammonium salt molybdenum complex
(Above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst) Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

In the present invention, the amount of the reinforcing charge control agent used is determined by the toner production method including the amount of the main charge control agent, the type of the binder resin, the presence or absence of additives used as required, and the dispersion method. Although it is not particularly limited, it is preferably used in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. Preferably, the range is 0.3 to 5 parts by weight. 10
When the amount exceeds the weight part, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller increases, the flowability of the developer decreases, and the image density decreases. the lead.

In order to impart a releasability to the produced color toner, it is possible to include wax in the produced toner. The wax has a melting point of 40-
The temperature is 120 ° C, particularly preferably 50 to 110 ° C. When the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while when the melting point is too low, the offset resistance and durability may decrease. The melting point of the wax is determined by a differential scanning calorimetry ( DS
C). That is, the melting peak value when a few mg of the sample is ripened at a constant heating rate, for example (10 ° C./min), is defined as the melting point.

Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketones, fatty acid metal salt wax, and fatty acid ester wax. And partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols, carnauba waxes, and the like. Polyolefins such as low molecular weight polyethylene and polypropylene can also be used. In particular, a polyolefin having a softening point of 70 to 150 ° C by a ring and ball method is preferable,
Further, a polyolefin having a softening point of 120 to 150 ° C is preferable.

As the external additive, inorganic fine particles can be preferably used. The primary particle size of the inorganic fine particles is 5
mμ to 2 μm, preferably 5 μm to 50 μm.
It is preferably 0 mμ. Further, the specific surface area by the BET method is preferably from 20 to 500 m2 / g. The usage ratio of the inorganic fine particles is 0.01 to
Is preferably 5% by weight, in particular 0.01 to 2.0
% By weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous Examples include earth, chromium oxide, cerium oxide, pengara, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

In addition, polymer-based fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as methacrylate and acrylate copolymers, silicone, benzoguanamine, and nylon, and thermosetting. Polymer particles made of a conductive resin.

Such a fluidizing agent is subjected to a surface treatment,
Hydrophobicity can be increased to prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate-based coupling agent, an aluminum-based coupling agent, and the like are preferable surface treatment agents.

Examples of the cleaning property improving agent for removing the post-transfer developer remaining on the photoreceptor and the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, for example, fine particles of polymethyl methacrylate, Examples include polymer fine particles produced by soap-free emulsion polymerization of polystyrene fine particles and the like. Polymer fine particles have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
Are preferred.

(Method of Manufacturing Two-Component Full Color Toner)
The production method of the present invention has a step of mechanically mixing a toner component containing at least a binder resin, a main charge controlling agent and a coloring material, a step of melt-kneading, a step of pulverizing, and a step of classifying. In a method for producing a toner, a particle powder that is not adopted as a standard product obtained in a pulverizing or classifying step is mechanically mixed with at least a raw material and a toner component.

According to such a structural feature, pulverization,
Classification step in generated standard products to adopted not particulate and coarse particles be reused (non-standard product) does not change with the developer in the case of not reusing chargeability, developability, has durability,
A low-cost two-component full-color toner can be provided.

The term "non-standardized product" as used herein refers to a fine or coarse particle which has not been adopted as a standardized product having a desired particle size obtained in the pulverizing process after the step of melt-kneading, or the desired product generated in the subsequent classification process. Fine particles and coarse particles that do not become standardized in particle size. In the mixing process of such nonstandard products,
From non-standard product 1 to other raw materials 99, non-standard product 50
It is preferable to mix the other raw materials 50 by weight. More preferably, the other raw materials 99 for the nonstandard product 1 and the other raw materials 70 for the nonstandard product 30.
Mix by weight ratio.

Normally, when the by-product is returned to the kneading step, the binder resin as a nonstandard product is again subjected to a high shearing force in the kneading step, and the obtained developer becomes brittle, which causes problems in storage stability and durability. However, the dispersion of the coloring material and the charge controlling agent may be excessively advanced, and the desired charging characteristics and color characteristics may not be obtained.However, when the main charge controlling agent of the present invention is used, the interaction with the binder resin may occur. strongly,
It seems that the effect of the shear energy received repeatedly is suppressed.

The mixing step of mechanically mixing at least the binder resin, the main charge controlling agent, the pigment, and the developer component containing the nonstandard product is carried out under ordinary conditions using an ordinary mixer with rotating blades. There is no particular limitation. After the above mixing step is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used.

It is important that the melt kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be cut. Specifically, the melt-kneading temperature should be determined with reference to the softening point of the binder resin. If the temperature is lower than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

After the completion of the above-mentioned melt-kneading step, the kneaded material is pulverized. In this pulverization step, it is preferable to first perform coarse pulverization and then finely pulverize. At this time, a method of crushing by colliding with a collision plate in a jet stream or a method of crushing with a narrow gap between a rotor and a stator that rotates mechanically is preferably used.

After the completion of the pulverizing step, the pulverized product is classified in a gas stream by centrifugal force or the like, thereby producing a toner having a predetermined particle size, for example, an average particle size of 4 to 12 μm. In this case, it is particularly effective when the volume average particle diameter is 5 to 9 μm and the particle diameter is small and the particle size distribution is sharp such that 10% by number or less of toner particles having a particle diameter of 4 μm or less exist. In other words, the smaller the particle size and the sharper the distribution, the more fine particles that are nonstandard products are generated. At this time,
By including the charge control agent, the components in the fine particles become almost the same as the components in the product, and the product can be easily produced by kneading the fine particles again.

In preparing the toner, the above-mentioned hydrophobic silica fine particles may be further added to the toner produced as described above in order to enhance the fluidity, storability, developability and transferability of the toner. Inorganic fine particles such as powder may be added and mixed.
A general powder mixer is used for mixing the external additives, but it is preferable that the internal temperature can be adjusted by providing a jacket or the like. In order to change the history of the load applied to the external additive, the external additive may be added during or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. First, a strong load may be applied first, and then a relatively weak load may be applied, or vice versa.

Examples of mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauter mixer, and a Henschel mixer.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and percentages are by weight unless otherwise specified. (Example 1) 1200 parts of water and 540 parts of carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) are thoroughly stirred with a flasher. Here, polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / M
n; 4.0, Tg; 60 ° C.)
After mixing and kneading, 1000 parts of xylene was added, and the mixture was further kneaded for 1 hour. After removing water and xylene, the mixture was rolled and cooled and pulverized with a pulperizer to obtain a master batch pigment. (MB-1)

600 parts of water Pigment Blue 15: 3 1200 parts of a water-containing cake (solid content: 50%) is thoroughly stirred with a flasher. Here, polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / M
n; 4.0, Tg; 60 ° C.)
After mixing and kneading, 1000 parts of xylene was added, and the mixture was further kneaded for 1 hour. After removing water and xylene, the mixture was rolled and cooled, pulverized with a pulperizer, and further passed through a three-roll mill for two passes to obtain a master batch pigment. (MB-2)

Polyester resin 100 parts (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / Mn; 4.0, Tg; 60 ° C.) 5 parts of the above master batch (MB-1) 5 parts of the above master batch (MB-2) 0.5 part Main charge control agent (LR-147 manufactured by Nippon Carlit Co.) 2 parts The above materials were mixed by a mixer, melt-kneaded by a two-roll mill, and the kneaded material was rolled and cooled. Thereafter, an impingement plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industries, Ltd.) using a jet mill and a wind classifier (DS classifier; manufactured by Nippon Pneumatics, Inc.) using a swirling flow were used to obtain a volume average particle size of 9.1 μm.
m and 4 μm or less were 14.7% by number of colored particles.
(The fine particles collected at this time are referred to as BK1 fine powder)
0.5 wt% of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed with a mixer to obtain a black toner. (BK1)

Next, a toner is formed again using the fine particles collected at this time. 100 parts of a polyester resin (acid value: 3, hydroxyl value; 25, Mn; 4500, Mw / Mn; 4.0, Tg; 60 ℃) the masterbatch (MB-1) 5 parts The above masterbatch (MB-2) 0. 5 parts Main charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) 2 parts BK1 fine powder 25 parts The above-mentioned material is made into a toner similarly to BK1, and the volume average particle diameter is 9.0 μm, and 4 μm or less is colored particles of 15.2% by number. I got (BK1 re) The particle size distribution was measured with a Coulter counter TAII of Coulter.

Hereinafter, Y, M, and C toners are prepared in the same manner. (Example 2) 1200 parts of water 600 parts Pigment Yellow 17 water-containing cake (solid content 50%) is thoroughly stirred with a flasher. Here, polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / M
n; 4.0, Tg; 60 ° C.)
After mixing and kneading, 1000 parts of xylene was added and kneading was further performed for 1 hour. After removing water and xylene, the mixture was rolled, cooled, pulverized with a pulperizer, and further passed through three rolls to obtain a master batch pigment.

100 parts of polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / Mn; 4.0, Tg; 60 ° C.) 5 parts of the above master batch 5 parts Main charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) ) 2 copies

After mixing the above-mentioned materials by a mixer, they were melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the case of the developer BK1 to obtain colored particles having a volume average particle size of 9.2 μm and 4 μm or less of 13.6% by number. Further, 0.5 wt% of hydrophobic silica (H2000, manufactured by Clariant Japan KK) was added and mixed with a mixer to obtain a yellow toner (Y1, Y1).

(Example 3) 600 parts of water 1200 parts of Pigment Red 57-1 water-containing cake (solid content 50%) is thoroughly stirred with a flasher. Here, polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / M
n; 4.0, Tg; 60 ° C.)
After mixing and kneading, 1000 parts of xylene was added, and the mixture was further kneaded for 1 hour. After removing water and xylene, the mixture was rolled and cooled, pulverized with a pulperizer, and further passed through a three-roll mill for two passes to obtain a master batch pigment.

Polyester resin 100 parts (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / Mn; 4.0, Tg; 60 ° C.) 5 parts of the master batch 5 parts Main charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) ) 2 copies

After mixing the above-mentioned materials by a mixer, they were melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were carried out in the same manner as in the case of the developer BK1 to obtain colored particles having a volume average particle size of 9.1 μm and 4 μm or less of 16.5% by number. Further, 0.5 wt% of hydrophobic silica (H2000, manufactured by Clariant Japan KK) was added and mixed with a mixer to obtain a magenta toner (M1, M1 re).

(Example 4) 1200 parts of 600 parts of water, 1200 parts of a pigment-containing cake (solid content: 50%) of water, are thoroughly stirred with a flasher. Here, polyester resin (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / M
n; 4.0, Tg; 60 ° C.)
After mixing and kneading, 1000 parts of xylene was added, and the mixture was further kneaded for 1 hour. After removing water and xylene, the mixture was rolled and cooled, pulverized with a pulperizer, and further passed through a three-roll mill for two passes to obtain a master batch pigment.

Polyester resin 100 parts (acid value; 3, hydroxyl value; 25, Mn; 4500, Mw / Mn; 4.0, Tg; 60 ° C.) 3 parts of the above master batch 3 parts Main charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) 2 parts) The above materials were mixed by a mixer, then melt-kneaded by a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, pulverization and classification were performed in the same manner as in the example of the production of the developer BK1, and the volume average particle size was 9.0 μm.
45.7 μm or less of colored particles of 15.7% by number were obtained. Further, 0.5 wt% of hydrophobic silica (H2000, manufactured by Clariant Japan KK) was added and mixed with a mixer to obtain a cyan toner (C1, C1 re).

Comparative Examples 1 to 4 The charge control agent was LR-14.
7 in place of zinc salicylate derivative (Bontron E8
BK1, Y1, M1, and C1 and the same raw materials and manufacturing method as in Example 1 except that the production was performed in the same manner as in Example 1 except that the production was performed in the same manner as in Example 1.
1, bk1 re, y1, y1 re, m1, m1 again, c1, c
1 re).

(Example 5) Coloring with a volume average particle diameter of 9.0 µm and 4 µm or less of 14.9% by number was carried out under the same conditions as in Example 1 except that the amount of fine powder in Example 1 was changed to 40 parts by weight. Particles were obtained.

(Comparative Example 5) Under the same conditions as in Comparative Example 1 except that the amount of the fine powder in Comparative Example 1 was changed to 40 parts by weight, 13.7% by volume of 9.1 μm and 4 μm or less were colored. Particles were obtained.

The heat resistance storage stability of the toner alone was evaluated. In addition, Ricoh's ImagioColor2800
Was used to evaluate the matching, and the background fog and toner scattering to the developing section were observed. Heat resistance is 50 ℃
Observe the state of the toner when stored for 24 hours in the environment.

Table 1 shows the results.

[0064]

[Table 1]

(Evaluation) Storage stability 性: very good: good △: slightly deteriorated (no substantial problem) ×: blocking Ground covering ○: good △: slightly bad (acceptable level) ×: bad

[0066]

According to the present invention, by using a specific CCA, even if nonstandard products (especially fine powder) generated during the process which has been conventionally discarded can be effectively used, there is a concern that the toner may be stored under heat. The deterioration of the performance was also suppressed, and there was no particular problem in the evaluation on the actual machine. Thus, according to the present invention,
It is possible to provide a low-cost two-component full-color developer having the same chargeability as a developer that is not reused even if the fine particles and coarse particles other than the standard product generated in the pulverization and classification processes are reused even if they are reused. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Masuda 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Kosuke Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Ricoh Co., Ltd. (72) Inventor Tamotsu Kajihara 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H005 AA21 AB02 CA25 DA02 EA05 EA07

Claims (5)

[Claims] At least a raw material having a binder resin, a colorant, and a negatively chargeable color toner containing a compound represented by the following general formula (I) is mixed and melt-kneaded.
A method for producing a two-component color developer, comprising mixing nonstandard powder particles generated during pulverization and classification with the raw materials. Embedded image [Wherein, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (including a condensed ring) )
, B represents boron and X + represents a cation. ] 2. The method for producing a two-component color developer according to claim 1, wherein the nonstandard powder particles are mixed in an amount of 30% by weight or less based on the raw material. 3. The negatively chargeable toner according to claim 1, wherein the volume average particle diameter is 5 to 9 μm, and particles having a particle diameter of 4 μm or less are present in 10% by number or less. A method for producing a two-component color developer. 4. Raw materials having at least a binder resin, a coloring material, and a negatively chargeable color toner containing a compound represented by the following general formula (I) are mixed and melt-kneaded.
A two-component color developer comprising non-standard powder particles generated during pulverization and classification, and the raw materials. Embedded image [Wherein, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (including a condensed ring) )
, B represents boron and X + represents a cation. ] 5. The two-component toner according to claim 4, wherein the negatively chargeable toner has a volume average particle size of 5 to 9 μm, and particles having a particle size of 4 μm or less are present in 10% by number or less. Color developer.