JPH02288848A - Compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 to R3 are 1-4C alkyl, 6-20C (substituted) aromatic group or 7-20C aralkyl; R4 is 14-22C alkyl, 6-20C (substituted) aromatic group or 7-20C aralkyl; A(-) is molybdate anion, tungstate anion or heteropoly-acid anion containing molybdenum or tungsten atom]. EXAMPLE:A compound expressed by formula II. USE:A compound useful as a toner which is an electrophotographic developer. Developing powder using the above-mentioned compound is capable of providing a quantity of electrification suitable for developing electrostatic images by friction with a carrier and keeping the quantity of electrification even in repetition of development constant with homogeneous distribution of the electrification maintained constant. PREPARATION:A quaternary ammonium chloride or bromide, etc., is mixed with molybdic acid or a salt thereof, tungstic acid or a salt thereof or a heteropoly-acid salt in water to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Graduation Application] The present invention relates to a compound useful in toner, which is an electrophotographic developer.

[Prior art]

Electrophotography generally involves forming an electrostatic latent image on a photoconductor made of a photoconductive substance, developing this image with a powder developer to make it visible, and then fixing it with heat or a solvent. be.

As a developer for such electrophotography, a mixture of a fine particle powder called a toner consisting of a resin and a colorant, and a microscopic glass bead or iron powder called a carrier is used.

Since the photoconductor layer can be positively or negatively charged,
Exposure under the original produces a positive or negative electrostatic latent image. Therefore, if the negative electrostatic latent image is developed with positively charged developer powder, a positive image matching the original is generated. However, when a positively electrostatic latent image is developed with negatively charged developer powder, the black and white tones are reversed and a negative image of the original, that is, a positive negative image is obtained.

Generally, developer powder is a fine powder made by mixing synthetic resin with coloring agents such as dyes and pigments.

The charging characteristics of developer powder are controlled by the resin, which is its main component, and the desired triboelectric charging characteristics are usually obtained by adding a charge control agent.

(Problems to be Solved by the Invention) As charge control agents, dyes and pigments such as oil black, nigrosine (Japanese Patent Publication No. 48-25669), aniline black, crystal violet, metal-containing dyes, and azo dyes have been known. In addition, as a colorless charge control agent, quaternary ammonium salt (JP-A-57-11936
4), metal soaps, etc. are known.

However, these control agents are susceptible to decomposition or deterioration due to humidity, temperature, light, and mechanical shock, and when used in toner, their charging characteristics may deteriorate due to environmental changes or long-term use. This has disadvantages such as changes in the image quality and adversely affecting the resulting image.

The object of the present invention is to provide a compound useful in toners that overcomes the above-mentioned drawbacks.

[Means for solving problems]

That is, the present invention relates to the following general formula (1) (wherein R,, R2 and R3 are each independently an alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms, Represents an aralkyl group having 7 to 20 carbon atoms, R4 is an alkyl group having 14 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
0 aralkyl group, and Ae represents a molybdate anion, a tungstate anion, a heteropolyacid anion consisting of molybdenum or tungsten) and is a compound useful for electrophotographic toners. In the toner according to the present invention, in particular, in general formula (1), A
It is thought that the excellent effects described below are produced due to the anion represented by e. In general formula (1),
Examples of alkyl groups for R, , R2 and R3 include methyl group, ethyl group, propyl group, and butyl group, and examples of alkyl groups for R4 include tetradecyl group, hexadecyl group, octadecyl group, and hexyl group. etc. can be mentioned. Further, examples of aromatic groups for R1, R2, R3 and R4 include phenyl group, naphthyl group, tolyl group, benzyl group, p-chlorobenzyl group, phenethyl group, and anthryl group.

Examples of anion Ae include molybdic acid, tungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphotungstic acid.
Examples include inorganic anions containing molybdenum or tungsten atoms, such as molybdic acid, silica molybdic acid, phosphotungsten molybdenum, or chromium molybdic acid.

The compound represented by the general formula (1) can be easily produced by mixing quaternary ammonium chloride, bromine salt, etc. with molybdic acid or molybdate, tungstic acid or tungstate, or heteropolyacid in water. can be generated and obtained separately.

Binder resins used in electrophotographic toners using the compound of the present invention include monomers of styrene and its substituted products such as polystyrene and polyvinyltoluene, styrene-substituted styrene copolymers, and styrene-acrylic acid esters. copolymers, styrene-methacrylate copolymers, styrene-acrylonitrile copolymers,
Examples include polyvinyl chloride, polyethylene, silicone resin, polyester, polyurethane, polyamide, epoxy resin, modified rosin, and phenol resin.

The developing powder according to the present invention can be prepared by melting and combining the compound of formula (1) in a weight ratio of 1 to 50% with respect to the synthetic resin, solidifying it, and then crushing it with a ball mill or other crusher, or by using a synthetic resin. It can be produced by adding a polymerization initiator to a monomer, adding thereto a compound of formula (1) in a weight ratio of 1 to 50% based on the monomer, and polymerizing the mixture while suspending it in water. At this time, there is no problem in adding other coloring agents, carbon bra, glue, etc. as dyes.

The developer powder produced in this way provides an amount of charge suitable for developing an electrostatic image through friction with the carrier, and the amount of charge remains constant even after repeated development, and the charge distribution is uniform. held constant.

Further, the charge control agent according to the present invention provides excellent charging characteristics even when used in a so-called one-component one-hener containing magnetic iron powder.

〔Example〕

Hereinafter, the present invention will be illustrated by giving examples and application examples of the compounds of the present invention as toners, but the present invention is not limited by these examples and application examples. In the examples, "parts" indicate "parts by weight" unless otherwise specified.

Production Examples of Compounds Example 1 C+611:+J(CII+)31/6 (MO702
4) Dissolve 3.2 parts of 6e (compound No. 1) trimethylhexadecyl ammonium chloride in 35 parts of water. In this, 2.5 parts of ammonium molybdate and 1 part of water.
A two-part aqueous solution is added. The precipitated white precipitate was separated daily, thoroughly washed with water, and then dried to obtain 3.5 parts of crystals.

The results of elemental analysis were as follows.

Example 2 ■ Clall, I□N (CH3) 31/10 (Hz singing 2
04□] 10θ (Compound No. 2) 1-limethyloctadecyl ammonium chloride 3.5
1 part was dissolved in 40 parts of water, and a solution consisting of 3.2 parts of ammonium paratungstate and 20 parts of water was poured into the solution.

The precipitated white crystals were separated daily, washed with water, and dried to obtain 5.7 parts.

Elemental analysis value Example 3 A solution of 70 parts of ammonium phosphate and 800 parts of water was added, and the precipitated white crystals were dried on the mouth side to obtain 73 parts.

Elemental analysis value Example 4 (Compound No. 4) ■ C++, H33N (CII3): + 1/6 (HzW
+zO4o) 6e(〃 ■ C2GH41N(Clh)] 1/4 [5iWI2
040'l '''' (〃 (Compound No. 3) 1'19 parts of trimethylhenzyl ammonium chloride was dissolved in 200 parts of water, and phosphorus molybde〃 7 (〃 Example 8 (Compound No. 8) (! Implementation) Example 18 (Compound No. 18) Example 13 (Compound No. 13) Example 22 (Compound No. 22) ■ ■ ■ Cl6F133N(CH3)31/4 (MoeOz6
:l '''Example 26 (Compound No., 26) ■ C+6H3J(CH3)+ 1/7 (PMO11039) 'θ Application example 1 ■ C+6H3J(Ct13)il/6 (MO70Z4)
1 part of the compound represented by 6e (compound 1) and 5 parts of carbon black are heated and kneaded with 100 parts of styrene-n-butyl methacrylate copolymer. After cooling, the mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet pulverizer, and classified to obtain a powder having a particle size of 10 to 15 μm. When this black powder was mixed with an iron powder carrier at a weight ratio of 5:150 and shaken, the toner was positively charged and the amount of charge was 23 μC/
It was g. When this toner was used to produce images using a commercially available copying machine, images with clear image quality could be obtained both initially and after copying 10,000 copies.

Application examples 2 to 30 are summarized in Table 1. The method for preparing the toner was the same as in Application Example 1 except that the compounds were different.

Comparative Examples 1 and 2 Toners were prepared in the same manner as in Application Example 1, except that the quaternary ammonium compounds shown in Table 2 were used instead of the quaternary ammonium compounds shown in Application Example 1.

The quaternary ammonium salt used in Table Comparative Example 1.2 has a different anion structure from Application Example 9.10.11.

When these toners were used to compare the initial image quality, the image quality after 10,000 copies, and the image quality under high temperature and high humidity conditions, the results shown in Table 3 were obtained, demonstrating the superiority of the toner according to the present invention. Ta.

Further, Table 4 shows changes in the amount of charge of the toners obtained in Application Example 10 and Comparative Example 2 during long-term shaking.

Table 4: Approximately 100 pulses per minute when the powder is placed in a polypropylene container
The mixture was shaken using a shaker that reciprocated twice. ) As shown in Table 4, compared to Application Example 10, the toner in Comparative Example 2 had a lower charge level, and the amount of charge decreased with shaking time, clearly demonstrating the superiority of the toner of the present invention. be.

Claims (1)

[Claims] 1. General formula (1) below ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1, R_2 and R_3 each independently represent an alkyl group having 1 to 4 carbon atoms, R_4 represents an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and R_4 is an alkyl group having 14 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms. represents an aromatic group, an aralkyl group having 7 to 20 carbon atoms, and A^■ represents a molybdate anion, a tungstate anion, a heteropolyacid anion containing molybdenum or a tungsten atom). 2. Formula, C_1_6H_3_3N^■(CH_3)_3
The compound according to claim 1, which is 1/6 [Mo_7O_2_4]^■. 3. Formula, C_1_8H_3_7N(CH_3)_2・C
_2H_51/10(H_2W_1_2O_4_2)＾
1^0^■ The compound according to claim 1. 4. ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Compound described in claim 1.