JP2003280279A - Charge controlling agent and toner containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge controlling agent to be used for controlling the electrification property of an electrophotographic toner, to provide a positive charge toner for electrostatic charge image development by using the above agent, and to provide a charge controlling agent which is colorless or in a pale color and can be used for toners of various colors such as a black toner and color toners, which is excellent in electrification characteristics, particularly saturation electrification amount and electrification stability with time, and to provide a positive charge toner for electrostatic charge image development containing the above agent. <P>SOLUTION: The charge controlling agent comprises polyamine having a piperadine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain, and the toner contains the above agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge control agent used for controlling the chargeability of an electrophotographic toner and a positively chargeable toner for developing an electrostatic charge image using the charge control agent.

[0002]

2. Description of the Related Art In copying machines and printers utilizing the principle of electrophotography, electrostatic charges are formed on a photoconductor composed of an inorganic photoconductor such as selenium or an organic photoconductor such as polyvinylcarbazole or phthalocyanine. A developing method is used in which a latent image is formed and a visible toner image is formed by supplying a pre-charged dry toner to the latent image.

The dry toner used for developing an electrostatic latent image is a one-component system in which magnetic powder such as iron powder is kneaded into toner particles, and a mixture of toner particles and magnetic powder. The two-component system used is roughly classified. The one-component system charges the surfaces of the toner particles by friction between the toner particles and the like, and the two-component system mixes and agitates the toner particles and the magnetic powder to charge the surfaces of the toner particles. Charging characteristics of toner particles such as charge rising property, charge stability over time, and saturated charge amount greatly affect the quality of electrostatic printing.Therefore, it is possible to control these physical properties and use the toner in a stable state at all times. When producing toner particles, a charge control agent having a positive charge or a negative charge is often added internally.

As a charge adjusting agent for imparting a positive charge to black toner, nigrosine has been often used conventionally. However, since nigrosine is colored, it is difficult to apply it to color toners, the demand of which is increasing in recent years, and the saturation charge amount is high, but the stability with time of charging is inferior.
When used in a high-speed printing machine, the charge rising property is poor,
There is often a problem that fog (a phenomenon in which spot-like stains occur on the non-image area) is likely to occur.

As a positive charge adjusting agent other than nigrosine, JP-A-62-53944 and JP-A-3-27052 disclose a positive charge adjusting agent using a quaternary ammonium salt. Since the quaternary ammonium salt is colorless or light-colored and has excellent stability over time with charging, it can be applied as a charge adjusting agent for color toners. But,
There is a problem that the saturated charge amount is inferior to that of nigrosine. Further, in Japanese Patent Laid-Open No. 6-348061,
Although a positive charge adjusting agent using a polyamine having a repeating structure of an alkylene group or a phenylene group and an imino group is disclosed, this is a low melting point compound, so that it is easily colored when kneaded with a toner resin, and thus it is used for a color toner. However, there is a problem that it is difficult to apply it as the charge control agent. Also,
JP-A-58-171060 discloses a colorless positive charge control agent using a polyamine having a repeating unit in which a phenylimino group and a piperazine ring are bonded via a methylene group, which is kneaded. In this case, there was a problem that the dispersibility in the binder resin for toner was poor.
As described above, at present, no charge control agent that is colorless or light-colored, has excellent charging characteristics, and is applicable to color toners has not yet been found.

[0006]

SUMMARY OF THE INVENTION The problems to be solved by the present invention are colorless or light-colored, and can be applied to toners of any color regardless of black toner and color toner, and the charging characteristics, especially the saturated charge amount and charging time A charge control agent having excellent stability and a positively chargeable toner containing the charge control agent for developing an electrostatic charge image are provided.

[0007]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a charge control agent comprising a polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain. I will provide a.

In order to solve the above problems, the present invention also provides a toner containing the charge control agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The charge control agent of the present invention is a polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain. As the quaternary ammonium salt structure, a structure represented by the general formula (1), (2) or (3) is excellent in thermal stability and is particularly preferable.

[0010]

[Chemical 4] General formula (1)

[0011]

[Chemical 5] General formula (2)

[0012]

[Chemical 6] General formula (3)

In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a methyl group, an n-butyl group or another alkyl group having 1 to 4 carbon atoms. R ⁵ represents an alkylene group having 4 to 15 carbon atoms or a polymethylene group, which may have a substituent such as a phenyl group. Specific examples of R ⁵ include a butylene group, a hexylene group, an octylene group,
Examples thereof include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group and a pentadecamethylene group. Above all,
A polymethylene group having 4 to 15 carbon atoms is preferable, and a polymethylene group having 6 to 12 carbon atoms is particularly preferable.

R ⁶ is an alkyl group having 1 to 18 carbon atoms,
Or an aralkyl group, for example, methyl group, ethyl group, n-propyl group, n-butyl group, iso-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n -Dodecyl group, benzyl group,
A 2-phenylethyl group and the like can be mentioned.

M represents an anion. As anions,
1-naphthol-3-sulfonate anion, 1-naphthol-4-sulfonate anion, 1-naphthol-5
Sulfonate anion, 1-naphthol-8-sulfonate anion, 2-naphthol-6-sulfonate anion,
Naphthol sulfonate anion such as 2-naphthol-7-sulfonate anion, tetrafluoroborate anion (BF ₄ ⁻ ), hexafluorophosphate anion (PF ₆
^- ), Hexafluoroantimonate anion (SbF ₆
^- ) And other fluorine-containing inorganic anions, molybdate anions, tungstate anions, and other metal oxo acid anions. Among them, the naphthol sulfonate anion is preferable, and the 2-naphthol-6-sulfonate anion is particularly preferable.

As the piperazine-1,4-diyl structure of the polyamine used in the present invention, the structure represented by the general formula (4) is particularly preferable.

[0017]

[Chemical 7] General formula (4) (In formula, R < ¹ > -R < ⁵ > represents group similar to the structure of said General formula (1)-(3).)

The polyamine used in the present invention may have a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain, and is represented by the above general formula (4). It is preferably composed of a repeating structure of a structure and at least one structure selected from the structures represented by the general formulas (1) to (3). There is no particular limitation on this repeating order. A structure represented by the general formula (4),
The combination with the structures represented by the general formulas (1) to (3) is not particularly limited, and, for example, the structure represented by the general formula (1) and the structure represented by the general formula (4) can be used. The polyamine may have, or the polyamine having all the structures represented by the general formulas (1) to (4) may be used.

The polyamine has 4 to 15 carbon atoms represented by R ⁵ in the general formulas (1) to (4).
The alkylene groups or polymethylene groups of may be the same or different. Further, one part of a plurality of R ⁵ 's may be an alkylene group having a small number of carbon atoms such as a methylene group, an ethylene group or a propylene group, or a polymethylene group having a large number of carbon atoms such as a hexamethylene group or a decamethylene group. However, if the proportion of the methylene group is too large, the resulting polyamine will have a very high melting point and become very hard, and the dispersibility in the binder resin will tend to be poor during kneading. If the proportion of the propylene group is too large, the resulting polyamine has a strong hydrophilicity derived from the piperazine group and has a strong affinity for water, so that water in the air is adsorbed when compounded in the toner,
The amount of charge tends to decrease. Therefore, the proportion of the alkylene group having a small number of carbon atoms is preferably 10% or less in terms of mol with respect to all the plurality of R ⁵ having a repeating structure.

In the charge control agent of the present invention, the ratio of the piperazine-1,4-diyl structure to the quaternary ammonium salt structure in the polyamine is 99: 1 to 1: 9 in terms of mol.
9 is preferable, and 95: 5 to 30:70 is particularly preferable. Within this range, it is possible to obtain a charge control agent having a high saturated charge amount and excellent stability over time in charging.

The polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain, which is used in the charge control agent of the present invention (hereinafter abbreviated as polyamine used in the present invention), is used. It can be synthesized by a known and commonly used method. For example, a polyamine having a piperazine-1,4-diyl structure in the main chain and a quaternary ammonium salt structure represented by the general formula (1) can be prepared by piperazine reaction at an alkyl (or It is alkylated (or aralkyl) with an aralkyl) halide and further neutralized with an alkali to synthesize an N-alkyl (or aralkyl) piperazine in which one imino group of piperazine is alkyl (or aralkyl) (under these conditions, One imino group is easily alkylated or aralkylated, while the other imino group has a reduced basicity, so it is extremely unlikely to be further alkylated or aralkylated.) Then, this and piperazine With a reaction temperature of 70-
It can be obtained by conducting polycondensation reaction with a dihalide such as dichloroalkane at 80 ° C. to obtain a polyamine, neutralizing it, and then anion-exchanging a halogen ion in the polyamine with a salt such as a naphtholsulfonate.

The polyamine having a piperazine-1,4-diyl structure in the main chain and a quaternary ammonium salt structure represented by the general formula (2) is piperazine at a reaction temperature of 70 to 80 ° C. Alkylation (or aralkyl) with an alkyl (or aralkyl) halide and further neutralization with an alkali to synthesize N, N′-dialkyl (or diaralkyl) piperazine, and then a mixture of this and piperazine is reacted at a reaction temperature. At 70 to 80 ° C. for polycondensation reaction with a dihalide such as dichloroalkane to obtain a polyamine, which is neutralized and then anion-exchanged with halogen ions in the polyamine with a salt such as naphtholsulfonate to obtain a polyamine. be able to.

Further, a polyamine having a piperazine-1,4-diyl structure in the main chain and a quaternary ammonium salt structure represented by the general formula (3) reacts with a mixture of piperazine and triethylenediamine. By polycondensation reaction with a dihalide such as dichloroalkane at a temperature of 70 to 80 ° C. to obtain polyamine, further neutralization, and finally by anion exchange of halogen ion in polyamine with a salt such as naphthol sulfonate, Obtainable.

In addition, a compound obtained by reacting a mixture of piperazine and a dialkylamine in an amount twice that of piperazine with a dihalide such as dichloroalkane at 70 to 80 ° C. and then neutralizing the mixture, and piperazine A mixture of
It can be obtained by polycondensation with a dihalide such as dichloroalkane at a reaction temperature of 70 to 80 ° C. to obtain a polyamine, and anion exchange of a halogen ion in the polyamine with a salt such as a naphtholsulfonate.

Instead of the piperazine used in the above method, 2-methylpiperazine, 2-ethylpiperazine, 2
-Butylpiperazine, 2,3-dimethylpiperazine,
2,3,5-trimethylpiperazine, 2,3,5,6-
What can react with the imino group of the piperazine skeleton such as tetramethylpiperazine can be used without particular limitation. These compounds may be used alone or in combination of two or more.

Specific examples of the alkyl (or aralkyl) halide used in the above method include methyl chloride,
Ethyl chloride, n-propyl chloride, isopropyl chloride, n-butyl chloride, n-hexyl chloride, n-octyl chloride, methyl bromide, ethyl bromide, n-butyl bromide, n-hexyl bromide, n-octyl bromide, methyl iodide , Alkyl iodides such as ethyl iodide and n-butyl iodide, and aralkyl halides such as benzyl chloride, 2-phenylethyl chloride, benzyl bromide and benzyl iodide.

Examples of the dihalide used in the above method include 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane and 1,8-dichlorooctane. , 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-
Dichloroundecane, 1,12-dichlorododecane,
1,13-dichlorotridecane, 1,14, -dichlorotetradecane, 1,15-dichloropentadecane, 1,
6-dibromohexane, 1,8-dibromooctane,
1,6-diaiodohexane, 2,2-dimethyl-1,
3-dichloropropane etc. are mentioned. Among these, 1,6-dichlorohexane, 1,8-dichlorooctane and 1,10-dichlorodecane are particularly preferable.

The dihalide can be used alone or in combination of several kinds. Also, dichloromethane, 1,2
A small amount of a dihalide having a small number of carbon atoms such as dichloroethane or 1,3-dichloropropane, or a dihalide having a large number of carbon atoms may be used together. But,
When the amount of dichloromethane used is too large, the melting point of the obtained polyamine increases, and when the polyamine and the binder resin are kneaded, the dispersibility in the binder resin tends to deteriorate, and 1,2-dichloroethane is also used. , 1,3
-If the amount of dichloropropane or the like used is too large, the affinity of the polyamine for water remains strong, so that water in the air is adsorbed during blending with the toner, and the charge amount tends to decrease. The compounding ratio of these dihalides having a small number of carbon atoms is preferably 10% by mass or less of the total amount of dihalides.

The salts used in the above method include 1-naphthol-3-sodium sulfonate and 1-naphthol-
Sodium 4-sulfonate, sodium 1-naphthol-5-sulfonate, sodium 1-naphthol-8-sulfonate, sodium 2-naphthol-6-sulfonate, sodium 2-naphthol-7-sulfonate, 1-
Naphthol-3-sulfonate, potassium 1-naphthol-4-sulfonate, potassium 1-naphthol-5-sulfonate, potassium 1-naphthol-8-sulfonate, potassium 2-naphthol-6-sulfonate, 2-
Naphthol sulfonates such as potassium naphthol-7-sulfonate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium tetrafluoroborate, sodium hexafluorophosphate, potassium hexafluorophosphate, ammonium hexafluorophosphate, Fluorine-containing inorganic salts such as sodium hexafluoroantimonate, potassium hexafluoroantimonate, ammonium hexafluoroantimonate, lithium molybdate, sodium molybdate, potassium molybdate, lithium tungstate, sodium tungstate, potassium tungstate, etc. A metal oxo acid salt is mentioned. Among them, sodium 2-naphthol-6-sulfonate is particularly preferable.

The triethylenediamine used in the above method is, instead, tetramethylethylenediamine, tetraethylethylenediamine, tetra-n-butylethylenediamine, N, N, N ', N'-tetramethyl-1,3.
A tertiary amine such as -propanediamine, N, N, N ', N'-tetramethyl-1,9-nonanediamine may be used.

As the dialkylamine used in the above method, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-hexylamine, di-n-octylamine, dibenzylamine,
Examples include N, N-methyl, benzylamine, N-methylaniline and the like.

The mixing ratio of N-alkyl (or aralkyl) piperazine or N, N'-dialkyl (or aralkyl) piperazine synthesized by the above-mentioned method, or a tertiary amine such as triethylenediamine, and piperazine is in terms of mol. The range of 99: 1 to 1:99 is preferable, and 9 is particularly preferable.
The range of 5: 5 to 30:70 is preferable. The mixture is previously N-alkyl (or aralkyl) as in the method above.
After synthesizing piperazine, new piperazine may be mixed, or when synthesizing N-alkyl (or aralkyl) piperazine, alkyl (or aralkyl) halide is reacted with excess piperazine to give N-alkyl (or aralkyl). ) A mixture of piperazine and unreacted piperazine may be obtained. On the other hand, the mixing ratio of the mixture of the tertiary amine and piperazine and the dihalide is 4: in terms of mol.
It is preferably in the range of 1 to 1: 4, and 2: 1 to 1: 1.
A range of 2 is especially preferred.

It is also possible to synthesize a polyamine leaving an imino group at the terminal and to react a small amount of formalin with the imino group. At this time, if the amount of reaction of formalin is too large, the melting point of the obtained polyamine increases, and the dispersibility in the binder resin tends to become poor at the time of kneading. Therefore, the amount of reaction of formalin is 0 for 1 mol of imino group. It is preferable to keep it below 1 mol.

The number average molecular weight of the polyamine used in the present invention is preferably in the range of 500 to 50,000, and is 2,0.
The range of 00 to 30,000 is particularly preferable. When the number average molecular weight of the polyamine is less than 500, the melting point of the polyamine is low, and the polyamine tends to scatter during kneading when processing into a toner, and the number average molecular weight of the polyamine is 50,0.
When it exceeds 00, the dispersibility at the time of the kneading tends to be poor, which is not preferable.

The charge adjusting agent comprising a polyamine used in the present invention is useful as a positively chargeable charge adjusting agent for controlling the chargeability of toner used in electrophotography and the like.

The method of internally adding the charge control agent of the present invention to the toner is not particularly limited. For example, the compound used as the charge control agent is pre-ground and, if necessary, further classified, and then the ground product is obtained. , A toner resin, a colorant, and other toner constituent components, and a method of mixing and melting and kneading.

When the charge control agent of the present invention is internally added to the toner, the addition amount is 0.1 with respect to 100 parts by mass of the binder resin.
The range of ˜15 parts by mass is preferable, and the range of 0.5˜10 parts by mass is particularly preferable. When the amount of the charge control agent used in the toner is less than 0.1 parts by mass, the rising property at the time of charging tends to be poor, or the toner tends to scatter, and the amount of the charge control agent used is 15 parts by mass. If it is more than the amount, the charge amount of the toner when frictionally charged tends to decrease with time, and the charging stability tends to be poor.

By adding the charge control agent of the present invention by the above method, a positively chargeable toner can be obtained. Further, other charge control agents can be used in combination within a range that does not impair the performance of the charge control agent and the purpose of use of the toner. Further, the charge control agent of the present invention can be used in combination with a negatively chargeable charge control agent as necessary for adjusting the charge amount when producing a toner, and not only the positively chargeable toner but also the negatively chargeable toner can be used. It can also be used as a charge control agent for toner.

As the binder resin used in the toner of the present invention, known resins used for electrophotography can be used. Specific examples of the resin include polystyrene,
Styrene / (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid ester / acrylonitrile copolymer, styrene / butadiene copolymer, styrene /
Styrene resin such as vinyl chloride copolymer, styrene / maleic acid copolymer, polyester resin, epoxy resin,
(Meth) acrylic resin, phenol resin, xylene resin, vinyl chloride resin, polyurethane resin, polyvinyl butyral resin, etc. may be mentioned. Above all, styrene /
(Meth) acrylic acid ester resin and polyester resin are particularly preferable. Usually, one kind of these resins is used, but two or more kinds can be used together if necessary.

As the colorant used in the toner of the present invention, various known organic pigments, inorganic pigments, dyes and the like can be used. Specific examples of the colorant include black pigments such as carbon black; blue pigments such as phthalocyanine blue, aniline blue, and ultramarine blue; green pigments such as malachite green, phthalocyanine green, and brilliant green; quinacridone, rose bengal, permanent red, Red pigments such as Irgasin Red and Toluidine Red; yellow pigments such as Bengin Yellow, Quinoline Yellow, Fast Yellow G, and Hansa Yellow; triarylmethane dyes, azo dyes, nigrosine dyes, and the like.

To the toner of the present invention, additives usually used in toners, such as higher fatty acids or metal salts thereof, natural or synthetic waxes, etc., can be added as required.

The toner of the present invention can be applied to both a two-component developer and a one-component developer. For example, when the toner of the present invention is used as a two-component developer, the toner is mixed with carrier powder, and the carrier powder used at that time is, for example, iron powder, ferrite powder, nickel powder, or the like. Magnetic powder, glass beads, etc., as well as a coating carrier whose surface is treated with a resin.

When the toner of the present invention is used as a one-component developer, for example, an appropriate amount of magnetic fine powder such as iron powder or ferrite powder is added and dispersed in the form of magnetic one-component at the time of toner production, or It is used in the form of non-magnetic single component that does not contain magnetic powder.

The charge adjusting agent comprising a polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain of the present invention is compared with the conventionally used quaternary ammonium salt type. In addition, it has a high saturated charge amount, and is far superior to Nigrosine in terms of stability with time of charge. Further, since the polyamine is a light color,
It is extremely useful as a charge control agent for not only black toner but also color toner.

[0045]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, all "parts" and "%" are based on mass unless otherwise specified.

(Synthesis Example 1) 100 g of piperazine and 150 g of ethanol were charged and dissolved in a reaction vessel equipped with a reflux condenser, a thermometer, a decanter and a stirrer. The contents were heated to 40 ° C., 36.6 g of benzyl chloride was added dropwise while maintaining the temperature within a range not exceeding 50 ° C., and stirring was continued for another 30 minutes.
5.3 g was added and the contents were stirred at 80 ° C. for 1 hour,
The produced N-benzylpiperazine (hydrochloride) was neutralized. Then, 170.3 g of 1,6-dichlorohexane was added dropwise at the same temperature over about 1 hour, and a polyamine (hydrochloride) synthesis reaction was carried out while stirring for 4 hours.
Next, after distilling off 90 g of ethanol, an aqueous solution prepared by dissolving 77.7 g of 98% caustic soda in 160 g of water was added,
The polyamine (hydrochloride) was neutralized at 0 ° C. for 1 hour. Then, after diluting the content with 300 g of water and returning to room temperature to separate the aqueous layer, 81.2 g of sodium 2-naphthol-6-sulfonate having a purity of 87.5% and 500 g of water were added, and at 70 ° C. Chloride ions in the produced polyamine were ion-exchanged with 2-naphthol-6-sulfonate anion over 1 hour. Finally, the content was filtered, washed with water, and then dried at 110 ° C. for 3 hours to obtain 226 g of polyamine (P-1) having a plurality of structures of the following formula. This polyamine (P-1) is light in color and has a melting point of 114 to 130 ° C.
(DSC measurement value), number average molecular weight (hereinafter abbreviated as Mn).
The value is 5,90 for polymethylmethacrylate conversion.
It was 0.

[0047]

[Chemical 8]

[0048]

[Chemical 9]

(In the formula, R ^{1 to} R ⁴ are hydrogen atoms, R ⁵ is a hexamethylene group, R ⁶ is a benzyl group, and M is a 2-naphthol-6-sulfonate anion.)

(Synthesis Example 2) In Synthesis Example 1, 1,6-
Polyamine (P-2) was reacted in the same manner as in Synthesis Example 1 except that 85.0 g of 1,6-dichlorohexane and 100.7 g of 1,8-dichlorooctane were used instead of 170.3 g of dichlorohexane. 235 g were obtained. This polyamine (P-2) is light in color and has a melting point of 115 to 126 ° C.
Mn was 5,500.

(Synthesis Example 3) In Synthesis Example 1, 1,6-
Polyamine (P-3) was reacted in the same manner as in Synthesis Example 1 except that 102.2 g of 1,6-dichlorohexane and 92.7 g of 1,10-dichlorodecane were used instead of 170.3 g of dichlorohexane. 251 g were obtained. This polyamine (P-3) is light in color and has a melting point of 110 to 126 ° C.
Mn was 5,600.

(Synthesis Example 4) In Synthesis Example 1, 1,6-
Polyamine (P-4) was obtained in the same manner as in Synthesis Example 1 except that 126.7 g of 1,6-dichlorohexane and 34.9 g of 1,4-dichlorobutane were used instead of 170.3 g of dichlorohexane. 215 g were obtained. This polyamine (P-4) has a melting point of 109 to 121 ° C., and Mn is
It was 4,900.

Synthesis Example 5 In Synthesis Example 1, 2,5-dimethylpiperazine 13 was used instead of 100 g of piperazine.
The reaction was performed in the same manner as in Synthesis Example 1 except that 3 g was used to obtain 241 g of polyamine (P-5). This polyamine (P-5) has a melting point of 112 to 128 ° C. and Mn of 5,700.
Met.

Synthesis Example 6 In Synthesis Example 1, 1-chlorooctane 4 was used in place of 36.6 g of benzyl chloride.
The reaction was performed in the same manner as in Synthesis Example 1 except that 3.0 g was used, and 220 g of polyamine (P-6) was obtained. This polyamine (P-6) has a light color and a melting point of 115 to 136 ° C. and Mn.
Was 5,900.

Synthesis Example 7 In Synthesis Example 1, sodium 2-naphthol-6-sulfonate (87.5% purity)
The reaction was performed in the same manner as in Synthesis Example 1 except that 70.8 g of sodium 1-naphthol-4-sulfonate (89.2% purity) was used instead of 81.2 g, and polyamine (P-
215 g of 7) was obtained. This polyamine (P-7) was light-colored and had a melting point of 116 to 133 ° C. and Mn of 5,500.

(Synthesis Example 8) 15.0 g of piperazine and 150 g of ethanol were charged and dissolved in a reaction vessel equipped with a reflux condenser, a thermometer, a decanter and a stirrer.
While heating the contents to 75 ° C and maintaining this temperature,
41.8 g of n-hexyl chloride was added dropwise, and further 30
After continuing stirring for 1 minute, 18.4 g of sodium carbonate was added, and the content was further stirred at 80 ° C. for 1 hour to neutralize the produced N, N′-di-n-hexylpiperazine (dihydrochloride). The reaction was carried out. Then, further piperazine 85.0g
After adding and dissolving, 170.3 g of 1,6-dichlorohexane was added dropwise at the same temperature over about 1 hour, and a reaction for synthesizing polyamine (hydrochloride) was performed while stirring for 4 hours. Next, after distilling off 90 g of ethanol, an aqueous solution prepared by dissolving 75.3 g of 98% caustic soda in 157 g of water was added, and the polyamine (hydrochloride) was neutralized at 90 ° C. for 1 hour. Then, after diluting the content with 300 g of water and returning to room temperature to separate the aqueous layer, sodium 2-naphthol-6-sulfonate having a purity of 87.5% 97.4.
g and 500 g of water were added, and chlorine ions in the produced polyamine were ion-exchanged with 2-naphthol-6-sulfonate anion at 70 ° C. for 1 hour. Finally, the content was filtered, washed with water, and then dried at 110 ° C. for 3 hours to obtain 235 g of polyamine (P-8) having a plurality of structures of the following formula. This polyamine (P-8) has a light color and a melting point of 123-
148 degreeC and Mn were 5,300.

[0057]

[Chemical 10]

[0058]

[Chemical 11]

(Wherein R ^{1 to} R ⁴ are hydrogen atoms, R ⁵ is a hexamethylene group, R ⁶ is an n-hexyl group, and M is a 2-naphthol-6-sulfonic acid anion).

(Synthesis Example 9) 100 g of piperazine, 18.5 g of triethylenediamine and 178 g of ethanol were charged and dissolved in a reaction vessel equipped with a reflux condenser, a thermometer, a decanter and a stirrer. 6
-Dichlorohexane (194.7 g) was added dropwise over about 1 hour, and the reaction for synthesizing polyamine (hydrochloride) was performed while stirring for 4 hours. Next, after 120 g of ethanol was distilled off, an aqueous solution of 94.1 g of 98% caustic soda dissolved in 210 g of water was added, and the polyamine (hydrochloride) was neutralized at 90 ° C. for 1 hour. Then, after diluting the content with 500 g of water and returning to room temperature to separate the aqueous layer,
93.0 g of sodium 2-naphthol-6-sulfonate having a purity of 7.4% and 400 g of water were added, and chlorine ions in the produced polyamine were ionized into 2-naphthol-6-sulfonate anion at 70 ° C. for 1 hour. Exchanged. Finally, the content was filtered, washed with water, and then dried at 110 ° C. for 3 hours to obtain a polyamine (P-9) having a plurality of structures of the following formula.
264 g was obtained. This polyamine (P-9) is a light color,
The melting point was 133 to 152 ° C, and the Mn was 5,200.

[0061]

[Chemical 12]

[0062]

[Chemical 13]

(In the formula, R ^{1 to} R ⁴ are hydrogen atoms, R ⁵ is a hexamethylene group, and M is a 2-naphthol-6-sulfonate anion.)

Example 1 Polyester resin for toner [glass transition temperature (Tg) = 61 ° C., acid value≈7, mass average molecular weight (hereinafter abbreviated as Mw) ≈10,000, Mn≈)
4,700] 100 parts, the polyamine (P
-1) 1.5 parts, 5 parts of carbon black "MA-100" manufactured by Mitsubishi Chemical Co., Ltd. and 2 parts of polypropylene wax "Viscor 550P" manufactured by Sanyo Kasei Co., Ltd. were premixed with a Henschel mixer, and then After melt-kneading with a heating roll mill and cooling to room temperature, the mixture was finely pulverized with a jet mill and further classified to prepare a black toner as a powder having an average particle size of 10 μm.

(Examples 2 to 9) Instead of the polyamine (P-1) obtained in Synthesis Example 1 in Example 1, Synthesis Examples 2 to 2 were used.
A black toner was prepared in the same manner as in Example 1 except that each of the polyamines (P-2) to (P-9) obtained in No. 9 was used.

(Comparative Example 1) Synthesis Example 1 in Example 1
A black toner was prepared in the same manner as in Example 1 except that the compound (P-10) represented by the following formula was used in place of the polyamine (P-1) obtained in.

[0067]

[Chemical 14]

Comparative Example 2 Synthesis Example 1 in Example 1
Example except that 3 parts of "Bontron N-04" (resin kneaded product = containing about 55% as a nigrosine base), which is Nigrosine manufactured by Orient Chemical Co., was used in place of the polyamine (P-1) obtained in Example. A black toner was prepared in the same manner as in 1.

(Toner Evaluation Method) (A) Measurement of Charge Amount: 4 g of each of the toners obtained in Examples 1 to 9 and Comparative Examples 1 and 2 and 96 g of silicone resin-treated ferrite carrier were placed in a plastic bottle having a capacity of 100 ml. Place this plastic bottle on a ball mill and stir at a rotation speed of 200 rpm for 3 minutes, 10 minutes, 30
After a lapse of minutes and after a lapse of 60 minutes, sampling was performed to measure the charge amount of each sample. To measure the charge amount, blow-off charge amount measuring device "TB-200" manufactured by Toshiba Chemical Co., Ltd.
It was used. The results are summarized in Tables 1 and 2.

[0070]

[Table 1] [Table 1]

[0071]

[Table 2] [Table 2]

(B) Printing Test Using the toners obtained in Examples 1-9 and Comparative Examples 1-2,
A printing test was conducted using a commercially available magnetic two-component developing machine, and the optical density (OD) of the solid printed image was measured with a Macbeth optical densitometer for the 10th sheet and the 50,000th sheet after the start of printing.
The results are summarized in Tables 3 and 4. As a result,
Examples 1 to 9 are OD at the 10th sheet and the 50,000th sheet after the start of printing.
Was almost unchanged, but in Comparative Examples 1 and 2, O
D decreased by 5% or more.

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[Table 3] [Table 3]

[0074]

[Table 4] [Table 4]

(Example 10) Polyester resin for toner [glass transition temperature (Tg) = 61 ° C., acid value≈7, Mw≈
10,000, Mn≈4,700] 100 parts, Synthesis example 1
0.7 parts of the polyamine (P-1) obtained in Step 1, and a blue pigment "KET BLUE 106 (CIPig.No.B)" manufactured by Dainippon Ink and Chemicals, Inc.
-15-4) "and 2 parts of polypropylene wax" Viscor 550P "manufactured by Sanyo Kasei Co., Ltd. were premixed with a Henschel mixer, then melt-kneaded with a heating roll mill, and then cooled to room temperature. This was finely pulverized with a jet mill and further classified to obtain a blue toner as powder having an average particle size of about 10 μm.

(Examples 11 to 14) In Example 10, instead of the polyamine (P-1) obtained in Synthesis Example 1, the polyamine (P-2) obtained in Synthesis Example 2, 5, 8 or 9 was used. ,
A blue toner was obtained in the same manner as in Example 10 except that (P-5), (P-8) or (P-9) was used.

(Comparative Example 3) In Example 10, instead of the polyamine (P-1) obtained in Synthesis Example 1, a compound (P-
A blue toner was obtained in the same manner as in Example 10 except that 10) was used.

With respect to each of the blue toners obtained in Examples 10 to 14 and Comparative Example 3, a charge amount measurement and a print test were performed in the same procedure as in (A) and (B) of Example 1, and the results are shown in Table 5. And shown in Table 6 collectively.

[0079]

[Table 5] [Table 5]

[0080]

[Table 6] [Table 6]

(Example 15) Polyester resin for toner [glass transition temperature (Tg) = 65.6 ° C., acid value≈10 m]
gKOH / g, Mw≈10,000, Mn≈4,80
0] 100 parts, polyamine (P-1) obtained in Synthesis Example 1
0.7 parts, red pigment "KE" from Dainippon Ink and Chemicals, Inc.
T RED 309 (CI Pig.No.R-122) "6 parts and (Sanyo Kasei Co., Ltd. polypropylene wax" Viscole 5 "
2 parts of "50P" were premixed with a Henschel mixer, then melt-kneaded with a heating roll mill, and then cooled to room temperature. This was finely pulverized with a jet mill and further classified to obtain a red toner as powder having an average particle size of 10 μm.

(Examples 16 to 19) Instead of the polyamine (P-1) obtained in Synthesis Example 1 in Example 15, the polyamine (P-2) obtained in Synthesis Examples 2, 3, 5, and 8 was used. ,
A red toner was obtained in the same manner as in Example 15 except that (P-3), (P-5), and (P-8) were used.

Comparative Example 4 In Example 15, instead of the polyamine (P-1) obtained in Synthesis Example 1, (P-10)
A red toner was obtained in the same manner as in Example 15 except that was used.

With respect to each of the red toners obtained in Examples 15 to 19 and Comparative Example 4, the charge amount was measured by the same procedure as in (A) of Example 1, and the results are shown in Table 7.

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[Table 7] [Table 7]

(Example 20) Polyester resin for toner [glass transition temperature (Tg) = 65.6 ° C., acid value≈10,
Mw≈10,000, Mn≈4,800] 100 parts, polyamine (P-1) 0.7 part obtained in Synthesis Example 1, yellow pigment “Toner Yellow HG (CIPig.
No. 180) "and 2 parts of polypropylene wax" Viscor 550P "manufactured by Sanyo Kasei Co., Ltd. were premixed with a Henschel mixer, and then melt-kneaded with a heating roll mill and then cooled to room temperature. This is finely pulverized with a jet mill and further classified to obtain a powder having an average particle size of 10 μm.
A yellow toner was obtained.

(Examples 21 to 24) In Example 20, instead of the polyamine (P-1) obtained in Synthesis Example 1, the polyamine (P-3) obtained in Synthesis Examples 3, 4, 6 and 7 was used. ,
A yellow toner was obtained in the same manner as in Example 20 except that (P-4), (P-6), and (P-7) were used, respectively.

(Comparative Example 5) In Example 20, instead of the polyamine (P-1) obtained in Synthesis Example 1, a compound (P-
A yellow toner was obtained in the same manner as in Example 20 except that 10) was used.

With respect to each of the yellow toners obtained in Examples 20 to 24 and Comparative Example 5, the charge amount was measured by the same procedure as in (A) of Example 1, and the results are shown in Table 8.

[0090]

[Table 8] [Table 8]

From the above results, the toner to which the charge adjusting agent comprising the polyamine of the present invention is added has an average charge amount of +1.
It was found that 0 to 11 μC / g was excellent in stability with time of charging and was at a considerably high level. All print tests were also good. On the other hand, the compound (P-10)
The toner to which was added had relatively good stability over time in charging, but had a low average charge amount. Also, Bontron N-0
The toner to which No. 4 was added had a high average charge amount, but was considerably inferior in stability with time of charging.

[0092]

Industrial Applicability The charge control agent of the present invention comprises a polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain, and has a charging property, particularly a saturated charge amount and a charging property. Excellent stability over time. Further, since it is a light color, it is possible to obtain a clear color image with good color reproducibility especially when applied to a color toner.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H005 AA06 CA15 CA28 DA03                 4J043 PA02 PA04 QB20 RA08 RA09                       SA06 SA43 SA47 UA381                       UB011 XB15 ZA41 ZA60                       ZB05

Claims (3)

[Claims] 1. A charge control agent comprising a polyamine having a piperazine-1,4-diyl structure and a quaternary ammonium salt structure in the main chain. 2. The charge control agent according to claim 1, wherein the quaternary ammonium salt structure is at least one structure selected from formulas (1) to (3). [Chemical 1] General formula (1) General formula (2) General formula (3) (In formula, R < ¹ > -R < ⁴ > respectively independently represents a hydrogen atom or a C1-C4 alkyl group, R < ⁵ > is a C4-C15 alkylene group or Represents a polymethylene group, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, or an aralkyl group, and M represents a naphtholsulfonic acid anion, a fluorine-containing inorganic anion, or a metal oxo acid anion.) 3. A toner containing the charge control agent according to claim 1.