JP3345474B2 - Charge control agent composition and toner containing the composition. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition useful for a toner which is an electrophotographic developer and an electrophotographic toner containing the composition.

[0002]

2. Description of the Related Art In electrophotography, an electrostatic latent image is formed on a photoconductor made of a photoconductive material or the like, developed with a powder developer, visualized, and fixed with heat or a solvent. The method is general. As such a developer for electrophotography, a mixture of a fine particle powder composed of a resin called a toner and a colorant and a fine iron powder or a ferrite powder called a carrier is used. Since the photoconductor layer can be positively or negatively charged, exposure under the original results in a positive or negative electrostatic latent image. When a negative electrostatic latent image is developed with a positively charged developing powder, a positive-positive image corresponding to the original is generated. Generally, the developing powder is a fine particle powder obtained by mixing a coloring agent such as a dye or a pigment with a synthetic resin. The charging characteristics of the developing powder are governed by the resin which is the main component thereof, but usually a desired frictional charging characteristic is obtained by adding a charge control agent.

[0003]

Generally, electrophotographic toners use particles in which carbon as a coloring agent, a coloring pigment, or a charge controlling agent for controlling a charge amount is dispersed in a thermoplastic resin. . As the charge controlling agent, for example, nigrosine, aniline black, quaternary ammonium, metal complex dyes and the like are often used. In order to disperse these in the resin, a method of adding and kneading carbon or a charge controlling agent to the heat-melted resin is often used. However, in general, fine particles such as carbon and a charge controlling agent are likely to form large secondary particles by agglomeration of primary particles, and also have a compatibility with the resin, so that they do not readily mix uniformly with the resin. Various problems remain in the performance of the toner. In particular, uniform dispersion of the charge control agent in the resin is very important, and it is said that this dispersibility greatly affects various characteristics of the toner. At present, to solve these problems, it is necessary to cope with the use of a twin-screw heating kneader to which a strong shear is applied or a method of operating the heating kneading for a long time. However, this method has problems in that a large amount of electricity and heat is required, productivity is low, and facility costs are high.

Further, even with the toners produced by these methods, the uniform dispersibility of the charge control agent and carbon in the resin is not yet sufficient, and the problems of instability of the charging performance and the scattering of the toner still remain, which is a great solution. Had been an issue.

[0005]

Means for Solving the Problems As a result of various studies to solve these problems, the present inventors have found that a charge control agent obtained by adding carbon during the production process of a metal complex salt dye as a charge control agent. It has been found that a composition obtained by mixing a metal complex dye and carbon in the presence of a solvent, or a composition obtained by mixing a metal complex dye and carbon in the presence of a solvent has a characteristic that dispersibility in a resin is extremely good. In addition, the inventors of the present invention determined that a toner using the charge control agent composition prepared as described above solves the above-mentioned problems, that is, problems such as unstable charging performance and toner scattering. Was completed.

As the metal complex dye used as the charge control agent, known dyes are used. For example, metal complex dyes used as charge control agents include C.I. I. Solvent Black 22, C.I. I. Solvent Violet 2
1, JP-B-43-17995, JP-B-43-27
596, JP-B-44-6397, and JP-A-5
7-141452, JP-A-58-208750, JP-A-58-185653, and JP-A-59-185.
No. 78361, JP-A-59-93457, JP-A-59-228259, and JP-A-60-1005
No. 46, JP-A-60-101546, JP-A-61-91667, JP-A-61-155463, JP-A-61-155644, and JP-A-3-14-1.
No. 07864, JP-B-3-57473 and JP-A-3-149568.

The present invention relates to a charge control obtained by adding carbon during the production process of the metal complex dye represented by the general formula (1) or (2) or by mixing the metal complex dye and carbon by a wet method. It is an object of the present invention to provide a composition comprising an agent and carbon and a toner containing the composition.

That is, the present invention provides: A charge controlling agent composition for forming an electrophotographic toner by mixing with a resin, wherein at least one kind of charge controlling agent selected from metal complex salt dyes represented by the following general formulas (1) and (2): A charge controlling agent composition for toner formation, comprising a composition in which an agent and carbon are mixed in the presence of water and / or an organic solvent (excluding radically polymerizable monomers) and dried. It is.

[0009]

Embedded image

[0010]

Embedded image

{In the general formula (1), M ₁ represents a chromium, cobalt or iron atom, and in the general formula (2), M ₂ represents a titanium, zirconium or silicon atom. Q _1-4 represent N or CH, and Z _1-8 represent O, NH, COO. A
_1-4 and B _1-4 are a phenyl group, an acetyl group or a naphthyl group, and as a substituent, a C _1-8 alkyl group;
C _1-4 alkoxy group, C _1-4 alkyl sulfone group, C _1-4 alkylamino sulfone group, acetylamino group, sulfonamide group, benzoylamino group, phenyl sulfone group, nitro group, halogen atom, hydroxyl group , −
_{COOH, -SO 3 H, -S0 2} CH 3, -COOR 1
[R ₁ is a C _1-30 alkyl group or a C _6-30 aryl group], -CONHR ₂ [R ₂ is a C _1-30 alkyl group or a C _6-30 aryl group] or C
_It may contain _{5 to 12} cyclic alkyl groups (including substituted cyclic alkyl groups). A _1-4 and B _1-4 may be the same or different from each other. X is H ⁺ , K ⁺ , Na ⁺ ,
^{1 / 2Mg 2+, 1 / 2Ca} 2+, 1 / 2Ba 2+, N
Represents H ₄ ⁺ or a quaternary ammonium cation represented by the following general formula (3).

[0012]

Embedded image

[In the general formula (3), n1 represents an integer of ₁ to 3. R _{3 to 6} each represent a hydrogen atom, C _{1 to} C ₃₀
Alkyl group, _C7-30 aralkyl group, _C6-30
An amino group, an ether group, a thioether group, an alkoxy group, a hydroxyl group, a carboxamide group, a sulfonamide group, a urethane group, a chloromethyl group, a nitro group, a halogen atom (F, CL, B
_r), an aromatic group of _{C 6 to 30,} an aromatic heterocyclic group _{C 6 to 30} may include one or more. Also R
_A quaternized amino group may be contained in groups _{3 to 6} .
Further, two of R ₃ to R ₆ may be bonded to each other to form an alicyclic ring or an aromatic ring. ]}

The metal complex dye represented by the general formula (1)
Is specifically exemplified by the following structural formulas.
(6).

[0015]

Embedded image

{In the general formula (4), Y1 ⁺ is H ⁺ , Na
⁺ , K ⁺ , and NH ₄ ⁺ . }

[0017]

Embedded image

{In the general formula (5), Y 2 ⁺ is H ⁺ , Na
⁺ , K ⁺ , and NH ₄ ⁺ . }

[0019]

Embedded image

{In the general formula (6), Y3 ⁺ is H ⁺ , Na
⁺ , K ⁺ , and NH ₄ ⁺ . }

Further, examples of the organic cation represented by X ⁺ in the general formula (1) include the following.

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

In general, a metal complex salt dye is obtained by reacting a mordant dye obtained by diazotization and coupling with a metal salt, further purifying it in several steps, and separating, drying and pulverizing. In the metal complex dye obtained as a result, primary particles are liable to grow into secondary particles during the compression and drying steps during filtration. The metal complex dye having such a large particle diameter is difficult to make finer even if a pulverizing step is added. When the toner is manufactured, the metal complex dye is kneaded into the resin together with the carbon or the like. However, even if the mixture is heated and kneaded for as long as possible with strong shear, the resin cannot be uniformly dispersed in the resin. In particular, it becomes more difficult when the compatibility with the resin is poor.

On the other hand, in the present invention, a charge control agent composition is prepared by adding carbon during the production of the charge control agent, separating a mixture of the generated charge control agent and carbon, and drying the mixture. Carbon may be added before or after the synthesis step of the charge control agent or during the synthesis step, or may be added during or after the purification step after the completion of the reaction. Preferably, carbon is added after the completion of the reaction step or the purification step, the mixture of the charge control agent and the carbon is filtered and dried.

Alternatively, the charge control agent composition of the present invention can also be obtained by mixing the dried charge control agent and carbon in the presence of an appropriate solvent and drying the resulting mixture. The charge control agent and the carbon can be mixed by adding a small amount of a solvent to the mixture of the charge control agent and the carbon, kneading the resulting mixture to form a slurry, and stirring and mixing the slurry. Solvents that can be used here include water, organic solvents, and mixtures of water and organic solvents. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, and butanol, ketones such as acetone and methyl isobutyl (MIBK), dimethylformaldehyde, and dimethylsulfamide.

Charge control in the charge control composition of the present invention
The mixing ratio of the agent and carbon is 20: 1 to 1:20 by weight.
Is preferable.

The charge controlling agent composition of the present invention obtained as described above can be directly used for producing a toner after drying. If necessary, the material may be further pulverized and classified before use. The charge control agent composition of the present invention obtained as described above is one in which the primary particles of the charge control agent and the carbon of the fine particles are very well classified and mixed, and exhibits excellent dispersibility in the resin. Things.

However, even if the metal complex salt dye and carbon, which were once taken out as a dry product, were mixed with each other between powder dry products, the metal complex salt dye remained in the form of secondary particles, and the carbon was also in an agglomerated state, so-called lumpy state. It is very difficult to uniformly disperse and mix. Even if these are dispersed in the resin by heating and kneading, uniform dispersion cannot be easily performed as described in the problem.

In contrast, it was found that when the composition of the metal complex salt dye and carbon prepared according to the present invention was mixed with a resin by heating, the metal complex salt dye and carbon were extremely easily and uniformly dispersed in the resin. In addition, since the toner particles are uniformly dispersed well, the instability of charging of the toner and the scattering of the toner, which were problems in the related art, can be solved.

The carbon which can be used in the present invention can be used irrespective of pH, particle size, hue and the like. Also,
It is not limited to carbon that has been used for conventional toners, but satisfies blackness as a toner,
Any material can be used as long as it is uniformly dispersed with the charge control agent required for the present invention.

Suitable resins for the toner include styrene and its substituted homopolymers such as polystyrene and polyvinyltoluene, styrene-substituted styrene copolymers, and styrene-acrylate copolymers. , Styrene-methacrylate copolymer, styrene-acrylonitrile copolymer, polyvinyl chloride, polyethylene, polyester, silicone resin, polyurethane, polyamide, epoxy resin, modified rosin,
A phenol resin or the like can be used alone or as a mixture.

In order to improve fixability and adhesiveness, for example, low molecular weight polyethylene, low molecular weight polybutene, low molecular weight polypropylene, or maleic acid ethyl ester, maleic acid butyl ester, stearic acid ethyl ester, stearic acid butyl ester, balmitin Fatty acid esters such as cetyl acid ester, or stearic acid amide, oleic acid amide, balmitic acid amide,
Amide waxes such as lauric amide and ethylene bisstearylloamide, carnauba wax and the like can be used.

Further, examples of the carrier suitably usable in the toner of the present invention include coating carriers such as an iron powder carrier, a ferrite carrier, a silicon carrier, an acryl-modified silicon carrier, and a fluorine-modified silicon ferrite carrier. be able to.

On the other hand, the charge control agent composition of the present invention can also be used for a so-called one-component toner.

[0049]

Next, the present invention will be described in more detail by way of examples.

Example 1 19.9 parts of 4,6-dinitro-2-aminophenol was stirred with 10 parts of concentrated hydrochloric acid and 400 parts of water, and then ice-cooled to 0 to 5 ° C., and sodium nitrite was added. Nine parts were added, and the mixture was stirred at the same temperature for 2 hours for diazotization. This diazotized product is treated at 0-5 ° C with 300 parts of water and sodium hydroxide 1
The mixture was poured into a mixture of 0 part and 26.3 parts of 3-hydroxy-2-naphthoanilide to perform a coupling reaction to obtain a monoazo compound. The paste of the separated monoazo compound is dissolved in 150 parts of ethylene glycol, 5 parts of sodium hydroxide and 17.4 parts of sodium chromium salicylate are added, and the mixture is stirred at 110 to 120 ° C. for 2 hours to perform chromization. The mixture was cooled to 50 ° C., and 10 parts of hydrochloric acid was added to the contents to obtain acidity of Congo Red. In this, 3
After adding 50 parts of carbon (Cabot Co., Ltd., Regal 400R) and stirring for 2 hours, the mixture was filtered and dried to obtain a charge control agent composition 1. In the charge control agent composition 1, the composition weight ratio of the following compound (1) to carbon was 5:35.

[0051]

Embedded image

Next, 16 parts of the composition and 200 parts of a styrene-acrylic copolymer resin (Hymer TB1000; manufactured by Sanyo Chemical Industry Co., Ltd.) were preheat-mixed, heated and kneaded with a heating twin-screw kneader for 10 minutes, cooled, and then jet-milled. The mixture was pulverized and classified into particles having a particle size of 5 to 25 μm by airflow classification. The obtained powder was subjected to a surface treatment with colloidal silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) to obtain a toner.

To 5 parts of the toner, 100 parts of an iron powder carrier (TEFV 200/300, manufactured by Nippon Iron Powder Co., Ltd.) was mixed to prepare a developer. Further, the developer was put in a developing device, continuous copying was performed, and an image test was performed. As a result, the initial toner charge amount of the 10,000th sheet was −25.4 μC.
/ G, and a clear black image was obtained. The image quality and charge amount were the same even for 200,000 sheets, and there was no toner scattering or offset. In addition, 35 ° C, 85%
Even in a high-temperature and high-humidity environment of RH and a low-temperature and low-humidity environment of 10 ° C. and 30% RH, image quality equivalent to that of copying under normal temperature and normal humidity environment was obtained. Also, neither toner scattering nor offset occurred.

Example 2 After 5 parts of compound (1) was stirred and dispersed in 100 parts of water at room temperature, 35 parts of the same carbon as in Example 1 was added, stirred, filtered, and sufficiently washed with water. , Dried, compound (1)
A composition 2 having a composition ratio of carbon and carbon of 5:35 was obtained.

Next, except that composition 1 was replaced by composition 2.
A toner was prepared in the same manner as in Example 1. When this toner was put into the developing device, continuous copying was performed, and an image test was performed. At the start, a good image was obtained. The image quality was unchanged after 50,000 sheets, and toner scattering and offset occurred. Did not. Furthermore, good image quality was obtained without being affected by high-temperature and high-humidity and low-temperature and low-humidity environments.

Comparative Example 1 Compound (1) (2 parts), carbon (Cabot Corp. Regal 4)
00R) 14 parts and 200 parts of a styrene-acrylic copolymer resin (Hymer TB1000; manufactured by Sanyo Chemical Industries, Ltd.) are preliminarily mixed, heated and kneaded in a heated twin-screw kneader for 10 minutes, cooled, jet-milled, and air-flow classified. Particle size 5-25 μm
Was classified. The obtained powder was subjected to colloidal silica R-97.
2 (product of Nippon Aerosil Co., Ltd.) to obtain a toner.

Further, an image test was performed in the same manner as in Example 28. The initial toner charge amount of the 10,000th sheet is −24.0.
It decreased to μC / g. The image was clear black, but 2
From the 0,000th sheet, the toner charge amount decreased to −17.3 μC / g. The image was unclear and fogging and toner scattering occurred.

After the completion of the reaction in the same manner as in the method described in Example 1, carbon was added to the charge control agent, and
Were prepared and used in Examples 3-16. In addition, the toners produced using the toner manufactured in the same manner as in Comparative Example 1 using the charge control agent and carbon or the like were used in Comparative Examples 2 to 3.
No. 15. The results are shown in Tables 5 to 8.

In each table, the resin used and the evaluation criteria for each evaluation item are as follows.

Resin used for toner production A: Styrene-acrylic acid copolymer [Hima-SBM-
73 manufactured by Sanyo Chemical Co., Ltd.] B: Styrene-acrylic acid copolymer [Hymer TB-1
000 Sanyo Chemical Co., Ltd.] C: Polyester [HP-313 Nippon Synthetic Chemical Co., Ltd.]
D) Polyester [HP-320 Nippon Synthetic Chemical Co., Ltd.]
E: Polyester [Average molecular weight 15,000] F: Styrene-n-butylacrylic acid copolymer [Average molecular weight 20,000] G: Polyethylene-vinyl acetate copolymer [Average molecular weight]
18,000]

The charge amount of the toner was measured by a blow-off method based on the initial charge amount and the charge amount on the 50,000th running sheet.

Judgment: な し No practical problem × No practical problem

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

According to the present invention, there is provided a composition of a charge controlling agent and carbon obtained by adding carbon during the production process of a metal complex dye as a charge controlling agent, or a composition of a metal complex salt dye and carbon obtained by a wet method. Very well dispersed and mixed. Further, the composition has good dispersibility in a resin,
Further, by producing a toner using the charge control agent composition of the present invention, it was possible to solve various problems such as instability of charging performance and scattering of toner.

Continuation of the front page (56) References JP-A-64-35457 (JP, A) JP-A-1-250962 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9 / 097 G03G 9/09

Claims (8)

(57) [Claims] 1. An electrophotographic toner is formed by mixing with a resin.
A charge controlling agent composition, comprising the general formula (1):
At least one selected from the metal complex dyes represented by (2)
The above charge control agent and carbon are dissolved in water and / or organic solvent.
Mixed in the presence of a solvent (excluding radically polymerizable monomers)
Containing a dried composition for forming a toner.
Charge control agent composition. Embedded image Embedded image {In the general formula (1), M ₁ represents a chromium, cobalt, or iron atom, and in the general formula (2), M ₂ represents a titanium, zirconium, or silicon atom. Q _1-4 represent N or CH, and Z _1-8 represent O, NH, COO. A _1-4 , B
_1-4 phenyl group, an acetyl group or a naphthyl group, examples of the substituent include an alkyl group of _{C 1 to 8,} alkoxy group of _{C 1-4,} alkyl sulfone group of _{C 1-4,} C
_1-4 alkylaminosulfone groups, acetylamino groups, sulfonamide groups, benzoylamino groups, phenylsulfone groups, nitro groups, halogen atoms, hydroxyl groups, -CO
_{OH, -SO 3 H, -S0 2} CH 3, -COOR 1 [R
₁ is an alkyl group or an aryl group _{C 6 to 30} of the _{C 1~30], - CONHR 2 [} R 2 is a cyclic alkyl aryl or _{C 5 to 12} alkyl or _{C 6 to 30} of the _{C 1 to 30} Groups (including substituted cyclic alkyl groups). A _1-4 and B _1-4 may be the same or different from each other. X is H ⁺ , K ⁺ , Na ⁺ , 1 / 2Mg
^{2+, 1 / 2Ca 2+, 1} / 2Ba 2+, represents a quaternary ammonium cation of _NH ^{4 +} or the following general formula (3). Embedded image [In the general formula (3), n ₁ represents an integer of ₁ to 3.
R ₃ to R ₆ each represent a hydrogen atom, a C ₁ to C ₃₀ alkyl group, a C ₇ to C ₃₀ aralkyl group , or a C ₆ to C ₃₀ aryl group, and in each group, an amino group, an ether group,
Thioether group, alkoxy group, hydroxyl group, carboxamide group, sulfonamide group, urethane group, chloromethyl group, nitro group, halogen atom (F, CL, Br), C
_{6 to 30} aromatic groups, C _{6 to 30} aromatic heterocyclic groups
Or more. In the group of R _3-6
May contain a quaternized amino group. Also, R _3-6
Of these, two may combine with each other to form an alicyclic or aromatic ring. ]} 2. The charge control agent composition for forming a toner according to claim 1, wherein carbon is mixed in the step of producing the charge control agent. 3. After completion of the reaction step of the charge control agent or after purification
The carbon is mixed after the completion of the above step.
3. The charge control agent composition for forming a toner according to item 1. 4. The weight ratio of the charge control agent to carbon is 20:
The charge control agent composition for forming a toner according to any one of claims 1 to 3, wherein the charge control agent ratio is 1 to 1:20. 5. The charge control agent composition for forming a toner according to claim 1, wherein the metal complex dye is a compound represented by the general formula (4). Embedded image {In the general formula (4), Y1 ⁺ is H ⁺ , Na ⁺ , K ⁺ , N
Represents H ₄ ⁺ . } 6. The charge control agent composition according to claim 1, wherein the metal complex dye is a compound represented by the general formula (5). Embedded image {In the general formula (5), Y2 ⁺ is H ⁺ , Na ⁺ , K ⁺ , N
Represents H ₄ ⁺ . } 7. The charge control agent composition for forming a toner according to claim 1, wherein the metal complex dye is a compound represented by the general formula (6). Embedded image {In the general formula (6), Y3 ⁺ is H ⁺ , Na ⁺ , K ⁺ , N
Represents H ₄ ⁺ . } 8. An electrophotographic toner comprising the charge control agent composition according to claim 1 and a resin.