JPH04186371A - Toner for electrostatic developing - Google Patents

Abstract

PURPOSE:To enhance the dispersion property of a coloring material and a charge adjuster in a toner and increase the staining power and stabilize the quantity of electrification of the toner by adding a specific phthalocyanine derivative to a toner composition. CONSTITUTION:At least a colorant and a phthalocyanine derivative indicated by the expression I are blended in a binder resin for a toner and the toner is formed by melting, kneading, crushing and classifying the blended materials. In the expression I, Pc indicates phthalocyanine residual group that may be substituted by halogen atom, A -CH2-, -CO-, -SO2-, or -CH2NHCOCH2NH-, R' hydrogen atom, lower alkyl group or (-CH2CHR<2>-O=)1H, R<2> hydrogen atom or methyl group, (l), (m) both an integral number of 1 to 30 and (n) an integral number of 1 to 4. Thereby the dispersion property of a coloring material and a charge adjuster in the toner is enhanced and the staining power of the toner is increased and the quantity of electrification is stabilized.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to developers for electrophotographic devices, and more particularly to component or two-component toners.

(Prior Art) In recent years, electrophotography, electrostatic recording, and electrostatic printing (hereinafter referred to as electrophotography) have made remarkable progress.
(R,M, 5chaffert, Focal pr
After uniformly charging the surface of the photoreceptor and exposing an image corresponding to the original, the charge on the exposed area is eliminated or reduced, forming an electrostatic latent image. I do. Next, an electrostatic charge developing toner (hereinafter sometimes abbreviated as toner) is electrostatically deposited on the electrostatic latent image to perform development and make the electrostatic latent image visible. In this case, the amount of toner attached changes depending on the amount of charge on the surface of the photoreceptor, and as a result, a toner image with shading is formed. This toner image can be used on paper, cloth, or
The image is transferred to a support such as a polymer film, and generally heated directly or indirectly to be fixed on the surface of the support.

There are many known developing methods in electrophotography, and they can be roughly divided into two-component methods, in which a carrier consisting of fine particles (50 to 300 μm) of iron powder, ferrite, glass, etc., and a mixture of toner are used as a developer. There is also a component development method that uses a developer consisting only of a development method and toner.

In either method, charge is generally injected into the toner triboelectrically.

As a representative example of the two-component development method, U.S. Patent No. 2.618.5
The cascade method described in No. 52 and U.S. Pat.
, 874, 063. These methods provide relatively stable images. However, problems with the two-component development method have also been pointed out, such as contamination of the carrier surface by toner, etc., and deterioration of image quality due to changes in triboelectric charging properties due to variations in the mixing ratio of carrier and toner.

In recent years, in response to the growing need to faithfully copy color originals, development of full-color copiers has become active. Generally, to obtain a multicolor image, the original is exposed to light using a color separation filter, and the above process is repeated multiple times using color developers such as yellow, magenta, and cyan, and the toner images are superimposed. The technology for producing color images has been established. However, the problem with this technology is that in order to transfer toner to a transfer material such as paper and obtain a color image, the second color is transferred onto the transfer material on which the first color toner has been transferred, and then Since it is necessary to perform multiple transfer in which a third color is transferred to the paper, a transfer drum is required to hold the transfer material, compared to black and white copying where only one transfer is normally performed. or become large. Furthermore, the size, thickness, and material of the transfer material are limited.

Furthermore, the transfer efficiency of the solid areas of the toner transferred to the second and third colors may decrease, resulting in the desired hue not being reproduced, or in line areas, the toner of the second and third colors may scatter around the lines, resulting in blurred characters. This causes other problems such as a decrease in sharpness. Therefore, in recent years, an electrophotographic process has been developed that involves repeating charging, exposing, and developing multiple times to form a plurality of toner images of different colors on a photoreceptor, and then simultaneously transferring toners of two or more colors. An object of the present invention is to provide a toner composition which is not limited to the above-mentioned one-component or two-component development method, but which has excellent dispersibility of a coloring substance and a charge control agent.

(Problems to be Solved by the Invention) The present inventors have determined that the structural formula of the compound and the crystal growth and
As a result of intensive research into the relationship with anti-aggregation effects, we found that by adding certain compounds to toner compositions,
It has been discovered that the dispersibility of coloring substances and charge control agents can be improved, the coloring power of toner can be increased, and the stability of charge amount can be achieved. It is something to improve.

An object of the present invention is to provide a toner for electrostatic charge development which has a high coloring power and a stable charge amount by uniformly and stably dispersing coloring substances, charge control agents, magnetic powder, etc. in a toner resin. .

(Means for Solving the Problems) That is, the present invention blends at least a colorant and a phthalocyanine derivative represented by the following general formula (1) into a binder resin for toner, and melts, kneads, crushes, and classifies the mixture. The present invention relates to an electrostatic charge developing toner characterized by the following characteristics.

General formula (I) (where Pc is a phthalocyanine residue optionally substituted with a halogen atom, A is -CH, -, -C0-,
-SO, -1 or -CH2NHCOCH2+.

R' is a hydrogen atom, a lower alkyl group, or -CH, CH
R''-0-)H, R2i;!Hydrogen atom or hamethyl group,!
.

m is an integer of 1 to 30, and n is an integer of 1 to 4. represents. ) As binder resins for toners, styrene copolymers such as polystyrene, styrene-butadiene copolymers, styrene-acrylic copolymers, etc., polyethylene, and ethylene-vinyl acetate copolymers, which are conventionally used as toner resins, can be used. , ethylene copolymers such as ethylene-vinyl alcohol copolymers, and thermoplastic resins such as phenolic resins, epoxy resins, and polyester resins.

Colorants include pigments and dyes; specifically, inorganic pigments include carbon black, such as furnace black, channel black, chromates, such as chloride and zinc yellow, ferrocyanides, such as navy blue, and sulfides. ,
For example, silver vermillion, cadmium yellow, zinc sulfide, antimony white, etc., oxides such as zinc white, titanium white, iron black, iron black, copper oxide, manganese dioxide, metal powders such as aluminum powder, bronze powder, etc., and organic Examples of pigments include nitroso pigments such as Naphthol Green B and Naphthol Green Y, nitro pigments such as Naphthol Yellow 81 and Lysol Fast Yellow 2G, and azo pigments such as Permanent Red 4R, Brilliant First Scarlet, Hansa Yellow, Lysol Red, and Lake. Red C, Lake Red D, Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, etc., Phthalocyanine pigments, such as Phthalocyanine Blue, Phthalocyanine Green, etc., Basic dye pigments, such as Rhodamine Lake, Malachite Green Lake, Methyl Violet Lake, etc. , acid dye pigments such as peacock blue lake, niosine lake, quinoline yellow lake, etc., and other dyes such as quinacridone red, quinacridone violet, perylene red, perylene scarlet, isoindolinone yellow, dioxazine violet, aniline black, and organic fluorescent pigments. , azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, and naphthalimide dyes.

The amount of the colorant used is 0.5 to 10% by weight, more preferably 1 to 7% by weight based on the weight of the toner.

Specific examples of phthalocyanine derivatives used in the present invention include the following.

CuPc 5O2N [(CIIzCHCHzO)
J() 2 (a) CuPc CHzNH(
CHzCHzO) zsH(e)CuPc CHJH
COCHJ[(CHzCHzO)J)z (g)Cu
Pc CHJ ((Ci(zcHzO) 3(lH'
l 2 '(j) By adding the phthalocyanine derivative of the present invention, a toner with excellent coloring power can be provided. The effect can be obtained by adding the phthalocyanine derivative in an amount of 0.1 to 20% by weight of the coloring agent used.

Moreover, from an economical point of view, it is more preferable to use 0.1 to 10
The desired effect can be obtained by adjusting the amount added in % by weight.

Furthermore, the phthalocyanine derivative of the present invention can provide similar effects in the above-mentioned blending amounts with respect to the dispersion of magnetic powder added when used as a magnetic component toner or a weakly magnetic toner.

Regarding charge control agents, some are classified as dyes and others are classified as resins. Some are also classified as static stabilizers and antistatic agents. Specifically, typical examples of those that impart positive chargeability to the toner include nigrosine-based oil-soluble dyes, crystal violet, triphenylamine, and quaternary ammonium salts. Furthermore, it is also possible to improve the level of positive charge by using a resin in which the amount of acid amide groups introduced is controlled as the copolymer resin constituting the toner. Furthermore, a quaternary ammonium salt or an antistatic agent may be added to stabilize charging. Typical examples that impart negative chargeability include metal complex dyes such as halatin dyes and orazole dyes. The toner of the present invention contains each of the above materials.
By adding in the range of 5 to 10 weight Q (i), it is possible to control the desired amount of charge. Of course, the above adjuvants, charge stabilizers, and antistatic agents may be used alone or in combination of two or more. It is possible.

Addition of the phthalocyanine derivative having the structural formula shown in the present invention also has the effect of accelerating charging and improving stability over time. Generally, the above-mentioned charge adjusting agent and charge stabilizing agent are used in a proportion of 0.5 to 10% of the toner constituents.
By adding the present phthalocyanine derivative, the desired effect can be obtained.

The toner according to the present invention is produced by thoroughly melting and kneading binder resin, colorant, phthalocyanine derivative, charge control agent, magnetic powder, etc. using a hot melt kneading machine such as a hot roll, kneader, or extruder, and then mechanically crushing and classifying. You can also manufacture it by doing so.

Furthermore, the toner according to the present invention requires the addition of silica as an external additive. The purpose of adding silica is to improve the fluidity of the toner and to control the amount of toner charge. If the amount added is less than 0.05% by weight, it will not be effective in controlling the fluidity and charge amount, and if it is more than 2% by weight, it will damage the photoreceptor or cause silica filming on the photoreceptor. 0
A range of 5 to 2% is preferred.

The toner of the present invention may contain other external additives, such as cleaning property improvers, i.e., higher fatty acid metal salts represented by zinc stearate, fluorine-based polymers, photoreceptor surface abrasives, i.e., cerium oxide, strontium titanate, A developability/transferability regulator, ie, a fine polymer powder such as alumina, tin oxide, molybdenum disulfide, steel oxide, or polymethyl methacrylate, can be added to the toner. The amount of these functional external additives added is preferably 0.05 to 3% by weight based on the toner.

The above-mentioned silica and various functional external additives can be added to the toner using a known mixer, such as a V-type mixer, a rotary container type mixer such as a turbis mixer, a ribbon type, a screw type, a rotary blade type, and others. A fixed container type mixer can be used as appropriate. The various components may be mixed all at once, or may be mixed in an order taking into consideration the properties of the toner.

(Example) The toner according to the present invention will be described below. The manufacturing method of the toner shown in each Example and Comparative Example is as follows.

After thoroughly mixing the material powders shown in each example and comparative example, they were heated and melted at 150 to 170°C, kneaded in a twin-screw extruder, cooled and solidified, and then pulverized and classified to obtain a predetermined average particle size. Aligned to. Thereafter, predetermined amounts of silica and other functional external additives were added, mixed in a Henschel mixer, and passed through a sieve to obtain a sample. The suitability of this sample was evaluated by modifying a commercially available copying machine.

Example 1 Styrene acrylic resin Hymer UNi3000 (manufactured by Sanyo Chemical Industries, Ltd.) 90 parts Carbon black MONARCH880 (manufactured by Cabot Corporation)
4 part wax
Viscole 550P (manufactured by Sanyo Chemical Industries, Ltd.)
3-part charge control agent Bontron N-01 (Orient Chemical Industry Co., Ltd.)
3-part phthalocyanine derivative (structural formula (a)) 0.5 parts External additive Aerosil R-972 (Nippon Aerosil @) 0
．． 3 parts Comparative Example 1 The same procedure as Example 1 was carried out except that the phthalocyanine derivative was not blended.

Example 2 Polyester resin Tufton NE600 (Kao Stock %
Formula% Phthalocyanine pigment Lionor Blue FG7350 (
Toyo Ink Manufacturing Co., Ltd.) 3 parts Wax Hoechst Wax PE130 (Hoechst) 4 parts Charge control agent Bontron E-84 (Orient Chemical Industry Co., Ltd.) 25 parts Phthalocyanine derivative (the above structural formula (b)) 0.5 parts Additive Aerosil R-972 (Nippon Aerosil Co., Ltd.) External additive Conductive tin oxide T-1 (Mitsui Kinzoku Co., Ltd.) 1 part Comparative Example 2 The same procedure as Example 2 was carried out except that the phthalocyanine derivative was not blended.

Example 3 Styrene acrylic resin Perfecta 9231 (Hitachi Chemical Co., Ltd.) 74 parts Carbon black Mitsubishi Carbon #44 (Mitsubishi Chemical Industries, Ltd.) 3 parts Magnetic powder
KBC-250 (Kanto Denka Kogyo Co., Ltd.) 15 parts Wax Mitsui Hiwax 320P (Mitsui Petrochemical Industries Co., Ltd.) 4 parts Charge adjuster Aizen 5pilon Black TR
H (Hodogaya Chemical Industry Co., Ltd.) 2.5 parts Phthalocyanine derivative (Structural formula (C) above) 1.5 parts External additive Aerosil R-812 (Nippon Aerosil Co., Ltd.) External additive FORAPLON 100OVLD (Showa Denko K.K.) 0.3 parts Comparative Example 3 The same procedure as Example 3 was carried out except that the phthalocyanine derivative was not blended.

Example 4 Polyester resin Nichigo Polyester HP-30
1 (Nippon Gosei Kagaku Kogyo Co., Ltd.) 89.5 parts Pigment Br1llint Carmine 6BA (
Toyo Ink Manufacturing Co., Ltd.)
, 3-part wax viscoel 550P (
Mitsubishi Chemical Industries, Ltd. % Charge control agent Bontron P-51 (Orient Chemical Industries, Ltd.) 1.5 parts Lunapel 912 (Arakawa Chemical Industries, Ltd.) 3 parts Phthalocyanine derivative (the above structural formula (C)) 0.1 part Additive Aerosil R-976 (Nippon Aerosil Co., Ltd. % Aluminum Oxide C (Nippon Aerosil Co., Ltd.) 0.02 parts Comparative Example 4 The same procedure as Example 3 was carried out except that the phthalocyanine derivative was not blended.

The evaluation results of each example and comparative example are summarized in Table-1.

(Effects of the Invention) By adding the compound of general formula (I) to the toner composition, the dispersibility of the coloring substance and charge control agent was improved, the coloring power of the toner was increased, and the amount of charge was stabilized.

Patent applicant: Toyo Ink Manufacturing Co., Ltd. 9th month of λ, 1991

Claims (1)

[Scope of Claims] 1. A static product characterized by blending at least a colorant and a phthalocyanine derivative represented by the following general formula (I) into a binder resin for toner, melting, kneading, pulverizing and classifying the mixture. Toner for charge development. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, Pc is a phthalocyanine residue that may be substituted with a halogen atom, A is -CH_2-, -CO-
, -SO_2-, or -CH_2NHCOCH_2-
, R' is a hydrogen atom, a lower alkyl group, or -CH_2
CHR^2-O-)H, R^2 is a hydrogen atom or a methyl group, l and m are each an integer of 1 to 30, and n is an integer of 1 to 4. represents. )