JPH036573A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain the compatibility with thermoplastic resins and thermal stability by incorporating a specific alkyl phenol metal complex compd. and/or alkyl phenol complex salt compd. into the toner. CONSTITUTION:The alkyl phenol metal complex compd. expressed by formula I and the alkyl phenol complex salt compd. expressed by formula II are incorpo rated as an electrostatic charge control agent into the toner. The alkaline metal ion as cation X of the alkyl phenol complex salt compd. expressed by formula II is exemplified by Li<+>, Na<+>, K<+>, etc. In the formula I, M1 denotes a bivalent metal. In the formula II, M2 denotes a trivalent metal or boron; X denotes a hydrogen ion, alkali metal ion (including substd. aliphat. ammonium ion), alicyclic ammonium ion or heterocyclic ammonium ion. The toner which has the excellent compatibility with the thermoplastic resins and temp. stability, is colorless and, therefore, forms sharp images and allows continuous use is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner for developing electrostatic latent images in electrophotography, electrostatic recording, and the like.

(Prior art) An electrostatic latent image can be visualized by adhering toner due to its electrostatic attraction, and is further fixed by heat or a solvent, or in some cases by pressure. In addition to developers, powder developers are commonly used.

This powder developer consists of a mixture of fine particle powder called toner, which is made by dispersing charge control agents, colorants, fluidizing agents, etc. in natural or synthetic resin, and fine iron powder or glass powder called douyaria. They can be roughly divided into two-component developers and one-component developers, which consist only of fine particle powder toner in which a charge control agent, colorant, fluidizing agent, ferrite, etc. are dispersed in a natural resin or composite R& resin. I can do it.

Two-component developers charge the toner through friction with the carrier, and the toner is visualized by adhering to the electrostatic latent image.
Development is accomplished by further fixing the image. A one-component developer charges the toner by friction with a brush-like or plate-like friction member that serves as a carrier, and attaches it to the electrostatic latent image. Some toners are charged by mutual friction with this ferrite. These developing toners maintain a positive or negative charge depending on the polarity of the electrostatic latent image being developed.

In order to maintain the charge of the toner, it has been proposed to utilize the triboelectricity of the resin, which is the main component of the toner, but this method has a low charge and a high solid surface resistance value, so it is difficult to obtain a good result. The resulting image will be easily blurred and blurred. For this reason, in order to maintain the necessary charge, dyes and pigments that impart charge, as well as charge control agents, are added.

However, conventional charge control agents generally have complex structures and lack stability, and are prone to decomposition or deterioration due to heat, mechanical shock, friction, changes in humidity conditions, etc., resulting in loss of their function as a charge control agent. .

Further, since it is a colored substance itself, it is suitable for toner of that color tone, but not suitable for toner of a different tone. Furthermore, since it is difficult to uniformly disperse the toner particles in a thermoplastic resin, there is a drawback that the amount of triboelectrification between toner particles obtained by pulverization varies. There have been a number of proposals to improve the drawbacks of these charge control agents, and different types of compounds have been proposed, but none have been found that are comprehensively satisfactory.

(Problems to be Solved by the Invention) The present invention aims to solve the drawbacks of conventional charge control agents. A colorless charge that has good compatibility with thermoplastic resins, has thermal stability above the resin melting temperature, imparts a uniform and sufficient charge to toner particles, and does not impair the color properties of the colored substance in the color toner composition. It is desired to develop a toner containing a conditioning agent.

(Means for Solving the Problems) The present inventors have completed the present invention as a result of repeated studies to solve the above-mentioned problems.

That is, an alkylphenol metal complex compound represented by the following general formula (I) % formula % () (in the formula, Ml represents a divalent metal), or - formula (I
I) ... (U) (However, in the formula, M2 represents a trivalent metal or boron,
An electrostatic charge image containing an alkylphenol complex salt compound represented by a hydrogen ion, an alkali metal ion (including substituted aliphatic ammonium ions), an alicyclic ammonium ion, or a heterocyclic ammonium ion as an electrostatic charge control agent. It is a phenomenon toner.

The alcohol phenol complex compound used in the present invention can be obtained in high yield by reacting an alkyl 7 ether synthesized by a known method with a metal salt or boric acid by a conventional method. By further neutralizing this, various complex salt compounds can be obtained such as copper sulfate, cobalt chloride, manganese chloride, lead nitrate, tin sulfate, calcium chloride, magnesium sulfate, barium chloride, aluminum sulfate, chromium chloride, chloride. Examples include ferric iron and titanium chloride.

Further, examples of the alkali metal ion as the cation X of the alkylphenol complex salt compound represented by formula (U) include L+, Na, K, and the like.

The aliphatic ammonium ion or alicyclic ammonium ion is represented by the general formula (I[[).

- Specific examples of R3, R2, R1 and R4 in formula (III) are shown in Table 1. Specific examples of heterocyclic ammonium ions are shown in Table 2.

Table 2 In addition to the above-mentioned furkylphenol metal complex compound or complex salt compound, the toner of the present invention is made of styrene and styrene substitutes such as polystyrene and polyvinyltoluene, taking into consideration adhesiveness, storage stability, fluidity, pulverizability, etc. monomers, styrene-substituted styrene copolymers, styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, styrene-acrylonitrile copolymers,
Polyvinyl chloride, polyethylene, silicone resin, polyester, polyurethane, polyamide, epoxy resin, phenol resin, etc. may be used singly or in combination. Also, known pigments and dyes can be used as coloring agents, but some of the best are Benzidine Yellow, Quinacridone, I! There are 7 talocyanine blue, copper 7 talocyanine green, etc.

In the present invention, the amount of the alkylphenol complex compound or complex salt compound added to the toner composition is:
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin.

The toner containing the alkylphenol metal complex compound or complex salt compound of the present invention is mixed with a carrier to provide a secondary developer, but it can also be used as a primary developer.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, in which parts by weight are abbreviated as parts.

Example 1 26.8 parts of 1.1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of sodium chloride were dissolved in 300 parts of water and heated to 80°C. Next, a solution of 13.6 parts of zinc chloride dissolved in 100 parts of water was gradually added. After that, 80
Continue stirring at ℃ for 2 hours, then cool to room temperature and adjust the pH.
After filtering the adjusted reaction product and washing with water, 50~
It was dried under reduced pressure at 60'C to obtain 32 parts of a waxy powder.

100 parts of styrene-acrylic copolymer resin, 1 part of carbon
2 parts and 1.5 parts of the alkylphenol zinc complex synthesized above.
The mixture was thoroughly mixed and heated to melt, cooled, and then pulverized using a jet mill to obtain a black toner.

A clear image without fogging was obtained from this toner, and a good copy image was obtained that remained unchanged even after repeated use over a long period of time.

1.26.8 parts of 1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of caustic soda were dissolved in 300 parts of water and heated to 80°C. Next, a solution of 23.8 parts of nickel chloride dissolved in 100 parts of water was gradually added. after that,
Continue stirring at 80°C for 2 hours, then cool to room temperature,
The pH was adjusted.

The reaction product was filtered, washed with water, and then dried under reduced pressure at 50 to 60°C to obtain 30 parts of pale yellow-green powder.

1. 100 parts of styrene-acrylic copolymer resin, 6 parts of copper phthalocyanine green and the alkylphenol nickel complex synthesized above. ! JS was mixed and melted by heating, and after cooling, the mixture was pulverized with a jet mill to obtain a green toner.

A clear image without fogging was obtained from this toner, and a good copy image was obtained that did not change even after repeated use over a long period of time.

Example 3 1.26.8 parts of 1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of caustic soda were dissolved in 300 parts of water and heated to 80°C. Next, 25 parts of copper sulfate was dissolved in 100 parts of water.
A solution in N was added slowly. Then, at 80℃
Continue stirring for an hour, then add 26.8 parts of 1-bis-(4-hydroxyphenyl)-cyclohetosan and 8 parts of gastric soda.
1 part was dissolved in 300 parts of water and heated to 80°C. Next, a solution of 31.6 parts of barium hydroxide dissolved in 100 parts of water was gradually added. Thereafter, the mixture was stirred at 80° C. for 2 hours, neutralized by adding hydrochloric acid, and then cooled to room temperature to obtain pale blue powder 31M5.

100 parts of styrene-acrylic copolymer resin, 6 parts of copper phthalocyanine, and 1.5 parts of the synthesized furkylphenol copper complex were pulverized in a (mix and heat melt, cool, and diene) mill. A blue tint was obtained.

This toner produces clear, fog-free images.
A good copy image was obtained with no change even after repeated use over a long period of time.

8 parts of K1 Salmon Gara and 1.6 parts of the synthesized alkylphenol barium complex were thoroughly mixed, heated and melted, cooled, and pulverized with a jet mill to obtain a red toner.

This toner produces clear, fog-free images.
A good copy image was obtained with no change even after repeated use over a long period of time.

K1 Nine Shadows 1.26.8 parts of 1-bis-(4-bitroxyphenyl)-cyclohetosan and 8 parts of caustic soda were dissolved in 300 parts of water and heated to 80°C. Next, add 6.2 parts of boric acid to 10 parts of water.
0 parts of the solution was slowly added. Thereafter, stirring was continued at 80° C. for 2 hours, then cooled to room temperature and neutralized. The reaction product was filtered, washed with water, and then dried under reduced pressure at 50 to 60°C to obtain 26 parts of colorless powder.

100 parts of styrene-acrylic copolymer resin, 6 parts of copper phthalocyanine blue, and 1.5 parts of the alkylphenol boron complex compound synthesized above were mixed (mixed, heated and melted,
After cooling, it was pulverized using a jet mill to obtain a blue toner.

This toner produces clear, fog-free images.
A good copy image was obtained with no change even after repeated use over a long period of time.

Example 6 26.8 parts of 1.1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of caustic soda were dissolved in 300 parts of water and heated to 80°C. *Aluminum chloride 12.
A solution of 1 part in 100 parts of water was slowly added. Thereafter, stirring was continued at 80° C. for 2 hours, then cooled to room temperature and neutralized.

The reaction product was filtered, washed with water, and then dried under reduced pressure at 50 to 60°C to obtain 27 parts of colorless powder.

100 parts of styrene-acrylic copolymer resin, 7 parts of benzidine yellow, and 1.5 parts of the alkylphenol aluminum complex compound synthesized above were thoroughly mixed, heated and melted, cooled, and pulverized with a jet mill to obtain a yellow toner. .

This toner produces clear, fog-free images.
A good copy image was obtained with no change even after repeated use over a long period of time.

K1 Salmon 1. 26.8'ff1S of 1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of caustic soda were mixed with 30 parts of water.
0 parts and heated to 80°C. Next, a solution of 13.5 parts of ferric chloride dissolved in 100 parts of water was gradually added. Thereafter, stirring was continued for 2 hours at 80'C, then cooled to room temperature and neutralized. The reaction product was filtered, washed with water, and then dried under reduced pressure at 50 to 60°C to obtain 28 parts of brown powder.

100 parts of styrene-acrylic copolymer resin, 12 parts of carbon black, and 1.5 parts of the above-synthesized arthro iron complex salt compound were mixed (mixed, heated and melted, and after cooling,
It was pulverized using a jet mill to obtain a black toner.

A clear image without fogging was obtained using this toner, and a good copy image was obtained without any change even after repeated use over a long period of time.

1. 26.8 parts of 1-bis-(4-hydroxyphenyl)-cyclohexane and 8 parts of caustic soda were dissolved in 300 parts of water and heated to 13.3 parts of zero-order chromium chloride. A solution prepared by dissolving 1 part in 100 parts of water was gradually added.
Continue stirring at 80°C for 2 hours, then cool to room temperature,
After filtering the neutralized 0 reaction product and washing with water, 50-6
It was dried under reduced pressure at 0° C. to obtain 28 parts of light gray powder.

100 parts of styrene-acrylic copolymer resin, 12 parts of carbon black, and 1.2 ml of the synthesized alkyl 7-enol chromium complex salt compound are thoroughly mixed and heated to melt. After cooling, the mixture is pulverized with a jet mill to form a black toner. Obtained.

This toner produces clear, fog-free images.
A good copy image was obtained with no change even after repeated use over a long period of time.

(Effects of the Invention) The charge control agent contained in the toner for developing electrostatic images of the present invention has excellent compatibility with thermoplastic resins and temperature stability, and is colorless, so images are clear and can be used continuously. toner.

Claims (1)

[Claims] 1. An alkylphenol metal complex represented by the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, M_1 represents a divalent metal.) Compound, or general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, in the formula, M_2 represents a trivalent metal or boron, and X represents a hydrogen ion, an alkali metal ion, an aliphatic ammonium ion (substituted 1. A toner for developing an electrostatic image, characterized in that it contains an alkylphenol complex salt compound represented by (including aliphatic ammonium), an alicyclic ammonium ion, or a heterocyclic ammonium ion.