JPS6388564A - Developer composition - Google Patents

Abstract

PURPOSE:To improve the environmental stability and stability with lapse of time of the electric charge of a toner by incorporating a high-polymer material having a sulfonic group bonded to an arom. ring into the titled compsn. CONSTITUTION:The high-polymer material having the sulfonic acid base bonded to the arom. ring is used in the developer compsn. prepd. by using a coloring agent and binder resin as essential components. The high-polymer material having the sulfonic acid base bonded to the arom. ring signifies the polymer having the group in which the sulfonic acid group bonded directly to the arom. ring such as benzene ring and naphthalene ring takes the form of a salt by neutralizing with a cationic component. The cation of the cationic component is exemplified by univalent or polyvalent metal cations such as Na<+>, K<+>, Li<+>, Ca<2+>, Mg<2+> and Al<3+>, ammonium ion, alkyl ammonium ion, pyridinium ion, quinolinium ion, imidazolium ion, etc. The developer compsn. having the excellent environmental stability and stability with lapse of time of the electric charge of the toner is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a developer composition for visualizing electrical latent images and electrical signals formed in electrophotography, electrostatic recording, etc., and particularly relates to a developer composition that has negative chargeability, phenomenal property, The present invention relates to a developer composition with excellent transferability.

Conventional technology Various methods are known for imparting charges to developer (toner), including friction, contact charging, ion irradiation, electrostatic induction using conductivity, and charge injection. However, the easiest and most widely used is friction.
Ori is carried out using the contact charging method.

In order to impart an electric charge to the toner, the developer used in this case is a two-component visual agent that mixes carrier particles with the toner that are charged in the opposite manner to the toner, as well as a two-component visual agent that mixes the toner with carrier particles that charge inversely to the toner. One-component developers are known that utilize frictional charging between toners.

When toner is charged by contact charging or frictional charging,
It is necessary to control chargeability by adding an electron-donating substance or an electron-attracting substance to the toner side or to the side of charge-imparting materials such as carriers and blades. Triboelectric development is complicated, and the grooves are not necessarily clear, but in general, electron-donating substances are positively charged and electron-withdrawing substances are negatively charged.

Conventionally, in order to control the charge of toner, (i) a dye agent, a surfactant [1 agent,
Free: Adding and mixing the powder, etc. (ii) As a binder resin, -COO, -CN, -CN, etc., -NO
The method of using a resinous substance having a functional group such as 2, -\1-12, etc. has been taken.

Problems to be Solved by the Invention However, these methods have not succeeded in controlling the temporal stability and environmental stability of toner chargeability.
I haven't reached the level where I can add @.

Furthermore, there are no known colorless or light-colored charge control agents that are sufficient for use in color applications.

Therefore, an object of the present invention is to provide a developer composition in which toner charging rises quickly, to provide a developer composition that allows control of the amount of toner charge and has a sharp charge distribution, and to provide an environment for toner charging. To provide a developer composition with excellent stability and stability over time, and therefore with improved developability and transferability to ensure good image quality at all times; It is an object of the present invention to provide a developer composition using a colorless or light-colored charge control agent that can be used for forming a charge control agent.

Means and Effects for Solving the Problems The above object of the present invention is to provide a developer composition containing a colorant and a binder resin as main components, in which a polymeric substance having a sulfonic acid group bonded to an aromatic ring is added. This was achieved by using

The polymeric substance having a sulfonic acid group bonded to an aromatic ring used in the present invention may be a sulfonic acid group directly bonded to an aromatic ring such as a benzene ring or a naphthalene ring, or may be neutralized with a cationic component to form a salt. It means a polymer in which a group is removed, and the cation of the cationic component is Na,
K, 1+, Zn”+, Ca2+, M(J”, A
Examples include -. + -valent or polyvalent metal cations such as 134, ammonium ions, alkylammonium ions, pyridinium ions, quinolinium ions, imidazolium ions, and the like.

The cationic component in the sulfonic acid group bonded to the aromatic ring in the present invention does not need to be one type, and two or more types of cationic components may be used.

These polymeric substances may be in the form of homopolymers, random copolymers, graft copolymers, block copolymers, or interpenetrating copolymers (IPN). 1) Polymerize a vinyl aromatic sulfonate such as Na salt, Zn salt, or ammonium salt of vinylbenzenesulfonic acid, or use other 8-monomers such as styrenes or methacrylates. , method of co-metalization with acrylates, dienes, etc., 2) above])
3) A method in which the polymer substance synthesized by the above method is further substituted with another cation by an ion exchange reaction; 3) A method in which a compound having a sulfonic acid group bonded to an aromatic ring is directly bonded to the polymer substance by a chemical reaction. .

The above-mentioned polymeric substance in the present invention may have any molecular weight depending on the purpose, but glass transition temperature TQ≧5
0'C and a number average molecular weight Mn≦10.000 are advantageously used.

In addition, the molar concentration of the sulfonic acid group bonded to the aromatic ring is based on the monomer unit having the sulfonic acid group bonded to the ``7'J aromatic ring, based on the total amount of the toner binder resin. , about 0.01 mol% to about 10 mol%, preferably
Preferably, it is about 0.1 mol% to 5 mol%.

The above-mentioned polymeric substance (t) in the present invention may be used alone as a fat, or may be used in combination with other polymers. When mixing 1, melt mixing,
Various methods can be applied, such as solution mixing, copolymerization, and emulsion mixing.

Other binder resins that can be used include styrene-based, acrylic-based, olefin-based, polyester, epoxy, polycarbonate, polyamide, polyurethane, silicone-based, fluorine-based, petroleum antislip, and the like.

In the developer composition of the present invention, known components can be used as the five-color polishing and other components. For example, dyes and pigments such as carbon black, cyan, magenta, and yellow colors can be used as coloring agents, and magnetic materials such as relaxed ferrite, conductivity regulators, inorganic materials such as metal oxides, reinforcing fillers, Antioxidants and the like can be added. Further, a known charge control agent may be used in combination.

The developer composition of the present invention may contain external additives. As external additives, conventionally known additives such as silica, carbon, alumina, titanium oxide, zinc oxide, fine resin powder, and tin oxide are used.

In the phenomenon agent composition of the present invention, the toner is prepared by a kneading and crushing method.
It can be produced by any known method such as a spray drying method or a direct polymerization method.

The particle size of the toner is preferably such that the average particle size d50 measured by Coulter counter method is in the range of 1 to 20 μm, more preferably in the range of 5 μm to 15 μm.

Examples Next, the present invention will be explained by examples.
It is not limited to these.

Example 1 Styrene/n-butyl methacrylate 60 parts
Copolymer to 1 (Cleaning 65°C1Hn=30000.Hw=70
000>Styrene/vinylbenzenesulfone 30 parts Na copolymer (vinylbenzenesulfone MNa approx. 3 m01%).

Tq=75°C, Hn=7000, )hv=100
00) Carbon black 10 parts Mix the above ingredients, crush them, particle size d50=13μ
The toner of No. m was prepared and the amount of charge was measured.

Sy, low temperature and low humidity (10'C, RH
It shows a high charge of approximately -30μc/g under all environments of 20%) and high temperature (90C, 80%RH), and the rise of charge is extremely fast, and the charge distribution was measured using the charge spectrograph method. As a result, the charge distribution was sharp,
No reverse polarity toner was observed.

The amount of charge was similarly measured on a carrier coated with a methacrylate copolymer, but in all environments it was about -
It exhibited a high charge level of 35 μC/SJ, and the charge distribution was also extremely sharp.

To this toner, approximately 0.7% by weight of hydrophobic silica fine powder and approximately 0.8% by weight of acrylic resin fine powder synthesized by soap-free emulsion polymerization are added and mixed, and the mixture is combined with a carrier to form a phenomenon agent and used for copying. When we conducted a running test with the machine FX-2300 (manufactured by Fuji Xerox Co., Ltd.), we found that there was no change in image quality even after a continuous copy test of 30,000 sheets, and it was stable against the environment and produced extremely good copies. .

Example 2 1.0% by weight of hydrophobic silica fine powder was added to the solution of Example 1 and mixed with HO to prepare a component phase [A type developer].

This phenomenon agent was installed in a single-component developing device with the following configuration, and a running test was conducted on a modified copying machine FX-2300. was gotten.

The amount of charge of the toner sampled from the current machine is approximately -1
It was 5 μC/g, and the charge distribution was also very sharp.

The one-component developing device consists of (1) cross-linked phenolic resin, reinforcing agent, and carbon black, and has an electrical resistivity of approximately 10 Ω.
diameter 20 willow developer roll, with a surface layer of cm, (2)
(3) a toner supply roll made of conductive rubber that supplies toner onto the developing roll; and (3) a silicone rubber that regulates the layer thickness of the toner supplied onto the developing roll by the toner supply roll and imparts an electric charge to the toner. It consists of a blade with a surface layer consisting of a reinforcing agent and a charge control agent. In this -component developing device, the toner is mainly mechanically supplied to the developing roll by a toner supply roll, and then charged by a blade pressed against the developing roll, and a toner layer of approximately 100% is formed on the developing roll. The image is formed, transported to the electrostatic latent image area by mirror force, and developed.

Example 3 In the toner constituent material of Example 1, Na + of the styrene/'vinylbenzenesulfonic acid copolymer was replaced with 1/2 Zn.
``+-substituted styrene/vinylbenzenesulfone MZ
A toner having a particle size d50 of 13 μm was obtained using the same formulation as in Example 1 except that the rl copolymer was adjusted.

When the charge amount of this toner was measured in the same manner as in Example 1, it was found that it was approximately -20 μC/cm in all environments compared to iron powder carrier.
It exhibited a good charge amount of g. Compared to the toner of Example 1,
Although the absolute amount of charge was somewhat low, this toner was even better in terms of environmental stability and sharpness of charge distribution.

This toner contains 0.7% by weight of hydrophobic silica fine powder and 0.7% by weight of hydrophobic silica fine powder.
When 5% by weight of fatty acid metal salt was added and mixed, and further mixed with a carrier, a continuous copying test of 30,000 sheets was performed using a copying machine FX-2300. Obtained.

Example 4 One part of Carphone Black 10 of the toner of Example 1 was mixed with cyan pigment (C,1, Piament Blue 1).
5:3) Magenta pigment (C,1, Pigment R
ed 57:1) Yellow pigment (C, 1, Pigmer
It Yellow 12) Three types of color toners each having a particle size d50 = 13 μm were produced by replacing it with 5 parts by weight. As in Example 1, charging the iron powder carrier♀
When measured, the three-color toners of cyan, magenta, and yellow showed an extremely uniform high charge amount of about -50 to -60tiC/7, and also had good charging rise, sharp charge distribution, and environmental stability. was also good. The above three primary color pigments are usually positively charged for cyan, magenta and yellow.
It is known as a highly negatively charged pigment, but in this way,
It is truly surprising that the negative influence on the chargeability of pigments can be overcome and charge control can be controlled. Moreover, the copolymer containing vinylbenzenesulfonic acid Na of the present invention,
It is a colorless and transparent resin that does not have any adverse effect on the color tone or optical properties of color toners.

Each of the three types of toner mentioned above has 0.00% hydrophobic silica fine powder.
7% by weight fatty acid gold salt and 0.8% by volume were added and mixed, and further mixed with a ferrite carrier at a toner concentration of 6% to prepare three colors of color 1 agents.

When a running test was carried out using a copying machine F

Example 5 A Na/ammonium salt mixed copolymer of styrene/vinylbenzenesulfone in which the Na of the styrene/vinylbenzenesulfone fliNa copolymer, which is the toner material of Example 1, was partially replaced with NH4+ was prepared. , otherwise the same formulation as in Example 1, particle size d 50 = 13μ
m toner was obtained.

When the charge amount of this toner was measured in the same manner as in Example 1, it was found that it was approximately -25 μC/9 in all environments with respect to iron powder carrier.
It showed good chargeability. The charging rise speed and the sharpness of the charge distribution were also very good.

To this toner, 0.7fffit% hydrophobic silica fine powder and 0.5@ffN% fat In gold salt were added and mixed,
Further mixed with carrier, current 9^11, copy 1Fx-2
Did you perform a continuous copy test of 30,000 sheets with 300?
I was able to get the good image quality I had hoped for.

Example 6 Styrene/butyl acrylate 50 parts by weight copolymer (TIj=65°C, Mn=170000, ) Iw
=420000) Styrene/butyl acrylate/
35-fold i-part vinylbenzenesulfone MZn copolymer (Ti;] = 60°C, ) fn = 7000, H
w=15000>(vinylbenzenesulfonic acid Z opening approximately 2
(Mo 1%) Low molecular weight polypropylene wax 5 parts Carbon black 10 parts The above components were mixed and pulverized to prepare a toner having a particle size d50=12 μm. When the charge ♀ was measured in the same manner as in Example 1, both the iron carrier and the methyl methacrylate copolymer-coated chitria exhibited stable chargeability of about -20 μC/g in all environments. Of course, the charging rise speed is fast, and the charge distribution is sharp and opposite) ~,
[No fresh toner was seen.

Furthermore, the charge amount was similarly measured for a ferrite carrier coated with a silicone resin (particle size: 70 μm) and a ferrite carrier coated with a copolymer of Par70 acrylate and methyl methacrylate, but the toner concentration, At about 5%, about -15 μC/9 to -20 uc/g
It showed a charging ♀ of ♀, and extremely good and stable charging property was confirmed δ2.

Further, 0.7% by weight of hydrophobic silica fine powder and 0.5% by weight of acrylic resin fine powder were added to this toner, mixed, and combined with the silicone-based resin coated carrier.
-2830<manufactured by Fuji Xerox Co., Ltd.) was used for a driving test. During a continuous 50,000 copy test, 19 copies were always stable and very good.

Comparative Example 1 Styrene/n-butyl methacrylate 90 parts ff1i rate copolymer (Tg=65°C, Hn=30000,) IW=700
00 > Carbon black 10 parts by weight The above components were kneaded, crushed, and classified, and the particle size d50 = 13μ
The toner of m was adjusted. Add and mix 3 parts by weight of the above toner to 100 parts by weight of iron powder carrier with particle size d = 100 μm ()
When the amount of charge was measured, a specific charge of -7 μC/g was obtained. Fi! The environmental dependence of the amount of charge! I acknowledged that
There was a noticeable decrease in the amount of charge under high humidity. Further, when the charge component I was measured using a charge spectrograph method, it was found that the charge distribution was wide and there were many toners of opposite polarity. Furthermore, the rise in the amount of charge was slow in all environments.

Comparative Example 2 Styrene/n-butyl methacrylate 88 parts by weight rate copolymer (T(]=65°C, Hn=30000. Hw=70
000> Sodium dodecylbenzenesulfonate 2 parts by weight Carphone black 10 parts by weight The above components were mixed and pulverized to obtain a toner with a particle size of 50=13 μm. When we measured the amount of charge on Comparative Example] and ri1, we found that it was about -7μG/''i in a normal environment, which is almost the same as Comparative Example 1. However, the chargeability under high humidity was that of Comparative Example 1. When the charge distribution was measured, it was found to be almost a reverse toner.The appearance of the rise in charging was approximately the same as in Comparative Example 1.

Effects of the Invention Since the developer composition of the present invention contains a polymeric substance having a sulfonic acid group bonded to an aromatic ring as a binding resin component, it has excellent negative chargeability, developability, and transferability. There is.

That is, the developer composition of the present invention has a quick rise in toner charge, allows control of the amount of charge on the toner, and has a sharp charge distribution, and has excellent environmental stability and stability over time in toner charge. There is. Therefore, the developability and transferability of conventional developer compositions are improved, and copies of good image quality can always be obtained. In general, since the polymer is colorless or light-colored, the developer composition of the present invention may be effective in forming color images. , one-component carrier imaging method that does not use a carrier.

Claims (1)

[Claims] A developer composition comprising a colorant and a binder resin as main components, the developer composition comprising a polymeric substance having a sulfonic acid group bonded to an aromatic ring.