JPS6263941A - Electric charge exchange controlling agent and developer composition - Google Patents

Abstract

PURPOSE:To form a developer compsn. of which the rise of electrostatic charge is fast and which permits the easy control of an electrostatic charge quantity and electric charge distribution by using an org. boron compd. constituted of an org. anionic component contg. boron and cationic component. CONSTITUTION:The org. boron compd. AD constituted of the org. anionic component A contg. boron and the cationic component D is used as an electric charge exchange controlling agent for a developer. The reason for the excellent electric charge exchangeability of the org. boron compd. AD is supposed to lie in that the exchange and transfer of the electrons and/or ions of the compd. itself or the composite material dispersed or dissolved with the compd. into a polymer, etc. are accelerated by the electron acceptability of the boron, the structure of the neutral salt type and the effect of the org. functional group. The boron- contg. org. anionic component A has a high effect of improving the charge exchangeability particularly when preferably >=2 arom. rings such as benzene ring or naphthaline ring are provided in the org. functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a charge exchange control agent and a developer composition using the charge exchange control agent.

More specifically, this invention relates to electronic latent fI! in electrostatic recording, etc. A developer composition for visualizing OT and electrical signals, especially chargeability (mainly negative chargeability).

The present invention relates to a developer composition having excellent developability and transferability, and a charge exchange control agent used in the developer composition.

[Conventional technology]

Developer (toner) that transforms electrical A1 images and electrical signals
Various methods are known for imparting a charge to a material, such as the II friction contact charging method, ion irradiation method, electrostatic induction method using conductivity, and charge injection method, but the easiest to use is (
, Matahiro (frictional contact charging method is used.

This frictional contact charging method uses a two-component developer in which carrier particles that are charged to the opposite polarity to the toner are mixed with the toner in order to impart an IK charge to the toner. One-component developers that utilize frictional electrification or mutual frictional electrification of toners are also known.

When charging toner using such contact charging or frictional charging methods, an electron-donating substance or an electron-withdrawing substance is added to the toner side or to the side of charge-imparting materials such as carriers and blades to make the charge α-characteristic. Take control. Although the triboelectric charging phenomenon is complex and its mechanism is not necessarily clear, generally electron-donating substances tend to be positively charged, and electron-withdrawing substances tend to be negatively charged.

Conventionally, in order to control the charge of toner, (1) dyes and pigments, surfactants, inorganic powders, etc. are added and mixed in the toner or on the surface of the toner particles, (11) as a binder resin, -
Halogens such as COOHl-CN, -C1, -NO,, -
Measures such as using a resin-like material having a functional group such as NH, etc. have been attempted, but they have not succeeded in controlling the temporal stability and environmental stability of toner chargeability, and there is no satisfactory method. It wasn't.

Furthermore, there has been no good charge control agent that is colorless or light-colored and can be used in color development.

[Problem that the invention seeks to solve]

Accordingly, it is an object of the present invention to provide a charge exchange control agent that can overcome the aforementioned problems in developer compositions.

Further, the object of the present invention is to quickly charge the battery (, 1 to 1!).
It is an object of the present invention to provide a developer composition that allows easy control of immersion and charge distribution.

It is an object of the present invention to provide a 3j1 compound composition which has excellent environmental stability and stability over time in charging properties, has improved transferability, and ensures good image quality. be.

Still another object of the present invention is to provide a color developer composition which has fast gamma topping (of banding), excellent control of banding device, charge distribution, etc.

[Means and effects for solving the problems] The present invention has been developed through intensive studies to create an organic boron compound (A) consisting of an organic anionic component (A) containing boron and a canonical component (D). The inventors have completed the present invention by demonstrating that the above-mentioned problems can be overcome by using AI)) as a charge exchange control agent in a developer.

This invention is a charge exchange control agent made of a diboron compound (AD) and a current acid agent composition containing the charge exchange control agent.

The boron-containing organic anionic component (A) of the organic boron compound (AD) used in the present invention has the general formula % formula % In the formula, R1s R@ 11 R1 and R4 are mutually independent organic groups, and each (Also, R1 and R1 and R, and R4 may be combined with the boron (B) to which they are bonded to form #I.

Examples of such a boron-containing organic anionic component (A) include the following.

5-1 In the formula, R represents an organic group.

6 On the other hand, the cationic component (D) is Ho and LielNa
", K", RbΦ, c3■, cue1Age, etc., alkali metals such as It7, Be2e, Mg2e,
Alkaline earth metal cations such as Ca2e, Zn''■, 5-■, ., 2e, Ba2e, other polyvalent metal cations, organic amine cations such as ammonium, alyalammonium, pyridinium, quinolinium, imidacillinium, etc. , sulfonium cations, phosphonium cations, and the like.

Organic boron compounds having a neutralized salt structure of these boron-containing organic anionic components (A) and cationic components (D)
The reason why AD) has excellent charge exchange control properties is not necessarily clear, but the reasons include (1) electron-accepting property of boron, (IL neutralized salt type structure, and (-1) organic functional group). It is presumed that this effect promotes the exchange and movement of electrons and/or ions in the compound itself and in the composite material in which the compound is dispersed or dispersed in a polymer or the like.

In addition, the boron-containing organic anionic component (A) represented by the above general formula has particularly charge exchange properties when it has one or more, preferably two or more aromatic rings such as a benzene ring or a naphthalene ring in the organic functional group. The improvement effect is large.

As described above, the charge exchange control agent and developer composition of the present invention are characterized primarily by the use of the boron-containing organic anion component (A) that takes advantage of the electron-accepting properties of boron.

Therefore, it can be effectively used mainly for controlling negative chargeability and promoting charge exchange of negatively chargeable materials. However, depending on the method of use, a compound represented by AD may be added to the positively chargeable material to further improve the charge exchange property or to control the conductivity of the material.

In addition, the # polarity of these organic boron compounds (AD) is thought to be determined by the composition or molecular size of the organic anionic component A and the cationic component forming the compound (AD), and the # polarity of the countercationic component (D Depending on the composition of ) or when the molecular size of (D) is large, (AD ), which is a neutralizing salt type compound of both, tends to exhibit positive charge control rather than negative charge control (
Become. In such a case, the characteristics of the compound will be determined by component (D) ζ rather than component (A).

The organic boron compound contained in the developer composition of the present invention is often colorless or light-colored (and has excellent charge control properties, so it can be used not only in black developers but also in color developers, which do not like coloring). It can be used extremely well for controlling the charging of materials.

As the organic boron compound used in the present invention, it is desirable to use a substance that is solid at room temperature and has a melting point or softening point of about 50'O or more. However, depending on the method of use, such as when treating only the surface layer of the developer, liquid substances can also be used. Furthermore, the liquid substance can be supported or impregnated with inorganic fine powder, resin fine powder, porous substance, gelling agent, etc., and can be used as an apparent body.

When an organic boron compound is used as a charge exchange agent Wa4 for controlling the charge of the developer of the present invention, the width of the developer is approximately 0.
By adding about 10% by weight to about 0.1 weight percent, preferably about 0.1 weight percent to about 5 weight percent, it is possible to improve the electrical properties of the developer very well.

The method of adding it to the developer is to disperse it inside the developer or to add it to the developer.
Not only do you do it, but you do it now! You can selectively add only one layer of the agent to the surface layer of the current II! It may be added and mixed outside the cutting area.

When it is added and mixed in the developer, it can be mechanically mixed with the binder resin by a method such as bath melt mixing, emulsion mixing, bath liquid mixing, etc. In addition, the binder resin can be polymerized in the presence of the organic boron compound of the present invention. However, the organic boron compound of the present invention may be mixed or mixed into the binder resin. In this case, a chemical bond may occur between the organic boron compound of the present invention and the binder resin or other additives in the developer.

As the binder resin for the developer composition, conventionally known binder resins can be used. For example, styrenes such as styrene, chlorostyrene, and vinylstyrene; monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate; methyl acrylate, ethyl acrylate , butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodesol methacrylate, etc. esters of α-methylene aliphatic monocarboxylic acids; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl butyl ether;
Examples include homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone, etc. Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, etc. Examples include styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene, and polypropylene.

Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin, and waxes.

Colorants include carbon black, oil black,
Black dye and pigment such as graphite: C, 1, PigmantYe
llowl, same 3. Acetoacetate arylamide monoazo yellow pigment (fast yellow type) of 74%, 971, 98, etc.: C, 1, IJgment Yellow 1
C,1,5olvent Yellow
ow 19 m 77% 79, C, 1, Disper
Yellow dyes such as se Yame ow 164: c, r.

Pigment Red 48, 49:1, 53:
Red or red pigments such as 1, 57:1, 81, 122, 5: C, l-8olvent Rad 52, 58. Red dye of grade 8; C, LPigment Bl
Dyes and pigments conventionally known for printing inks and other coloring applications can be used, such as fruit and vegetable dyes and pigments such as ue 15:3 steel phthalocyanine and its derivatives and modified products, as well as colored or colorless sublimable dyes.

These dyes and pigments may be used alone or in combination of two or more. Of course, it can be mixed with extender pigments and white pigments.

You may also adjust the color tone. Additionally, in order to improve the dispersibility of the binder component, the surface of the colorant may be treated with a surfactant, a coupling agent such as a silane coupling agent, or a polymer material, or a polymer dye or polymer may be used. Molecularly grafted pigments may also be used.

The binder resin and colorant are not limited to those exemplified above.

Further, the developer composition of the present invention can also be used as a magnetic toner by incorporating a magnetic material (for example, ferrite, etc.).

In addition, the developer composition of the present invention can also contain conventionally known charge control agents as other additives, as well as conductivity modifiers, inorganic substances such as metal oxides, reinforcing fillers, and antioxidants. etc. can also be used.

Furthermore, conventionally known external additives such as silica, carbon, alumina, titanium oxide, zinc oxide, fine resin powder, tin oxide, derivatives of higher fatty acids and their metal salts, etc. can be used.

The developer composition of the present invention can be produced by any method such as a cross-wire pulverization method, a spray dry method, or a direct mold method.

The particle size of the developer composition is an average particle size d measured by Coulter counter method. is 1 to 20 μm%, preferably 5 to 20 μm%
A 15 μm 9 degree one is good.

The developer composition of the present invention can be used as a so-called two-component developer that uses a carrier and a toner, or as a so-called one-component developer that does not use a carrier.

〔Effect of the invention〕

The present invention is an organic boron compound (AD) composed of a boron-containing organic anionic component (A) and a cationic component (D).
) and a developer composition containing the charge exchange control agent, and the developer composition using the charge exchange control agent of the present invention has an easy charge amount and charge distribution. can be controlled, charging rises quickly, developability,
It has excellent transferability and is suitable as a color developer.

In addition to being added to a developer, the charge exchange control agent of the present invention can be used in a carrier that imparts a charge to the toner, a charging member such as a charging blade, or a fixing roll that contacts the toner and has an electrical effect on the toner. It can also be used by being added to cleaning members, toner hoppers, and other constituent members of copiers and printers.

〔Example〕

Hereinafter, the charge exchange control agent and developer composition of the present invention will be explained with reference to Examples and Comparative Examples. In addition, parts in the following examples represent parts by weight.

Comparative example 1 0 styrene/n-butyl methacrylate copolymer (Tg
::65℃, Mn:8.000, Mw:;42,00
0) 100 parts 4 parts of magenta pigment (Carmine 6B) were melt-kneaded in a bath, pulverized, and classified to obtain a toner having an average particle size d, o:l: 12 μm. This toner was mixed with an iron powder carrier with an average particle diameter of approximately 100 μm (carrier/toner weight ratio -100/3), and the charging properties were measured, such as semi-uniform charge amount by blow-off tribo method and charge distribution by charge spectrograph method. , normal temperature and humidity, high temperature and high humidity.

Tests were conducted in each environment of low temperature and low humidity. Table 11 shows the results.
This is shown.

Table 1 As shown in the above table (one charge liter varied greatly depending on the environment, and the relationship between charge rise and the amount of reverse polarity toner was also unsatisfactory).

Example 1 0 Styrene/n-butyl methacrylate copolymer (same as Comparative Example 1) 100 parts 0 Magenta pigment (same as Comparative Example 1) 4 parts 0 Sodium tetraphenylboronate 1 part as in Comparative Example 1, Charging properties were evaluated in the same manner (semi-uniform particle diameter dlIQ-12 μm), and the results shown in Table 2 were obtained.

Compared to the comparative example, the environmental stability of the charge amount, the rise of the charge, and the sharpness of the charge distribution were significantly improved, and the product exhibited extremely good chargeability.

In addition to this toner, 0.7% by weight of hydrophobic silica fine powder,
Add and mix 0.8% by weight of fatty acid gold salt, and the average particle size is approximately 7.
5,000 yen using FX-2300 machine (manufactured by Fuji Xerox Co., Ltd.) using a color developer combined with a 0 μm ferrite carrier.
When a 0-sheet continuous copying test was conducted, extremely clear magenta images with no fogging were stably obtained.

Example 2 4 parts of the magenta pigment in Example 1 was replaced with 4 parts of cyan pigment (copper phthalocyanine), 4 parts of yellow pigment (disazo yellow), and 7 parts of carbon black, and semi-uniform particle size d, . A cyan toner, a yellow toner, and a black toner each having a thickness of 12 μm were obtained.

The charging properties of these three color toners were evaluated in the same manner as in Example 1. In the case of cyan, in all environments,
-13μc/f to -17μc/? , in the case of yellow, -12μc/l to -15μc/l; in the case of black, -14μc/t to -17μc/t, and one environment ζ
On the other hand, it was stable, and there were no problems with the rise of charging or the amount of toner with opposite polarity.

Example 3 Diameter 2 with a surface layer of electrical resistivity of approximately 1011Ω consisting of cross-linked phenolic resin, reinforcing agent and carbon black
A toner supply roll made of conductive rubber that supplies toner onto the development roll, and a surface layer made of silicone rubber, a reinforcing agent, and a charge control agent.
A blade that regulates the toner layer thickness and applies an electric charge to the toner, the toner is mainly mechanically supplied onto the developing roll by a toner supply roll, and then the toner is charged by a blade pressed against the developing roll, and the developing roll The photo above shows a modified FX-2300 copying machine (Fuji) incorporating a -component phenomenon device in which a single layer of toner is formed and conveyed to the electrostatic latent image section by mirror image force, where the phenomenon occurs. A continuous copying test of 5,000 sheets was conducted using a toner prepared by externally adding 1.0% by weight of hydrophobic silica fine powder to the magenta toner of Example 1 (manufactured by Xerox Corporation) without using a carrier. However, similar to Example 1, extremely good images were obtained.

Example 4, ,t? IJ ester resin (Tg,'l"C1 chloroform gel fraction: S: 15%)
100 parts 0 carbon black 10
Part O: 1 part of tetramethylammonium salt of dicatechol borate is melted and mixed;
Crush, classify, d. ; Prototype toner of 9μm was mixed with ferrite carrier of particle size 80μm.
Toner weight ratio = 100/3), and the same chargeability evaluation as in Example 1 was performed.

Blow-off electrostatic stitching is 17 μc/f to 12 μc/f in all environments.
It is stable at 1μc/l, and the charging rises quickly.
Almost no reverse polarity toner was observed. To this toner, 0.7% hydrophobic silica fine powder and 0.7% by weight methyl methacrylate resin fine powder were externally added and mixed, and FX-2
A repeated copy test of 10,000 sheets was performed using a 300 copy machine, and extremely good image quality was obtained.

Example 5 0 styrene/butyl acrylate copolymer (Tg; 60
'O1Mn; 4,000, Mw: 15,000)
50 parts Q styrene/butyl acrylate copolymer (T
gχ60℃1Mn; 160,000, -430,000) 50 parts 0 low molecular weight polypropylene 5 parts 0 γ-Fe20B
100 parts of fine powder is mixed by melting, pulverized,
Classified and semi-uniform particle size d. A sepia magnetic toner with a diameter of 12 μm was obtained. A modified F
When I performed a continuous copying test of 5,000 sheets with the machine, extremely clear sepia images were obtained.

Claims (1)

[Claims] 1. An organic boron compound (A) composed of an organic anionic component (A) containing boron and a cationic component (D)
A charge exchange control agent characterized by using D). 2. Organic boron compound (A) composed of an organic anionic component (A) containing boron and a cationic component (D)
A developer composition comprising D). 3. The developer composition according to claim 2, wherein the organic anionic component (A) containing boron has one or more aromatic rings in the molecule. 4. The developer composition according to claim 2, which contains an organic boron compound as a negative chargeability control agent.