JPH037768A - Organometallic complex salt compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 and R2 are H, nitro, methyl, Cl, sulfonamide or methyl sulfone; R is methyl, ethyl or phenylmethyl; M is Cr, Co or Fe; X is H, Na, K, ammonium or organic amine salt). EXAMPLE:A compound expressed by formula II. USE:An electric charge regulator used for toners employed in developing electrostatic latent images of electrophotography, electrostatic recording, etc. PREPARATION:A compound expressed by formula III is diazotized in water and the resultant diazo compound is then coupled with a coupling component in water or a mixture solution of water with an organic solvent, such as DMF, to synthesize a monoazo compound expressed by formula V. The resultant compound expressed by formula V is subsequently reacted with a metalating agent, as necessary, in the presence of sodium acetate, etc., in water or a mixture solution thereof with an organic solvent at 60-100 deg.C and pH 3-9.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an organometallic complex useful as a charge control agent for toners used in particular to develop electrostatic latent images in electrophotography, electrostatic recording, etc. .

Conventional technology In toners for electrostatic latent image phenomenon, it is difficult to control triboelectricity with only a binder resin, and it is widely used to add dyes, pigments, etc. for the purpose of improving this. Dyes and pigments that have been put to practical use in this field today include nigrosine dyes that impart a positive charge to the toner and organometallic complex dyes that impart a negative charge.

Problems to be Solved by the Invention As electrophotography and electrostatic recording media have become more multifunctional and faster, toners with better durability, environmental stability, resolution and contrast, and less fogging have been developed. There is a need for the development of charge control agents for the preparation of That is, an object of the present invention is to prepare a toner that is not affected by environments such as temperature and humidity, can withstand long-term use, has excellent image resolution and reproducibility, has high density, and provides images without fogging. To provide a charge control agent for

Means for Solving the Problems As a result of extensive research aimed at improving the above-mentioned problems, the present invention has been achieved. That is, the present invention provides formula (1) [in formula (1), R1
and R2 is an atom or group selected from a hydrogen atom, a nitro group, a methyl group, a chloro atom, a sulfonic acid amide group, or a methylsulfone group; R is a methyl group, an ethyl group, or a phenylmethyl group; M is chromium; Cobalt or iron atom
represents hydrogen, sodium, potassium, ammonium, or an organic amine salt, respectively] An organometallic complex salt compound represented by the following is provided.

The compound of formula (1) can completely solve the above problems when used as a charge control agent, and is an organometallic salt complex compound with a novel structure.

Type 2:1 metal complex compounds which do not contain a sulfone group in the molecule and have chromium, cobalt or iron as a binding metal are disclosed in, for example, JP-A-58-185653 and JP-A-61-101558.
, JP-A-63-281170, etc., all of which use beta-naphthol or petanaphthol derivatives as couplers. On the other hand, no specific example of a complex compound using alpha-naphthol as a coupler can be found.

This is for example Dyes and Pigment 9
(1988) pp. 153-163 “Die 13eei
nflusscmg des O/PVerhMITn
isses bei Azo kupplungen
mit 1-Naphthol inNichtwWb
This is believed to be because, as described in rigen Mcdien J, the 4-position of 1-naphthol takes precedence in the coupling reaction in water, and the coupling reaction to the 2-position is difficult to occur.

When M in formula (1) is cobalt, the compound of the present invention exhibits a clear blue to green hue, and is a 2: type 1 cobalt complex having absorption in the long wavelength band of the visible region. It is. Such compounds have excellent light resistance and can be used as dyes for dyeing polyamides, polyimides, etc.

The metal complex compound (1) of the present invention has the following formula [in formula (2),
R1 and R2 are as described above. ] The compound represented by the above is diazotized in water by a conventional method, and the resulting diazotized product is combined with the following formula [In formula (3), R is as described above. ] in water or a mixture of water and an organic solvent such as DMF or acetone to form the following formula (3) [In formula (3), R+, R2 and R is as described above. ] A monoazo compound represented by is synthesized, and then this monoazo compound is heated to pH 3 in water or a mixture of water and an organic solvent in the presence of a metallizing agent and, if necessary, sodium acetate, potassium acetate, etc. ~9 and can be obtained by reacting at a temperature of 60 to 100°C.

Specific examples of the compound represented by formula (2) include 5-nitro-2-aminephenol, 4-nitro-2-aminophenol, 4,6-dinitro-2-aminephenol, 4-chloro-2-aminephenol, 4-methyl-6-nitro-2-76=minophenol, 4-methyl-2-aminephenol,
5-methyl-2-aminephenol, 2-aminephenol, 4-sulfamoyl-2-aminephenol, 4
-methylsulfonyl 2-amine phenol and the like.

Specific examples of the coupling component represented by the formula (3) include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-phenylmethoxy-1-naphthol, and the like. (In addition, 4-ethoxy-
1-naphthol beam, hydro-
It can be synthesized by reaction of α-naphthoquinone and ethanol. ) Examples of metallizing agents used in the production of formula (I) include the well-known chromium (m) sulfate, chromium salicylate, chromium (m) chloride, cobalt (n) chloride, cobalt (II) sulfate, Examples include chromium (III) formate, iron (m) chloride, iron alum, and the like.

The thus obtained solution or dispersion of the organometallic complex of formula (I) in water or water and an organic solvent is reacted with ammonia or an organic amine to form an ammonia or organic amine salt. You can also do that.

Examples of the amine include methylamine, ethylamine, dimethylamine, ethanolamine, butylamine, hexylamine, 2-ethylhexylamine, 3-ethylhexylamine, and 3-ethylhexylamine.
Examples include butoxypropylamine, 3-isopropoxypropylamine, and the like.

The metal complex compound represented by formula (1) of the present invention has high thermal and storage stability, excellent chargeability, and has a small bulk specific gravity and a large surface area, so it is suitable as a charge control agent for toner.

Furthermore, the compound (1) generally shows negative results in mutagenicity tests, is stable against impact and heat, and does not decompose or burn. A toner containing (1) is negatively charged and provides a clear and stable image even under low humidity.

In producing the toner containing the metal complex of formula (1) of the present invention, known carbon black, phthalocyanine blue, iron black, etc. can be used as the colorant, and known acrylic esters can be used as the binder resin. , olefins,
Single polymers such as styrenes can be used. These binder resins are usually used in an amount of 10 to 10,000 parts per 1 part of the metal complex. Furthermore, when used as a two-component phenomenon agent, it can be mixed with carrier powder such as known iron powder, ferrite, glass beads, etc.

In addition, the metal complex compound of the present invention has excellent light resistance, heat resistance, water resistance, and high clarity, so it can be used as a coloring agent for various resins.
It can also be used as a paint.

EXAMPLES The present invention will be described below with reference to Examples, where parts are by weight.

Example 1 4.0 parts of 4.6-sinitro-2-aminephenol was added to 1
The mixture was dissolved in 0 parts of acetone, poured into 80 parts of ice containing 5 parts of 35% hydrochloric acid and 1.5 parts of sodium nitrite, and stirred for 3 hours to complete diazotization, yielding a reaction solution containing yellow crystals. Ta. A solution prepared by dissolving 3.5 parts of 4-methoxy-1-naphthol in 15 parts of acetone was poured into the reaction solution containing this diazonium salt, and a 10% aqueous sodium carbonate solution was added to adjust the pH to 9-10. The mixture was stirred at 5° C. for 5 hours to complete the coupling, and a reaction solution containing 7.2 parts of a monoazo compound represented by formula (4), which was dark blue in appearance and exhibited a green-blue color in acetone, was obtained.

Next, 8.0 parts of sodium acetate trihydrate and 2.8 parts of cobalt chloride hexahydrate were added to this reaction solution, the temperature was raised to 85-90°C, and the mixture was reacted for 3 hours to obtain 7.8 parts of crystals. Ta. This crystal had a black appearance and contained 7.6 parts of a compound whose structure was represented by formula (5).

Furthermore, I was added to the reaction solution containing the compound of formula (4) obtained in the same manner
) 50 parts of MF, 2.2 parts of chromium sulfate (IID) and 10 parts of sodium acetate were added, heated, and reacted at 90°C for 5 hours.
The reduced color was dark green.

The mixture was stirred at a temperature of 80° C. for 7 hours while adjusting the pH to 5 to 7 to obtain 8.1 parts of the compound of formula (6). (7) λma in acetone
x was 524 nm and 678 nm, and the color reduction was a dark line.

Example 2. 3.1 parts of 2-amino-5-nitrophenol to 60 parts of water
The mixture was heated and dissolved in 48% caustic soda, ice was added to bring the temperature to 10°C, and diazotization was performed with 1.5 parts of sodium nitrite and 8 parts of 35% hydrochloric acid. 4-methoxye-naphthol 3
．． An aqueous solution of 5 parts of 48% caustic soda dissolved in 50 parts of water was heated to 10°C with ice and poured into the reaction solution containing the diazonium compound. While keeping the temperature below 15℃,
The mixture was stirred overnight while adjusting the pH to 11.5 to 12 with a 0% aqueous sodium hydroxide solution to obtain a reaction solution containing a compound represented by formula (8) with a dark blue appearance. Next, 60 parts of sodium acetate and cobal chloride (COCl2.6H202) were added to this reaction solution.
Add 8 parts and raise the temperature to 800G while maintaining the pH between 6 and 7.
The mixture was stirred at this temperature for 10 hours. filter the product;
Dry grinding yielded 6.9 parts of a dark blue powder. This is the formula (
9) It is a metal complex salt represented by the following, exhibits a clear blue color in acetone, and has a λmax of 635 nm.

To the reaction solution containing the compound of formula (8) obtained in the same manner, 7 parts of sodium acetate, chromium chloride CrCIa.6H203,2
The mixture was heated to 90 to 95°C for 6 hours. House-to-house, dried, dried black powder expressed as 7,0 parts 3 4, dissolved in acetone in blue color, λmax is 625n
It was m.

In addition, a reaction solution containing the compound of formula (8) obtained in the same manner and ferric chloride in water were heated at 80°C while keeping the pH at 6 to 7.
When reacted for a period of time, a compound represented by the formula (Step 1) was obtained, which had a black-blue appearance and dissolved red in acetone.

A similarly obtained reaction solution containing the compound of formula (12) was reacted with an inorganic metal salt by the method described in Example 1, and the results were expressed by the following formulas (13), (14), and (15). 7.8 parts of a complex salt compound dissolved in brown color in acetone was obtained.

Example 3 2.5 parts of 2-amino-4-methylphenol was diazotized in a conventional manner, and an acetone solution of 5.0 parts of 4=phenylmethoxy-1-naphthol was added to the resulting reaction solution. The pH was maintained at 11-12 with caustic soda and stirred overnight. Dissolve in the mixture of formula (12) and keep the liquid temperature at 30'C,
2.5 parts of 3-butoxypropylamine was added to this, and the product was crystallized from the reaction solution to obtain a compound represented by formula (17).

A complex salt compound of was obtained. The reduced colors in acetone were purple, brown, and reddish-blue, respectively.

Example 4 A metal complex compound of formula (16) produced in the same manner as the method for synthesizing the metal complex of formula (9) in Example 2 is shown below.

10 parts of the compound in 180 parts of water and 20 parts of DMF
- 18- 23 Application example 1゜The above mixture was kneaded at 170°C (hot melt kn)
ea-ding) L, finely pulverized and classified to 15μ
A particle with a particle size of m was collected.

Separately, a comparative toner was prepared using a metal complex having the following structure as a charge control agent. 1 part of each toner and 9 parts of iron powder as a carrier were mixed, and the charge amount of both toners was tested by a 131ow-off test.
) and obtained the following results.

Charge amount μC/g Toner using formula (7) as a charge control agent -21,75
Formula (43) -11°00 Furthermore, high-quality images were obtained by copying with the toner containing Formula (7) as a charge control agent, and the images were stable and no fogging was observed even after repeated tests.

The compound of formula (7) exhibits a clear blue color when dissolved in an organic solvent. When used as a coloring agent for resins such as polyamide and polyester, it could be colored a bright blue color with excellent light and water resistance.

Application Example 2 Polyester resin 94 parts Carbon blank 4 parts Compound of formula (17) 2 parts A toner having a particle size of 15 μm or less was obtained in the same manner as in Application Example 1, and the amount of charge was measured and a continuous copying test was conducted. At the same time, a toner with high reproducibility and resolution can be prepared using formula (44).

Claims (1)

[Claims] 1. Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In formula (1), R_1 and R_2 are a hydrogen atom, a nitro group, a methyl group, a chlorine atom, a sulfonic acid amide group or an atom or group selected from methylsulfone group, R is methyl group, ethyl group or phenylmethyl group, M is chromium,
Cobalt or iron atom, X represents hydrogen, sodium, potassium, ammonium or organic amine salt respectively] Metal complex salt compound represented by