JPH0810363B2 - Developer for electrostatic image - Google Patents

Description

TECHNICAL FIELD The present invention relates to a developer for electrostatic charge images using a charge exchange control agent.

More specifically, it relates to a developer that visualizes an electric latent image and an electric signal in electrophotography, electrostatic recording, etc., and particularly relates to a developer having excellent chargeability (mainly negative chargeability), developability and transferability.

Conventional technology Developer (toner) that visualizes charge latent images and electrical signals
As a method for imparting an electric charge to the friction contact charging method,
Various methods such as an ion irradiation method, an electrostatic induction method using conductivity, and a charge injection method are known.
Further, the friction contact charging method is widely used.

As the developer used in the friction contact charging method, in addition to a two-component developer in which carrier particles having a polarity opposite to that of the toner in order to impart an electric charge to the toner are mixed with the toner,
There is also known a one-component developer that utilizes frictional electrification between a charging member such as a charging blade or a charging roll and toner, or frictional electrification between toners.

Problems to be Solved by the Invention When the toner is charged by such a contact charging or friction charging method, an electron-donating substance or an electron-attracting substance is attached to the toner side or the charge-giving material side such as a carrier or a blade. Is added to control the chargeability. The triboelectrification phenomenon is complicated and its mechanism is not always clear, but generally, the electron donating substance is positively charged and the electron withdrawing substance is negatively charged.

Conventionally, in order to control the charging of the toner, (i) a dye or pigment, a surfactant, an inorganic powder or the like is added and mixed in the toner or on the surface of the toner particles, (ii) as a binder resin, -COOH,- CN, halogen -Cl etc., -NO _2, a resin-like material having a functional group such as -NH _2, but means the like have been taken, over time stability of the toner charging property, environmental stability Was not successful and was not satisfactory.

In addition, there was no good charge control agent which is colorless or light and can be used for color development.

Therefore, an object of the present invention is to provide a developer containing a charge exchange control agent which can solve the above-mentioned problems.

Another object of the present invention is to provide a developer which has a fast rise of charging and which can easily control the amount of charge and the charge distribution.

Another object of the present invention is to provide a developer having excellent environmental stability of chargeability and stability over time, improved developability and transferability, and ensuring good image quality.

Still another object of the present invention is to provide a color developer in which charging rises quickly and the amount of charge and charge distribution can be easily controlled.

Means for Solving the Problems As a result of intensive studies, the present inventors have (i) carrier particles containing an organic substance having a fluorine-containing functional group on the surface and / or inside thereof, and (ii) a specific organoboron compound. The present invention has been completed by discovering that the above problems can be improved and overcome by a developer prepared by mixing toner particles containing

Therefore, the developer for electrostatic images of the present invention comprises (i) carrier particles containing an organic substance having a fluorine-containing functional group on the surface and / or inside, (ii) a boron-containing organic anionic component and a cationic component. The toner particles containing an organoboron compound represented by the following general formulas (a) to (h) having a neutralized salt structure of are mixed.

(In the formula, R represents an organic group,₁Is a hydrogen atom, halo
Gen atom, alkyl group, halogenated alkyl group, aryl
Represents an alkyl group or an aryl group, M Is a cation
And n represents an integer of 1 or more, provided that
When n represents an integer of 2 or more, R₁Of each other
It may be the same or different.
Yes. ) Hereinafter, the present invention will be described in detail.

In the present invention, the organic substance having a fluorine-containing functional group contained on the surface and / or inside of the carrier particles is a fluorine-containing polymer, and a fluorine-containing coupling agent, a fluorine-containing alcohol, a fluorine-containing surfactant, a fluorine-containing carboxylic acid. Fluorine-containing low molecular weight organic substances such as

As the fluorine-containing polymer, it is possible to use a homopolymer of a fluorine-containing monomer, a copolymer of a fluorine-containing monomer and another monomer, and a mixture of them and another polymer. . As the copolymer, besides the random copolymer, a graft copolymer having a fluorine-containing functional group in the side chain and a block copolymer can be used.

As the homopolymer of the fluorine-containing monomer, for example, fluoroolefin or perfluoroolefin polymer or copolymer, for example, polychlorotrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer , Tetrafluoroethylene-tetrafluoroethyl vinyl ether copolymer, etc., fluorine-containing vinyl ether polymer or copolymer, fluorine-containing silicone resin, perfluoroalkyl vinyl ether polymer or copolymer, perfluoroacrylate polymer or copolymer, Examples thereof include perfluoromethacrylate polymers or copolymers.

Examples of the other monomer copolymerizable with the fluorine-containing monomer include, for example, styrenes such as styrene, chlorostyrene, and vinylstyrene: ethylene, propylene, butylene,
Mono-olefins such as isobutylene: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and other vinyl esters; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methacrylic acid. Esters of α-methylene aliphatic monocarboxylic acids such as methyl, ethyl methacrylate, butyl methacrylate and dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl iso A vinyl ketone such as propenyl ketone can be used.

Further, as the resin that can be used by mixing with an organic substance having a fluorine-containing functional group, in addition to a polymer or copolymer composed of the above monomers, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified Examples include rosin, paraffin, and waxes.

In the present invention, the organoboron compound is an excellent charge control agent for negatively charged toner, but it should be noted that if the fluorine content in the carrier particles is too large, the toner particles cannot be sufficiently controlled to be negatively charged. .

Among them, perfluorocarbons are not only effective for lowering the surface energy of carrier particles with a small amount of fluorine content and extending the life of the developer, but also exhibiting good chargeability in combination with the charge control agent. It is a copolymer of a fluorine-containing vinyl compound such as acrylate and perfluoromethacrylate, and alkyl methacrylate and alkyl acrylates such as methyl methacrylate and butyl methacrylate, and a graft copolymer is particularly effective.

Examples of perfluoroacrylate and perfluoromethacrylate include the following.

CF ₃ CH ₂ OCOCH = CH ₂ CF ₃ CH ₂ OCOC (CH ₂ ) = CH ₂ CF ₃ CF ₂ CH ₂ OCOCH = CH ₂ CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₃ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₃ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₄ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂ CF ₃ ( CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₈ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₈ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ OCF ₂ CF ₂ CH ₂ OCOCH = CH ₂ CF ₂ OCF ₂ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₂ OCF ₂ CF ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₂ OCF ₂ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₃ OCF ₂ CF ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₃ OCF ₂ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH = CH ₂ C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH _{2 In the} present invention, In order to impart positive chargeability to the carrier particles, it is preferable to use a mixture of the above fluorine-containing polymer and a nitrogen-containing polar monomer homopolymer or copolymer. As the nitrogen-containing polar monomer, N-methylaminoethyl acrylate, N-ethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dibutylaminoethyl acrylate, N , Substituted amino group-containing acrylates such as N-diethylaminopropyl acrylate, aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methylaminoethyl methacrylate, N
-Substituted amino group-containing methacrylates such as -ethylaminoethyl methacrylate, 2-N, N-dicyclohexylaminoethyl methacrylate, N, N-dibutylaminoethyl methacrylate, 2-phenylaminoethyl methacrylate, 2-dibenzylaminoethyl methacrylate,
Aminostyrene, dimethylaminoethylstyrene, N-
Aminostyrenes such as methylaminoethylstyrene and dimethylaminoethoxystyrene, acrylamines such as allylamine and allylmethylamine, vinylamines,
Vinylquinolines and allylquinolines, acrylamides, N-vinylamides, 2-vinylpyridine, 3-
Vinyl pyridine, 4-vinyl pyridine, 2-methyl-5
-Vinyl pyridine, 2-methyl-6-vinyl pyridine,
5-ethyl-2-vinylpyridine, 2,6-dimethyl-5
-Vinyl pyridines such as vinyl pyridine, vinyl piperidines such as 2-vinyl pyridine, vinyl pyrroles such as 2-vinyl pyrrole, vinyl quinolines such as 4-vinyl quinoline, other vinyl carbazoles, vinyl imidazoles, vinyl pyrazolines , Vinylpyrrolidones, etc. can be used.

On the other hand, as the fluorine-containing coupling agent, for example, CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) Perfluorosilanes such as ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ can be cited.

Examples of the fluorine-containing alcohol include 1H, 1H, 9H-hexadecafluoro-1-nonanol, 1H, 1H-pentadecafluoro-1-octanol, and 1H, 1H, 11H-eicosafluoro-1-undecanol. I can give you.

Examples of fluorine-containing surfactants include perfluorocarboxylic acid salts, perfluoroalkyl phosphates, perfluoroalkyltrimethylammonium salts, perfluoroalkylbetaines, perfluoroalkylamine oxides, and the like.

The carrier particles are prepared using an organic substance having these fluorine-containing functional groups. For example, an organic substance having a fluorine-containing functional group may be used alone or in combination with another resin, etc.
Desired carrier particles can be prepared by coating the surface of iron powder, ferrite powder, alumina powder, silica powder, glass beads, nickel powder, magnetite powder, etc. having a particle size of about 20 μm to 200 μm. As a method of coating the surface of the fluorine-containing organic compound and the fluorine-containing resinous material on the surface, a known method such as a spray drying method, an air suspension coating method, or a method using a kneader coater can be used. Further, the coating may be a complete coating or a partial coating. The ratio of the organic material having a fluorine-containing functional group on the surface of the carrier is usually 0.01 to 10% with respect to the carrier core material in the case of the fluorine-containing resinous material, but the amount of the fluorine-containing component in the coating material is 30% or less is sufficient.

When a fluorine-containing polymer is used, it is most effective that the polymer is present on the surface of carrier particles, and the smaller the amount, the more preferable. Therefore, for example, it is particularly effective to use a graft copolymer of perfluoromethacrylate, perfluoroacrylate, etc. and methylmethacrylate, etc., or a block copolymer, and adjust the copolymer to be unevenly distributed on the carrier particle surface. Is.

From the same idea, first, for example, after coating with a methyl methacrylate polymer, a thin layer of a fluorine-containing polymer may be formed thereon by a top coat.

Alternatively, the coating resin layer containing no fluorine may be fluorinated by plasma treatment or the like.

Further, by mixing ferrite fine powder, magnetite fine powder, etc. having a particle size of about 0.01 μm to about 2 μm with the solution, melt, emulsion, etc. of the above-mentioned polymers, granulating and drying, A composite carrier in which ferrite particles of about 20 μm to about 200 μm are dispersed in a resin may be prepared.

When using fluorine-containing low molecular weight organic substances, the particle size should be about 20 ~
Carrier particles such as ferrite powder having a particle size of about 200 μm can be treated with a fluorine-containing low-molecular weight organic compound such as a fluorine-containing low molecular weight coupling agent, a fluorine-containing alcohol, a fluorine-containing carboxylic acid, and a fluorine-containing surfactant.

Also, ferrite fine powder having a particle size of about 0.01 to 2 μm,
After treating the magnetite fine powder or the like with the above-mentioned fluorine-containing low molecular weight organic substance, polyolefin, polystyrene, a polymer or copolymer such as polyacrylic, or a mixture thereof is dispersed, and carrier particles are obtained by granulating. You can also do it.

In the present invention, the general formula (a) used for the toner is used.
In the organoboron compound represented by (h) to (h), the cationic component is an alkali metal cation such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Be ²⁺ , Mg ²⁺ , Ca ^2+. , Sr ²⁺ , Ba ^{2+ and} other alkaline earth metal cations, Cu ⁺ , Ag ⁺ , Zn ²⁺ , Cd ²⁺ and other transition metal cations, other polyvalent metal cations, ammonium, alkylammonium, pyridinium , Alkylpyridinium, quinolinium, imidazolinium, and other organic amine cations, organic phosphonium cations, sulfonium cations, and the like. However, since the function of the charge control agent of the present invention depends on the size and strength of the cationic component, care must be taken in selecting the cationic component. Particularly, when the amount of the cationic component is large, the toner has a positive charging property, so that special attention is required. For the purpose of the present invention, among the above cationic components, metal cations, ammonium cations (N
H ₄ ⁺ ) is most suitable, and when organic amine cations and organic phosphonium cations are used, cations having the following structures are conveniently used.

(R ₄ to R ₇ are each hydrogen, a methyl group, an ethyl group,
It represents a lower alkyl group such as a butyl group, an arylalkyl group such as a benzyl group, and an aryl group such as a phenyl group and a tolyl group. Further, the alkylpyridinium cation sufficiently exhibits the function of the charge control agent of the present invention even when the alkyl group has a long chain.

Among the organoboron compounds used in the present invention, preferred are compounds represented by the above formula (a).

Further, typical compounds include compounds represented by the following general formula (I).

(Where R₂Is a hydrogen atom, halogen atom, lower alkyl
Group or halogenated methyl group, R₃Is a hydrogen atom or
Represents a halogenated methyl group, M₁ Represents a metal cation
I forgot. ) Specific examples thereof will be illustrated below.

Tetraphenylboron lithium Tetraphenylboron sodium Tetraphenylboron potassium Tetraphenylboron rubidium Tetraphenylboron cesium Tetraphenylboron silver Tetraphenylboron calcium Tetra (p-fluorophenyl) boron lithium Tetra (p-fluoro) Phenyl) sodium sodium tetra (p-fluorophenyl) boron potassium tetra (p-fluorophenyl) boron rubidium tetra (p-fluorophenyl) boron cesium tetra (p-fluorophenyl) boron silver tetra (p-fluoro) Phenyl) boron calcium Tetra (p-chlorophenyl) boron lithium Tetra (p-chlorophenyl) boron sodium Tetra (p-chlorophenyl) boron potassium Tetra (p-chlorophene) Ru) Boron rubidium Tetra (p-chlorophenyl) boron cesium Tetra (p-chlorophenyl) boron silver Tetra (p-chlorophenyl) boron calcium Tetra (p-tolyl) boron lithium Tetra (p-tolyl) sodium sodium Tetra (p-tolyl) boron potassium Tetra (p-tolyl) boron rubidium Tetra (p-tolyl) boron cesium Tetra (p-tolyl) boron silver Tetra (p-tolyl) boron calcium Tetrakis [3,5 -Bis (trifluoromethyl) phenyl] boron lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] boron sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] boron potassium tetrakis [3, 5-bis (trifluoromethyl) phenyl] boron rubidium tetraki Sus [3,5-bis (trifluoromethyl) phenyl] boron Cesiumum tetrakis [3,5-bis (trifluoromethyl) phenyl] boron silver Tetrakis [3,5-bis (trifluoromethyl) phenyl] boron Calcium The developer of the present invention is, as described above, the specific boron-containing organic anion component (A) which utilizes the electron accepting property of boron.
The main feature is to use. Therefore, it can be effectively used mainly for controlling the negative charging property and promoting charge exchange of the negative charging material. However, depending on the usage, a compound represented by AD is added to the positively chargeable material,
Further, it can be used for improving charge exchange property and controlling conductivity of material.

The charge polarity of these organoboron compounds (AD) is considered to be determined by the composition or molecular size of the organic anion component (A) and the cationic component (D) that form the compound (AD), respectively. Depending on the composition of the component (D) or when the molecular size of the cationic component (D) is large, the neutralizing salt type compounds (AD) of both are not the negative charge controllability but rather the positive charge controllability. Is easily expressed. In such a case, the characteristics of the compound are determined by the component (D) rather than the component (A).

Many of the organoboron compounds in the present invention are colorless or light-colored and have excellent charge controllability.
In addition to the black developer, it can be used very well for the charge control of a material such as a color developer which is not colored.

The organoboron compound has a melting point or softening point of about 50.
It is desirable to use a substance that is solid at room temperature above ℃.
However, depending on the method of use, such as when treating only the surface layer of the toner particles, liquid substances can also be used. Further, the liquid substance may be supported or impregnated with an inorganic fine powder, a resin fine powder, a porous substance, a gelling agent, etc., and apparently solidified before use.

The organoboron compound is added to the toner particles in an amount of about 0.01% by weight to about 10% by weight, preferably about 0.1% by weight to about 5% by weight. As a result, the electrical characteristics of the developer can be improved very well.

The addition method to the toner particles may be not only dispersing or dissolving inside the toner particles, but also selectively adding only to the surface layer of the toner particles or adding and mixing outside the toner particles.

When it is added and mixed into the toner particles, it is mechanically mixed with a binder resin by a method such as melt mixing, emulsion mixing, and solution mixing, and the binder resin is polymerized in the presence of the organoboron compound to form a binder. The organoboron compound may be mixed or dissolved in the resin. In this case, a chemical bond may be formed between the organoboron compound and the binder resin or other additives in the toner particles.

As the binder resin for the toner particles, conventionally known ones can be used. For example, styrenes such as styrene, chlorostyrene and vinyl styrene; monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; methyl acrylate and acrylic acid. Ethyl, butyl acrylate, dodecyl acrylate,
Octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; homopolymers of vinyl ketone such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone. Alternatively, a copolymer can be exemplified. Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer,
Examples thereof include styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene and polypropylene.

Furthermore, polyester, polyurethane, epoxy resin, silicone resin polyamide, modified rosin, paraffin and waxes can be mentioned.

Examples of colorants include black dyes and pigments such as carbon black, oil black, and graphite; acetoacetic acid arylamide monoazo yellow pigments (Fast Yellow) such as CI pigment yellow 1, 3, 74, 97, and 98. ; CI
Pigment Yellow 12, 13 and 14 etc. acetoacetic acid arylamide disazo yellow pigments; CI solvent
Yellow 19, 77, 79, CI Disperse Yellow 164 and other yellow dyes, CI Pigment Red 48, 4
9: 1, 53: 1, 57: 1, 81, 122, 5 etc. red or red pigments; CI Solvent Red 52, 58, 8 red dyes; CI Pigment Blue 15 : 3, etc., blue dyes and pigments such as copper phthalocyanine and its derivatives, modified products, and colored or colorless sublimable dyes, and the like, and conventionally known dyes and pigments for printing inks and other coloring applications can be used.

These dyes and pigments may be used alone or in combination of two or more. Of course, the color tone may be adjusted by mixing with an extender pigment or a white pigment. Furthermore, in order to improve the dispersibility in the binder component, the surface of the colorant is treated with a coupling agent such as a surfactant or a silane coupling agent, a polymer material, a polymer dye or a polymer graft pigment. May be used.

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

Further, the toner particles in the present invention can be used as a magnetic toner by including a magnetic material (for example, ferrite) therein.

In addition, the toner particles in the present invention, it is also possible to use a conventionally known charge control agent as another additive, also a conductivity adjusting agent, an inorganic substance such as a metal oxide, a reinforcing filler,
Antioxidants and the like can also be used.

Further, as an external additive, silica, carbon, alumina,
Conventionally known substances such as titanium oxide, zinc oxide, resin fine powder, tin oxide, higher fatty acids and derivatives thereof such as metal salts can be used.

The toner particles in the present invention can be manufactured by any method such as a kneading and pulverizing method, a spray drying method and a direct polymerization method.

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

Action Conventionally, carrier particles of a low surface energy substance such as a fluorine-containing resin have the advantage that the toner or the carrier of the toner component is less likely to be contaminated and the developer has a long life. The resin-based carrier particles also have a drawback that the toner particles cannot be sufficiently negatively charged. However, in the present invention,
When used in combination with toner particles containing an organoboron compound, the chargeability of the organoboron compound is simply
It does not cover poor chargeability due to carrier particles containing an organic compound having a fluorine-containing functional group, but exhibits very good chargeability, and deterioration resistance, which is a characteristic of an organic compound having a fluorine-containing functional group, is also unsatisfactory. I will never be told. Although the reason is not clear, the organoboron compound (AD) having a neutral salt structure of the boron-containing organic anionic component (A) and the cationic component (D) is (i) an electron of boron. Due to the acceptability, (ii) the structure of a neutralized salt type, and (iii) the effect of an organic functional group, the exchange and transfer of electrons and / or ions of the compound itself and the composite material in which the compound is dispersed or dissolved in a polymer or the like can be performed. It is presumed to be promoted and exhibit excellent charge exchange controllability. Due to the resonance stability of the phenyl group, it is presumed that the toner particles are sufficiently and stably charged even with respect to the carrier particles containing the organic substance having the fluorine-containing functional group.

Examples Hereinafter, the present invention will be described with reference to examples, but of course, the contents of the present invention are not limited to these examples. Unless otherwise specified, "part" in the examples is
Represents "parts by weight". Also, normal temperature and humidity are 22 ° C and 55% R.
H., 28 ℃, 85% RH for high temperature and high humidity, 10 ℃, 15% for low temperature and low humidity
It means the environment of RH.

Example 1 Perfluoromethacrylate 20 parts rate (A) / methyl methacrylate = 30/70 graft copolymer CH ₂ ═C (CH ₃ ) COOCH ₂ (CF ₂ ) ₆ CF ₃ (A) polymethyl methacrylate having the following structure 80 parts A mixture of the above components was coated on a spherical ferrite powder having an average particle size of 120 μm using a kneader coater to obtain carrier particles. The coating layer thickness of the carrier particles was calculated to be about 1 μm, and it was confirmed by a scanning electron microscope that the coating layer was in a good state.

In addition, ESCA confirmed that fluorine was unevenly distributed on the surface.

Styrene / n-butyl acrylate 100 parts Copolymer Cyan pigment (copper phthalocyanine) 6 parts Tetraphenylboron potassium 1 part The above components are melt-kneaded, pulverized and classified to have an average particle diameter of 12 μm.
Toner particles were obtained.

A developer was prepared by mixing these carrier particles and toner particles in a weight ratio of 100/2. When the chargeability of this developer was evaluated by the charge spectrograph method, the results shown in the table below were obtained.

Next, FX-2300 was prepared by adding 0.6 wt% of hydrophobic silica fine powder and 0.5 wt% of polymethylmethacrylate fine powder to the above toner particles and the above carrier particles.
It was mounted on a copying machine (manufactured by Fuji Xerox Co., Ltd.) and a copying test was performed on 30,000 sheets. As a result, stable and good images were obtained up to 30,000 sheets.

Comparative Example 1 A developer was prepared in the same manner except that potassium tetraphenylborate was not added to the toner particles of Example 1,
The chargeability was compared.

As described above, the toner particles to which potassium tetraphenylboron was not added could not have a sufficient negative charging property.

Comparative Example 2 A developer was prepared and measured in the same manner as in Example 1, except that the carrier particles of Example 1 were changed to ferrite particles coated with a methyl methacrylate homopolymer.

The toner particles were treated in the same manner as in Example 1, and the carrier particles were used to prepare a developer. When this developer was mounted on an FX-2300 copier and a copy test was conducted, fogging occurred from the point where the number of printed sheets exceeded 2000, and a bad image resulted when the number of printed sheets reached 5,000.

Example 2 20 parts of the following perfluoromethacrylate (B) / methyl methacrylate (= 30/70) copolymer CH ₂ ═C (CH ₃ ) COOCH ₂ —CF ₂ —CF ₃ (B) methyl methacrylate / dimethyl 80 parts Aminoethylmethacrylate (= 95/5) copolymer Using the mixture of the above components, iron particles having an average particle diameter of 100 μm were coated in the same manner as in Example 1 to obtain carrier particles.

Styrene / butadiene copolymer 50 parts (weight average molecular weight about 500000) Styrene / butadiene copolymer 50 parts (weight average molecular weight about 30000) Polypropylene wax 5 parts Carbon black 10 parts Tetraphenylboron sodium 1 part Melting the above ingredients Kneading, crushing, classifying, average particle size 12μm
Toner particles were obtained. When the same measurement as in Example 1 was performed using the above carrier particles and toner particles, a stable charging property of about -15 μc / g was exhibited in all environments of normal temperature and normal humidity, high temperature and high humidity, and low temperature and low humidity.

After treating the above toner particles in the same manner as in Example 1, a developer was prepared in the same manner using the above carrier particles,
Mounted on FX-2830 copier (manufactured by Fuji Xerox Co., Ltd.),
When a copy test of 20000 sheets was performed, good images were always obtained until the end.

Example 3 2.0 with respect to spherical ferrite particles having an average particle size of 120 μm
Weight% of perfluorosilane (C) having the following structure was dissolved in toluene, and ferrite particles were heat-treated in the solution to obtain carrier particles.

CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (C) Styrene / butadiene copolymer 100 parts Magenta dye (Rhodamine B type) 6 parts Tetraphenylboron cesium 1 part Melt kneading the above components Crushed, classified, average particle size 12μm
Toner particles were obtained. Using the toner particles and the carrier particles, the measurement was carried out in the same manner as in Example 1. As a result, -20 μc /
It showed a good chargeability of about g. After treating the toner particles in the same manner as in Example 1, a developer was prepared in the same manner by using the above-mentioned carrier particles and mounted on an FX-2300 copying machine, and a copying test of 5,000 sheets was conducted. Good image quality was obtained until the end.

Example 4 Styrene / n-butyl acrylate 100 parts Copolymer yellow pigment (Fast Yellow G) 6 parts Sodium tetraphenylboron 1 part The above components are melt-kneaded, crushed and classified to have an average particle size of 7 μm.
Toner particles were obtained. This was treated in the same manner as in Example 1, and then 0.5% by weight of tin oxide was externally added, and the carrier particles of Example 1 were used to prepare a developer in the same manner as in Example 1. When this developer was mounted on an FX-2300 copying machine and a copying test was performed on 10,000 sheets, a good image was always obtained.

Example 5 Styrene / n-butylmethacrylate 25 parts Rate / 2-vinylpyridine (= 70/25/5) copolymer Styrene / 5 parts CH ₂ ═CHCOOCH ₂ CF ₃ copolymer magnetite 70 parts (perfluorosilane treatment) Product) The above components were kneaded and pulverized by an extruder to obtain carrier particles having an average particle size of 50 μm. Example 2
After treating the above toner particles in the same manner as in Example 2, a developer was prepared using the above carrier particles. FX-
When mounted on a modified 2830 machine and tested for 5,000 copies, good images were always obtained.

Example 6 A toner having a particle diameter of 12 μm was obtained in the same manner as in Example 1 except that potassium tetraphenylboron was not added.
Toner particles were obtained. 0.1% by weight of potassium tetraphenylboron, 0.6% by weight of hydrophobic silica and 0.5% by weight of polymethylmethacrylate fine powder were externally added to the toner particles and mixed with the carrier particles of Example 1 to prepare a developer. . When this developer was mounted on an FX-2300 copying machine and a copying test of 5,000 sheets was performed, a good image was always obtained.

Example 7 Styrene / ethylene wax 60 parts (= 90/10) coexisting polymer Low molecular weight polyethylene 35 parts Ethylene / vinyl acetate copolymer 20 parts Cyan pigment (copper phthalocyanine) 5 parts The above components are melt-kneaded, ground and classified. , Average particle size 15μ
m toner particles are obtained. 1.0% by weight of hydrophobic silica fine powder was externally added to the toner particles, and a developer was prepared using the carrier particles obtained in Example 5. The resulting developer was mounted on the FX-2300 copier modified for pressure fixing,
When a copying test was performed on 3000 sheets by a pressure fixing method with a linear pressure of 20 kg / cm, good images were obtained. The charge amount of the toner particles during the copying test was stable at -12 to -16 μc / g.

Example 8 Polystyrene 60 parts Styrene / butadiene block 20 parts Copolymer ester wax 15 parts Cyan pigment (copper phthalocyanine) 5 parts The above components are melt-kneaded, pulverized and classified to have an average particle diameter of 12 μm.
Toner particles were obtained. 0.1% by weight of potassium tetraphenylboron and fine particles of hydrophobic silica were added to the toner particles.
1.0% by weight was externally impact-mixed and fixed on the surface of the toner particles for encapsulation. Further, a developer was prepared in the same manner as in Example 7 and a copy test was conducted. as a result,
Good images were obtained up to 3000 sheets. The charge amount of the toner particles during the copying test was stable at -13 to -16 μc / g.

EFFECTS OF THE INVENTION The toner particles containing a charge exchange control agent composed of an organoboron compound composed of a boron-containing organic anionic component and a cationic component according to the invention have very good chargeability themselves. However, in the present invention, since the toner particles are used in combination with the carrier particles containing the organic substance having the fluorine-containing functional group, the chargeability of the toner particles becomes extremely good, and the conventional charge control is unsatisfactory. Raw materials that were possible can also be made available.

Therefore, the developer of the present invention has a rapid rise in charging,
It has an appropriate charge amount and charge distribution, and is excellent in environmental stability and temporal stability. In particular, it is excellent when used as a negatively chargeable developer.

Further, most of the organoboron compounds in the present invention are colorless or light-colored, and therefore the developer of the present invention is also suitable as a color developer.

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Claims (2)

[Claims] 1. An organic material having (i) a fluorine-containing functional group is represented.
Carrier particles contained on the surface and / or inside, and (ii) containing
Neutralization salt structure of organic-organic anionic and cationic components
Organic compounds represented by the following general formulas (a) to (h)
A toner for an electrostatic charge image formed by mixing toner particles containing an elementary compound.
Image agent. (In the formula, R represents an organic group,₁Is a hydrogen atom, halo
Gen atom, alkyl group, halogenated alkyl group, aryl
Represents an alkyl group or an aryl group, M Is a cation
And n represents an integer of 1 or more, provided that
When n represents an integer of 2 or more, R₁Of each other
It may be the same or different.
Yes. ) 2. An organoboron compound represented by the following general formula (1):
A compound represented by claim 1
Developer for electrostatic images.(Where R₂Is a hydrogen atom, halogen atom, lower alkyl
Group or halogenated methyl group, R₃Is a hydrogen atom or
Represents a halogenated methyl group, M Represents a metal cation
I forgot. )