JP2802756B2 - Developer and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to electrophotography, electrostatic recording, electrostatic printing, etc.
The present invention relates to a developer used and an image forming method.
You. BACKGROUND OF THE INVENTION Generally, in electrophotography, a material made of a photoconductive material is used.
A latent image carrier having a photosensitive layer
After applying a charge, the photosensitive member is exposed by performing image exposure.
An electrostatic latent image is formed on the surface of the
To form a toner image. The resulting toner image
After the image is transferred to a transfer material such as paper,
The image is fixed to form a copied image. Photoconductors include selenium photoconductors, zinc oxide photoconductors, and sulfurized photoconductors.
Cadmium photoconductors and organic photoconductors are known
However, the selenium photoconductor crystallizes in a high temperature environment.
Poor image quality due to poor heat resistance and poor sensitivity
It has the problem of becoming an image. Also, zinc oxide photoreceptor
And cadmium sulfide photoreceptors
Photosensitivity is easily deteriorated at an early stage and fog is generated and it is unclear.
Image and poor durability, and poison to human body.
Sex is accused. On the other hand, the organic photoconductor composed of an organic semiconductor is described above.
No defects, good film-forming properties, low production cost, high sensitivity
Advantages such as temperature, durability, heat resistance, and no toxicity to the human body.
Is a preferred photoreceptor. The polarity of the electrostatic latent image formed on the surface of the organic photoreceptor and
Therefore, except for exceptional ones, negative electrostatic latent images are generally
It is mainly used. This constitutes the organic photoreceptor
With many types of photoconductive materials and high performance
This is based on the reason that There are two methods for developing an electrostatic latent image: a wet development method and a dry development method.
The type development method is known. The former wet development method uses liquid
There is a problem that it emits offensive odor due to the use of developer
High-speed copying requires high energy to dry materials
There is a problem that is difficult. The latter dry development method is
It does not have the above problems and is the preferred method for developing electrostatic latent images.
Is a new way. As a developer used in the dry development method, generally, a magnetic developer is used.
Non-magnetic toner containing no magnetic substance and carrier having magnetism
And a so-called two-component developer comprising
So-called one-component developer consisting of only magnetic toner
And is known. When developing using such a developer, the developer is composed
The formed toner has the opposite polarity to the negative electrostatic latent image on the photoreceptor surface
Must be positively charged. Charge the toner positively
Addition of a positively chargeable charge control agent or a two-component developer
In the case of, the toner is corrected by selecting a carrier.
To be triboelectrically charged. However, it is sufficient to simply charge the toner positively.
Good images cannot be stably provided for a long period of time. Immediately
That is, the toner rubs against another triboelectrification member to form a band.
Electricity, but if it is used many times,
Some of the components that make up the toner transfer to the triboelectric charging member
And the surface of the triboelectric member to which an appropriate triboelectric charge should be applied
And gradually imparts an appropriate triboelectric charge to the toner.
And the absolute value of the triboelectric charge of the toner decreases.
Fogging is likely to occur and the durability is impaired.
I will. Conventionally, to solve such a problem,
The following technologies have been proposed. (1) Metal oxidation treated with aminosilane coupling agent
Technology to contain fine powder. (JP-A-52-135739 and JP-A-56-123550) (2) Treatment with a silicone oil having an amino group in the side chain
Technology to contain fine inorganic powder. (JP-A-59-200252 and JP-A-59-201063) In the technique (1), aminosilane coupling
Metal powder treated with a toner agent makes the toner polarity positively charged.
Performance under normal humidity conditions.
Degree of improvement, but cleaning under low humidity environment
An image defect called a black spot on the image due to a defect
Occurs, and under high humidity environmental conditions, the chargeability decreases and
Occurs. In the technique (2), an amino group is added to the side chain.
Use of inorganic fine powder treated with silicone oil
Therefore, similar to the technique (1), the fine powder must be positively chargeable.
However, since the developer is highly dependent on the environment,
When forming an image under high humidity, fogging occurs and under low humidity
Causes black spots, which are defective cleaning. In order to improve the environmental dependency of such a developer,
No. 62-75539 discloses a fine powder of fluororesin and a positively chargeable resin.
A technology containing Rica has been disclosed.
According to the report, although the performance is improved to some extent,
Black spots occur due to poor beam cleaning,
The lack of scratches on the photoconductor and the deterioration of the developer
There is a point. As explained above, in any case,
It is difficult to obtain good images repeatedly in the background
is there. [Object of the Invention] The present invention has been made to solve the above-mentioned conventional problems.
The purpose is (1) Kleini
Good images can be obtained stably without the occurrence of printing defects
Providing a developer and an image forming method;
Developer and image that provide good images even in
Providing an image forming method, (3) good over many sheets
To provide a developer and an image forming method capable of obtaining a stable image
And there. [Means for Achieving the Object] The object of the present invention is to provide an ammonium salt as a functional group.
Having a structural unit represented by the following formula (A)
Inorganic fine particles surface-treated with xane and binder resin
A toner in which a colorant is dispersed and contained;
Mixed with organic fine particles having a small average particle size
And a developer characterized by the following. In addition, the above object of the present invention is to provide an electro-static
Step of developing latent image with developer, and cleaning unit
In image forming method having cleaning process with material
The photosensitive member is an organic photosensitive member,
The member is a cleaning blade, and the developer is
Formula (A) having a monium salt as a functional group:
Treated with a polysiloxane containing structural units
Colorants dispersed and contained in fine particles and binder resin
Toner and organic fine particles having an average particle size smaller than the toner particles.
Image as a developer characterized by being mixed with a developer
This can be achieved by a forming method. (Where R ₁ Represents a hydrogen atom, an alkyl group, an aryl group,
Alkoxy group, or And R _Two Represents a bonding group or a simple bond, R _Three , R _Four And R _Five Represents a hydrogen atom, an alkyl group,
And X represents a halogen atom. R ₁ ~ R _Five Represented by
Each of the groups includes those having a substituent. [Function and Effect of the Present Invention] In the present invention, specific inorganic fine particles are added to a developer.
By doing so, it has good positive chargeability and
Excellent, thereby achieving high developability in all environments,
A high-quality image free from fog can be obtained. Immediately
The specific inorganic fine particles are functionalized with an ammonium salt.
Surface treatment of inorganic fine particles with polysiloxane
It has been done. The functional group of the ammonium salt
Has a higher positive charge density than mino groups. For this,
High positive chargeability can be provided. Cups that are also monomers
Use a polysiloxane polymer instead of a ring agent.
With this, the surface of the inorganic fine particles can be uniformly covered
Therefore, hydrophilic sites and negative bands existing on the surface of inorganic fine particles
Electric sites (for example, -OH groups) remain on the surface
No humidity, which allows for high humidity
It is possible to provide a high normal electrical property which is the same as the lower one. And the fluidity of the developer is caused by the specific inorganic fine particles.
Is applied, so that toner particles are not aggregated
It becomes triboelectrically charged in a state. Ammonium which is relatively soft with low adhesion
Non-treated with polysiloxane having salt as a functional group
Fine particles are relatively easy to film.
Low adhesion to the surface and even if it adheres slightly
Easy cleaning with a cleaning blade
Can be. In addition, such specific inorganic fine particles
The toner particles adhered to the toner surface have low adhesion.
Contact with organic photoreceptor surface via specific inorganic fine particles
The toner on the surface of the organic photoreceptor.
The toner particles on the surface of the photoreceptor.
As the contact force can be reduced, the residual photoreceptor surface
The cleaning property of the toner is improved. Therefore, clini
Image defects called black spots caused by defective printing
No. In the present invention, the organic fine particles may be added to the developer.
Of the developer due to the spacer effect of the organic fine particles
Durability can be improved. Further, according to the developer of the present invention, the developer is formed on the surface of the organic photoreceptor.
Development cost is reduced because the developed negative electrostatic latent image is developed.
Detracts from the benefits of organic photoreceptors that are both toxic and non-toxic
Without a negative electrostatic latent image formed on the organic photoreceptor.
Good without scattering of developer particles and poor cleaning
It can be developed, especially when the fluidity of the developer is good.
Therefore, the magnetic brush of the developer uniformly arranged on the developing sleeve
Rush can be formed, and this is due to magnetic brush development
It can be preferably used for the method. [Specific configuration of the invention] Ammonium used for specific inorganic fine particles of the present invention
As a polysiloxane having a salt as a functional group, a positive band
Ammonium with high electrical conductivity and less occurrence of cleaning failure
Be a dimethylpolysiloxane having an aluminum base
preferable. Dimethyl polysilo with ammonium base
The siloxane is generally a structural unit represented by the following formula (A):
Is a dimethylsiloxane containing a position, for example, of the formula (B)
It is represented by a structural formula. (Where R ₁ Represents a hydrogen atom, an alkyl group, an aryl group,
Lucoxy group or And R _Two Is a linking group (eg, an alkylene group, an aryl
A len group, an aralkylene group, -NH-, -NHCO-, or
Examples include groups obtained by arbitrarily combining these groups),
Or a mere bond, R _Three , R _Four And R _Five Is water
X represents a halogen atom, an alkyl group or an aryl group;
Represents a gen atom. R ₁ ~ R _Five Each group represented by
Includes those that have. ) (Where R ₆ And R ₇ Represents a hydrogen atom, an alkyl group,
Represents an aryl group or an alkoxy group.
Those having a substituent are also included. R ₁ ~ R _Five , X is the above (A)
R in the formula ₁ ~ R _Five , X. m and n are respectively
Represents an integer of 1 or more. ) Also, Specific examples include those represented by the following structural formula.
However, the present invention is not limited to these. Polysiloxane having an ammonium salt as a functional group
As a method for obtaining
Organohalogenated silanes and especially ammonium bases
Polymerization Using Organohalogenated Silanes Having No
Method introduced by copolymerizing in a stage, Olga
Polysiloxy obtained by polymerization using halogenated silane
An organic group having an ammonium salt as a functional group
It can be obtained by a method of partially denaturing. This
Here, instead of the organohalogenated silane, an organoal
Coxysilane may be used. For some compounds,
Can also be obtained as a commercial product. Polysiloxane having an ammonium salt as a functional group
The inorganic fine particles used for surface treatment of
For example, silica, alumina, titanium oxide, barium titanate
System, magnesium titanate, calcium titanate, tita
Strontium phosphate, zinc oxide, chromium oxide, cell oxide
, Antimony trioxide, zirconium oxide, silicon carbide
Fine particles such as silicon. Such inorganic fine particles
Are the primary particles (particles in a state separated into individual unit particles)
Particles having an average particle size in the range of 3 μm to 2 μm.
Is preferred. In addition, as inorganic fine particles, there is a
Silica fine particles can be preferably used. silica
The fine particles are fine particles having a Si-O-Si bond,
Process and wet process.
However, those manufactured by a dry method are preferable, and
Silica produced by vapor phase oxidation of halogenated compounds
Fine particles are preferred. In addition, silica fine particles
In addition to silicon dioxide (silica), aluminum silicate
, Sodium silicate, calcium silicate, calcium silicate
Silicates such as lium, zinc silicate and magnesium silicate
Fine particles consisting of SiO _Two Over 85% by weight
Is preferred. The above ammonium salt is used as a functional group on the surface of the inorganic fine particles.
As a method for treating polysiloxane having
The technique described in the above can be used.
In a solution of polysiloxane dissolved in a solvent,
After dispersing, separate or spray dry the solvent
To remove and then dry and cure by heating
Method, or using a fluidized bed apparatus,
Spray a solution of xan in a solvent onto inorganic fine particles.
Cloth and then heat dry to remove solvent
A method of forming a film by using the method. The particle size of the specific inorganic fine particles thus obtained is
The average particle size of the primary particles is 3mμ ~ 2μm, especially 5mμ ~
It is preferably in the range of 500 mμ. Also, BE
Specific surface area by T method is 20 ~ 500m ^Two / g is preferred
No. The average particle size is too small or the specific surface area is too large
Sometimes, for example, use a blade-type cleaning device.
Inorganic particles easily slip through when cleaning
Cleaning failure may occur. On the other hand,
When the average particle size is too large or the specific surface area is too small
Means that the fluidity of the developer decreases and the chargeability becomes unstable,
As a result, durability may decrease. The specific inorganic fine particles may be external to the toner particle powder.
Is added to the toner particles and mixed.
It is contained in a worn state. The content ratio of the specific inorganic fine particles is from 0.1 to
Preferably 5% by weight, especially 0.1 to 2% by weight.
Preferably, there is. Content ratio of the specific inorganic fine particles
Is too small, the fluidity of the developer may decrease.
As a result, the triboelectricity of the toner becomes poor,
It is difficult to apply an appropriate amount of electrostatic charge to the toner
And fog may occur. In addition, the content ratio
Is too large, some of the specific inorganic fine particles
-May exist in a state free from particles,
The specific inorganic fine particles that have been released are separated from the inner wall of the
Deposits on the blades, regulating blades, etc.
Is not good enough to charge the toner
It is difficult to apply a positive charge to
Degradation may occur. The organic fine particles used in the present invention are larger than the toner particles.
Small diameter, for example, primary particles (separated into individual unit particles
It is preferable that the average diameter of the
More preferably, the thickness is about 0.1 to 2 μm. Organic fine particles
If the average diameter of the toner is too large, the triboelectrification of the toner is impaired.
Easy to be. On the other hand, when the average diameter of the organic fine particles is too small,
Sufficient cleaning properties cannot be obtained. The ratio of the organic fine particles is 0.01 to 3% by weight of the whole toner.
It is particularly preferably 0.1 to 2% by weight. Organic fine particles
If the ratio is too large, the triboelectric charging of the toner is
Cheap. On the other hand, when the average diameter of the organic fine particles is too small,
Cleanability cannot be obtained. As an organic substance for constituting such organic fine particles,
Although not particularly limited, a relatively hard and moderate polishing performance is obtained.
Therefore, a vinyl polymer is preferred. Such a vinyl
Polymers are produced by various polymerization methods such as emulsion polymerization and suspension polymerization.
Manufactured by the process, but with small diameter and spherical organic fine particles
The emulsion polymerization method is preferred from the viewpoint that the compound is efficiently obtained. Especially
Monomer itself to obtain phenyl-based polymer has emulsifying action
Emulsion polymerization method without emulsifier
It is preferable to obtain a vinyl polymer. On the contrary
When an emulsifier is used, friction of the toner due to the emulsifier is
Chargeability is impaired or frictional charge temperature / humidity
Dependence on the environment such as degree may increase. Acrylic polymers, styrene
Polymer, etc. can be preferably used.
Kuryl polymers are preferred. Acrylic polymers are mainly acrylic acid or
Acrylate, methacrylic acid or methacrylic acid
Single weight obtained by polymerizing monomers selected from esters
It is a union or copolymer. Such acrylic polymer
Acrylic monomers used to obtain
Crylic acid, methyl acrylate, ethyl acrylate,
N-butyl acrylate, isobutyl acrylate, acrylic acid
Propyl, n-octyl acrylate, dodecyl acrylate
, Lauryl acrylate, 2-ethylhexyl acrylate
, Stearyl acrylate, 2-chloroethyl acrylate
Phenyl acrylate, α-chloromethacrylate
, Methacrylic acid, methyl methacrylate, methacrylic acid
Ethyl, propyl methacrylate, n-butyl methacrylate
, Isobutyl methacrylate, n-octyl methacrylate
Dodecyl methacrylate, lauryl methacrylate,
2-ethylhexyl acrylate, stearyl methacrylate
, Phenyl methacrylate, dimethyl methacrylate
Noethyl, diethylaminoethyl methacrylate and the like
Can be Among acrylic polymers, especially polymethyl methacrylate
Rate is most preferred. By polymethyl methacrylate
This makes it easy to obtain uniform, small-diameter organic fine particles.
And has a latent image carrier of toner because it is relatively hard
Or adhesion roller cleaning performance
And high polishing performance can be obtained. Also,
Stable because there is no risk of impairing the triboelectric charging
Developing performance is obtained. Other acrylic polymers may be used as necessary.
The monomer may be copolymerized. In this case
50% by weight or more of acrylic monomer in monomer composition
Is preferably used. Such other monomers
As styrene, o-methylstyrene, m-methyl
Styrene, p-methylstyrene, α-methylstyrene,
p-ethylstyrene, 2,4-dimethylstyrene, pn
-Butylstyrene, p-tert-butylstyrene, pn
-Hexylstyrene, pn-octylstyrene, p-
n-nonylstyrene, pn-decylstyrene, pn
-Dodecylstyrene, p-methoxystyrene, p-fe
Nylstyrene, p-chlorostyrene, 3,4-dichloros
Styrene monomer such as styrene, acrylonitrile, meta
Acrylic acid such as acrylonitrile or acrylamide
Is a methacrylic acid derivative; vinyl acetate, vinyl butyrate, benzoate
Vinyl esters such as vinyl fragrance; vinyl methyl ether
, Vinyl ethers such as vinyl ethyl ether; vinyl
Vinyl ketones such as methyl ketone; butadiene, iso
Dienes such as prenes; unsaturated acids such as maleic acid and fumaric acid
Carboxylic acids; and others. The above organic fine particles are externally added to the toner particle powder.
It is preferable to use a mixture. Specifically, an example
For example, using a mixing device such as a V-type blender,
By mixing the powder and the organic fine powder, the toner particles
Preferably, organic fine particles are present on the surface of the particles. The developer of the present invention is basically a one-component developer.
Or a two-component developer. The toner contains a colorant and other components in a binder resin.
Is a particle powder configured to contain the additive of (1). Tona
The average particle size of the particles is preferably about 5 to 20 μm.
Good. The binder resin constituting the toner is particularly limited
Instead, a conventionally known resin can be used. Heat fixing
Suitable for the system include, for example, styrene resin,
Tylene-acrylic resin, styrene-butadiene resin
Fat, polyester resin, epoxy resin, polyamide tree
Fat, polyurethane resin and the like. Also,
Suitable materials for the pressure fixing method include polyethylene and poly.
Polyolefins such as propylene and polytetrafluoroethylene
Ethylenes-vinyl acetate copolymer, ethylene-acyl
Lylic acid ester copolymer, polyethylene-methacrylic acid
Polyethylene copolymers such as ester copolymers;
Ter; styrene-butadiene copolymer; beeswax, carna
Waxes such as Ubarou and microcrystalline wax
And higher fatty acids such as stearic acid and palmitic acid;
And its salts and esters; epoxy resins;
Rubbers such as butylene rubber, cyclized rubber, and nitrile rubber;
Lamide, chlorone-indene resin, maleic acid-modified resin
Enol resin; Phenol-modified terpene resin; Silicon
Resin; and the like. Vine for magnetic toner
Polyester resin, styrene-acryl
Ril-based resins are preferably used. Positively used as a binder resin for toner
The ester resin is composed of an alcohol monomer and a carboxylic acid monomer.
Obtained by condensation polymerization with the
Examples of the monomer include ethylene glycol and diethyl.
Len glycol, triethylene glycol, 1,2-pro
Pyrene glycol, 1,3-propylene glycol, 1,4-
Butanediol, neopentyl glycol, 1,4-bute
Diols such as 1,4-bis (hydroxymeth
Tyl) cyclohexane, and bisphenol A, hydrogen
Added bisphenol A, polyoxyethylenated bisphene
Knoll A, polyoxypropylene bisphenol A, etc.
Etherified bisphenols and other divalent alcohols
For example, a polyester monomer. Also carboxylic acid simple substance
As a body, for example, maleic acid, fumaric acid, mesacon
Acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid
Acid, isophthalic acid, terephthalic acid, cyclohexanedica
Rubonic acid, succinic acid, adipic acid, sebacic acid, malon
Acids, anhydrides of these acids, lower alkyl esters and lino
Examples include dimer of maleic acid and other divalent organic acid monomers.
I can do it. In addition to the above divalent monomers, if necessary
Thus, a trivalent or higher polyvalent monomer may be used. Trivalent or more
As polyhydric alcohol monomers, for example, sorbitol,
1,2,3,6-hexanetetrol, 1,4-sorbitan, pen
Taerythritol, dipentaerythritol, tripen
Taerythritol, sucrose, 1,2,4-butanetrio
1,2,5-pentanetriol, glycerol, 2-
Methylpropanetriol, 2-methyl-1,2,4-buta
Triol, trimethylolethane, trimethylol
Propane, 1,3,5-trihydroxymethylbenzene,
And others. In addition, trivalent or higher
As the boric acid monomer, for example, 1,2,4-benzenetrica
Rubonic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-cy
Chlohexanetricarboxylic acid, 2,5,7-naphthalenetri
Carboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4
-Butanetricarboxylic acid, 1,2,5-hexanetricarbo
Acid, 1,3-dicarboxyl-2-methyl-2-methyle
Carboxypropane, tetra (methylenecarboxy)
Methane, 1,2,7,8-octanetetracarboxylic acid,
Oleic acid trimer acids, anhydrides of these acids, and others.
I can do it. A toner preferably used as a binder resin for toner.
Tylene-acrylic resin is composed of styrene monomer and acrylic
This is a resin obtained by copolymerization with a monomer. Sushi
Specific examples of the len-based monomer include, for example, styrene, o-
Methylstyrene, m-methylstyrene, p-methylstyrene
Len, α-methylstyrene, p-ethylstyrene, 2,4
-Dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, p-
n-octylstyrene, pn-nonylstyrene, p-
n-decylstyrene, pn-dodecylstyrene, p-
Methoxystyrene, p-phenylethylene, p-chloro
Styrene, 3,4-dichlorostyrene and the like can be mentioned.
And these monomers may be used alone or in combination.
May be used in combination. Specific examples of acrylic monomers
Examples include acrylic acid, methyl acrylate,
Ethyl acrylate, n-butyl acrylate, isoacrylate
Butyl, propyl acrylate, n-octyl acrylate
, Dodecyl acrylate, lauryl acrylate, acrylic
2-ethylhexyl acrylate, stearyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, α-c
Acrylic acid such as methyl loracrylate or its es
Ters; methacrylic acid, methyl methacrylate, methacrylic acid
Ethyl acrylate, propyl methacrylate, n-methacrylate
Butyl, isobutyl methacrylate, n-methacrylate
Cutyl, dodecyl methacrylate, lauri methacrylate
2-methylhexyl methacrylate, methacrylic acid
Tearyl, phenyl methacrylate, dimethyl methacrylate
Aminoethyl, diethylaminoethyl methacrylate, etc.
Methacrylic acid or its esters; and others
These monomers may be used alone
However, a plurality of components may be used in combination. Colorants include, for example, carbon black,
Anine blue, benzidine yellow, nigrosine dye,
Aniline blue, calco oil blue, chrome yellow
ー, Ultramarine Blue, Dupont Oil Red, Key
Norin yellow, methylene blue chloride, maracai
Togreen Oxalate, Lamp Black, Rose Ben
Dyes and pigments such as gall can be used. Magnetic fine particles used when magnetic toner is used
Particles that are strongly magnetized in that direction by a magnetic field
Quality, such as iron, ferrite, magnetite
Ferromagnetic metals such as iron, nickel, cobalt, etc.
Is an alloy or compound containing these metals, ferromagnetic elements
Not included but shows ferromagnetism when appropriately heat treated
Alloys such as manganese-copper-aluminum
Or a Heusler alloy such as manganese-copper-tin
Alloys or chromium dioxide
You. Magnetic particles are bound to obtain uniform magnetic properties.
Is preferably dispersed and contained uniformly in the base resin.
From the viewpoint of such, the average particle size is preferably 50 to 2000 mμ.
And particularly preferably 100 to 1000 mμ. Also, magnetic fine particles
The content ratio of the toner is preferably 15 to 65% by weight of the magnetic toner.
And particularly preferably 25 to 55% by weight. The content ratio is too low
In the case of, toner scattering may occur.
If the proportion is excessive, a uniform magnetic
When it is difficult to form a toner layer and development unevenness occurs,
There is a case. Required to obtain the toner particles, in addition to the colorant
Examples of additives used in accordance with
Agents, release agents and the like. Use various pigments or dyes as charge control agents
be able to. Specifically, nigrosine, azo,
Quaternary ammonium salt or thiourea pigments or dyes
Can be used. These charge control agents can be combined
May be used. The content ratio of the charge control agent
100 parts by weight of fat, preferably 0.5 to 10 parts by weight, especially
Preferably it is 1 to 5 parts by weight. Examples of the release agent include polyolefin and fatty acid metal.
Salt, fatty acid ester, partially saponified fatty acid ester, high quality
Fatty acids, higher alcohols, liquid or solid paraffin
Wax, amide wax, polyhydric alcohol esthetic
, Silicone varnish, aliphatic fluorocarbon, etc.
Can be In particular, rings specified in JIS K2531-1960
The softening point as measured by the ball method is 80-180 ° C, especially 70-160
Polyolefin such as polyethylene, polypropylene, etc.
Are preferred. These release agents may be used in combination.
No. The content of the release agent is 100 parts by weight of the binder resin.
On the other hand, it is preferably 1 to 10 parts by weight. Used when the developer of the present invention is a two-component developer
Carriers of various configurations can be used.
In particular, if the surface of the magnetic particles is a silicone resin
Or carrier coated with fluorine resin
Is preferred. Examples of compounds used in resin-coated carriers include
Silicon varnish, silicone rubber, silicone resin
Or a silicone resin such as a cured product thereof;
Vinylidene fluoride-tetrafluoroethylene copolymer, tetraflu
Oroethylene, methyl methacrylate-methacrylic acid-
1,1-dihydroxyperfluoroethyl copolymer, styrene
Len-methacrylic acid-1,1,3-trihydroxyperfur
Using a fluororesin such as o-n-propyl copolymer;
Is preferred. The above substances may be used alone,
Alternatively, a plurality of types may be appropriately combined and used. Using such silicone resin or fluorine resin
In the resulting resin-coated carrier, the surface energy
Energy is significantly reduced, resulting in toner material or positive
Transfer of inorganic chargeable inorganic particles to carrier particles
And contamination of the carrier can be considerably suppressed.
It is possible to obtain a developer having excellent durability. In addition, silicone-based resins are
Those having an organic group such as a alkyl group or an aromatic group are preferred.
With organic groups such as methyl and phenyl
Is preferred. Silicone resin having such an organic group
Specific examples of the compound to be obtained include, for example,
Siloxane, methylphenylpolysiloxane, diphe
Nylpolysiloxane, modified products thereof, and the like.
it can. In particular, poly groups having methyl or phenyl groups
Siloxane has excellent negative charge properties and can be obtained using
That the resin-coated carrier and the toner are frictionally charged
Good positive triboelectric charge on the toner
it can. And, in the above organic group, a methyl group,
By appropriately selecting the content of the phenyl group, the carrier
Adjust properties such as hardness, toughness, and triboelectricity of the film
It is therefore possible to combine with a resin-coated carrier
The conditions required for the toner used are considerably relaxed,
There is an advantage that the selection range of the toner is wide. Fluorine resin for forming the carrier coating layer
Is particularly limited as long as it contains a fluorine atom.
However, for example, a compound represented by the following general formula or
A polymer obtained by polymerizing a monomer, vinylidene fluoride
An ethylene copolymer or the like can be preferably used. (Where R ₁₁ And R ₁₂ Is a hydrogen atom or methyl
Represents a group, n and p each represent an integer of 1 to 8, m, q
Represents an integer of 1 to 19, respectively. In addition, the monomer represented by the above general formula or
In particular, methacrylic acid-1,1-dihydroperfluoro
Ethyl, methacrylic acid-1,1,3-trihydroperfluoro
Ro-n-propyl and the like can be preferably used. Also, vinylidene fluoride-ethylene tetrafluoride copolymer
When used, these copolymer molar ratio is 75: 2
Those in the range of 5-95: 5 are preferred, especially 75: 25-8
Those in the range of 7.5: 12.5 are preferred. Specific examples of the fluorine resin include the following structural formula
Examples include, but are not limited to:
It is not something to be done. In the following structural formula, n is 1 or more.
Represents an integer. In particular, when a fluororesin-coated carrier is used, toner
Has a large effect of positively charging
Charge control agent does not have to be included in the toner
A developer having extremely high durability can be obtained. The magnetic particles constituting the carrier
Materials that are strongly magnetized in that direction, such as
Iron, nickel, Kovar including iron and magnetite
Metals or alloys such as
Particles made of a compound containing an element can be used,
In particular, ferrite particles that do not generate carrier scattering are preferred.
No. The method for producing the resin-coated carrier is not particularly limited.
But not used, for example, as a coating component
A coating solution prepared by dissolving a curing agent in a solvent
Apply to the surface, then heat and dry to remove the solvent
And, if necessary, heat-curing the coating layer.
Can be built. The average particle size of the carrier is preferably 20 to 200 μm.
More preferably, it is particularly preferably 40 to 150 μm. Cap
When the average particle size of the rear is too small, the carrier
So-called carrier adhesion that forms a fixed image
Elephants may occur, resulting in blurred images,
On the other hand, when the average particle size of the carrier is excessive, image unevenness occurs.
May be born. When performing image formation using the developer of the present invention,
The organic photoreceptor preferably used is, for example, aluminum
Organic compounds on a conductive support made of
Composed of a photoconductive semiconductor dispersed in a resin binder
Are formed by laminating photosensitive layers. The photosensitive layer may be, for example, an anthranthrone compound.
Products, perylene derivatives, bisazo compounds, phthalocyanines
Generates charge carriers by absorbing visible light such as nin-based compounds
Styrene-methyl methacrylate
Copolymer, polycarbonate resin, silicone resin, etc.
A carrier generation layer dispersedly contained in a binder resin of
For example, oxadiazole derivatives, triarylamine derivatives
Conductor, polyarylalkane derivative, hydrazone derivative
Derivatives, stilbene derivatives, styryltriarylamines
Transfer carriers generated in the carrier generation layer such as conductors
Carrier transport layer containing carrier transport material to be transported
Use of a function-separated type photosensitive layer composed of
Is preferred for improving the resolution. Next, an image forming process using the developer of the present invention will be described.
You. FIG. 1 shows an image formation using the developer of the present invention.
Of an image forming apparatus that can be suitably used for
Show. Reference numeral 10 denotes an organic photoreceptor for forming an electrostatic latent image.
The organic photoreceptor 10 has a rotary drum shape. This
Around the organic photoreceptor 10 from the upstream side in the rotation direction.
Toward the flow side, in order, corona charger 1, exposure optical system 2,
Magnetic brush developing device 3, electrostatic transfer device 4, separator 5, brake
A cleaning device 6 is disposed. In the above apparatus, the corona charger 1 is used to
The developing surface of the light body 10 is charged to a uniform potential, and then exposed.
Imagewise exposed surface of the organic photoreceptor 10 after being imagewise exposed by the optical system 2
An electrostatic latent image corresponding to the original is formed. And developing device
3. The toner corresponding to the original on which the electrostatic latent image has been developed
-An image is formed. The toner image on the organic photoreceptor 10 is electrostatic
The image is electrostatically transferred to the transfer paper 8 by the transfer device 4 and
8 is heated and fixed by the heat roller fixing device 7.
To form a fixed image. On the other hand, passed through the electrostatic transfer unit 4
The obtained organic photoreceptor 10 is cleaned by the blade-type cleaning device 6.
Surface remained after the surface was rubbed
After the toner is scraped, the surface is cleaned and
And to be subjected to a charging process by the corona charger 1.
You. Specific Examples Hereinafter, specific examples of the present invention will be described.
The invention is not limited to these examples. (Production of inorganic fine particles) (1) Inorganic fine particles A (for the present invention)
Dissolve polysiloxane having functional groups in xylene
Thus, a treatment liquid was prepared. Next, silica fine particles "Aerosil 200"
Into a mixer.
And a ratio such that the above-mentioned polysiloxane is 5% by weight.
After spraying, put these in a flask and stir
Remove the solvent xylene at a temperature of 200 ° C for 5 hours.
Leaving an ammonium salt as a functional group
Inorganic fine particles obtained by surface treatment of polysiloxane were obtained.
This is referred to as “inorganic fine particles A”. The inorganic fine particles A
The average primary particle size is 12mμ and the specific surface area by BET method is 11
5m ^Two / g. (2) Inorganic fine particles B (for the present invention)
Dissolve polysiloxane having functional groups in xylene
Thus, a treatment liquid was prepared. Next, silica fine particles "Aerosil 300"
Into a mixer.
And a ratio such that the above-mentioned polysiloxane is 7% by weight.
Other than spraying with
Thus, surface-treated inorganic fine particles were obtained. This is called "inorganic fine particle B"
And The inorganic fine particles B have an average primary particle diameter of 7 m.
μ, BET specific surface area is 126m ^Two / g. (3) Inorganic fine particles C (for the present invention)
Dissolve polysiloxane having functional groups in xylene
Thus, a treatment liquid was prepared. Next, silica fine particles "Aerosil 200" (Aero Japan
(Manufactured by Jill Co.) into a mixer.
And the above-mentioned polysiloxane is 10% by weight.
Other than spraying with
Thus, surface-treated inorganic fine particles were obtained. This is called "inorganic fine particle C"
And The inorganic fine particles C have an average primary particle size of 12
mμ, BET specific surface area 93m ^Two / g. (4) Inorganic fine particles D (for comparison) Silica fine particles “Aerosil 200” (Nippon Aerosil Co., Ltd.)
Made into a closed Henschel mixer heated to 100 ° C
The silica particles containing amino group
Solution of corn oil in isopropyl alcohol
(Viscosity 1200 cps, amino equivalent 3500)
Spray at a rate such that the silicone oil becomes 2.0% by weight.
Stir at high speed with fog, then dry at 150 ° C
The surface is treated with the amino group-containing silicone oil.
The obtained inorganic fine particles for comparison were obtained. This is called "inorganic fine particles
Child D ". (5) Inorganic fine particles E (for comparison) Silica fine particles "Aerosil 200" (Nippon Aerosil Co., Ltd.)
Made into a closed Henschel mixer heated to 100 ° C
The silica fine particles are
Γ-Aminopropyltriethoxysilicone as a coupling agent
The solution of orchid dissolved in alcohol is
At a rate such that the silane coupling agent becomes 5.0% by weight
Stir at high speed while spraying, then dry at 120 ° C
After drying, the amino group-containing silane coupling agent
Comparative inorganic fine particles whose surfaces were treated were obtained. these
This is referred to as “inorganic fine particles E”. (Production of Toner) Styrene-acrylic copolymer (monomer composition; polystyrene)
: Methyl methacrylate: butyl acrylate = 75: 1
0:15, glass transition point Tg = 59 ° C) 100 parts by weight and carbon
Black (Mogal L, manufactured by Cabot) 5 parts by weight
Ripropylene (Viscol 660P, manufactured by Sanyo Chemical Industries) 3
Parts by weight and premixed with a Henschel mixer
After that, it is melt-kneaded at a temperature of 120 ° C with an extruder
And then cooled, coarsely pulverized, and then jet milled
Finely pulverized and further classified to obtain a toner with an average particle size of 10 μm
Was. (Manufacture of carrier) Vinylidene fluoride-tetrafluoroethylene copolymer “VT-
100 ”(copolymer molar ratio 80:20, intrinsic viscosity = 0.95dl / g, die
Kin Industry Co., Ltd.) and methyl methacrylate copolymer “A
6 g of Clippet MF (Mitsubishi Rayon) and acetone
And mixed solvent of methyl ethyl ketone (mixing volume ratio = 1:
1) A coating solution is prepared by dissolving the coating solution in 500 ml.
Using fluidized bed equipment, spherical copper-zinc ferrite
1 kg of magnetic particles consisting of particles, and then 200 ° C
For 5 hours, then sieving the agglomerates
Having an average particle diameter of 82 μm having a coating layer having a thickness of about 2 μm.
m of carriers were produced. (Manufacture of developer) Inorganic fine particles shown in Table 1 were added to 100 parts by weight of the toner.
And organic fine particles in the amounts shown in Table 1 and
Mix with a Henschel mixer. 30 g of the toner thus produced and the above carrier 750
g was mixed to obtain a developer. (Actual photo test) An electrophotographic copier "U-Bi"
x1550 "(manufactured by Konishi Roku Photo Industry Co., Ltd.)
℃, relative humidity 80% high temperature and high humidity environment conditions and 20 ℃, 50%
Under normal temperature and humidity conditions
The following items were evaluated. Image density Copy original document with solid black and white background
The maximum density (Dmax) of the image obtained by
The density (fog) of the corresponding part is measured with a densitometer “Sakura Densit
Meter PDA-65 "(manufactured by Konishi Roku Photo Industry Co., Ltd.)
It was measured. Cleanability Repeated copying and visually check for black spots
did. The results are summarized in Table 2. According to the results in Table 2, when the comparative developer was used,
Fog occurs under high temperature and high humidity conditions,
-Black spots occurred due to poor cleaning.
On the other hand, when the developer of the present invention is used, high-temperature and high-humidity conditions
Even underneath and when making multiple copies
Demonstrates high developability and high image quality without fog
Images are obtained, and image defects due to poor cleaning also occur
do not do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of an image forming apparatus which can be suitably used for forming an image using the developer of the present invention. DESCRIPTION OF SYMBOLS 1 ... Corona charger 2, ... Exposure optical system 3 ... Magnetic brush developing device 4, ... Electrostatic transfer device 5 ... Separator, 6 ... Blade type cleaning device 7 ... Hot roller fixing device, 8 ...... Transfer paper 10 ... Organic photoreceptor

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 9/08

Claims (1)

(57) [Claims] The following formula (A) having an ammonium salt as a functional group
Inorganic fine particles surface-treated with a polysiloxane containing a structural unit represented by, a toner in which a colorant is dispersed and contained in a binder resin, and organic fine particles having an average particle size smaller than the toner particles are mixed. A developer. (Where R ₁ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or R ₂ represents a bonding group or a mere bond, R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents a halogen atom. Each of the groups represented by R _{1 to} R ₅ includes those having a substituent. ) 2. 2. The developer according to claim 1, wherein said inorganic fine particles are silica. 3. 2. The developer according to claim 1, wherein said organic fine particles have an average particle size of 0.01 to 5 [mu] m. 4. 2. The developer according to claim 1, wherein the magnetic particles further comprise a carrier coated with a silicone resin or a fluorine resin. 5. A step of developing an electrostatic latent image formed on the photoconductor with a developer, and an image forming method including a cleaning process using a cleaning member, wherein the photoconductor is an organic photoconductor, and the cleaning member is a cleaning blade. A toner in which a colorant is dispersed and contained in a binder resin and an inorganic fine particle whose surface is treated with a polysiloxane containing a structural unit represented by the following formula (A), wherein the developer has an ammonium salt as a functional group; An image forming method, wherein the developer is a mixture of organic fine particles having an average particle diameter smaller than that of the toner particles. (Where R ₁ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or R ₂ represents a bonding group or a mere bond, R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents a halogen atom. Each of the groups represented by R _{1 to} R ₅ includes those having a substituent. )