JP2675950C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION       [0001]     [Industrial applications]   The present invention is for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc.
, Especially a color toner.       [0002]     [Prior art]   It is well known in the art to form and develop an image on the surface of a photoconductive material by electrostatic means.
You.       [0003]   That is, U.S. Pat. No. 2,297,691 and JP-B-42-23910.
And a number of methods are known, such as Japanese Patent Publication No. 43-24748,
Using a photoconductive substance, an electric latent image is formed on a photoreceptor by various means.
Attach an extremely finely grounded inspection material called toner on the latent image
As a result, a toner image corresponding to the electrostatic latent image is formed.       [0004]   Next, if necessary, the toner is transferred to the surface of the image support such as paper, and then heated and heated.
The image is fixed by pressure or solvent vapor to obtain a copy. Also transfer toner image
In the case of having a step for removing the residual toner, a step for removing the residual toner is usually provided.
You.       [0005]   A developing method for visualizing an electric latent image using toner is described in, for example, US Pat.
No. 2,618,552 described in JP-A-2211,776.
The cascade developing method described in the specification, and US Pat. No. 2,874,063.
Described in the magnetic brush method and in the specification of US Pat. No. 3,909,258.
A method using a conductive magnetic toner is known.       [0006]   As a toner applied to these developing methods, a colorant is generally added to a thermoplastic resin. After mixing and dispersing, a fine powder is used. Polystyrene as a thermoplastic resin
Resin is the most common, but polyester resin, epoxy resin, acrylic resin
For example, a toluene resin or a urethane resin may be used. Carbon black is a coloring agent
Most widely used, and in the case of magnetic toners, iron oxide black magnetic powder is often used
Can be In the case of a system using a so-called two-component developer, the toner is usually made of glass.
It is used by being mixed with carrier particles such as beads and iron powder.       [0007]   The toner image on the final copy image forming member such as paper is placed on the support by heat, pressure, or the like.
Permanently established. Conventionally, this fixing process is often performed by heat.
I have.       [0008]   When a step of transferring a toner image is provided, the remaining toner on the photoreceptor is generally used.
A step is provided for removing the impurities.       [0009]   In recent years, the transition from mono-color copying to full-color copying has rapidly increased in copiers, etc.
Investigation and practical application of two-color color copiers and full-color copiers are increasing
It has been done. For example, “Journal of the Society of Electrophotography,” Vol 22, No. 1 (1983)
And “Journal of the Institute of Electrophotography,” Vol 25, No. 1, color like P52 (1986)
There are also reports of reproducibility and gradation reproducibility.       [0010]   However, it is not immediately compared with the real thing such as television, photographs, and color prints.
For those who see color images that are more beautifully processed than they are,
It is not always possible to satisfy the full-color electrophotographic image currently in practical use.
Not.       [0011]   Color image formation by full-color electrophotography generally uses three primary colors, yellow,
All colors are reproduced using three color toners of magenta and cyan.
You.       [0012]   First, light from a document is transmitted through color separation light, which is complementary to the color of the toner.
An electrostatic latent image is formed on the photoconductive layer through a filter, and then the development and transfer steps are performed.
After that, the toner is held on the support. This process is performed several times sequentially,
After overlapping the toner on the same support while fixing the
To obtain the final full-color image.       [0013]   Generally, in the case of a so-called two-component developing method in which a developer comprises a toner and a carrier,
In this case, the developer causes the toner to have a required charge amount and charge due to friction with the carrier.
It is charged to a polarity and develops an electrostatic image using electrostatic attraction.
To obtain a good visible image, the toner mainly determined by the relationship with the carrier
Must have good triboelectric charging properties.       [0014]   For today's problems such as those mentioned above, searching for carrier core agents and carrier coating agents and
Optimization of the toner amount, or study of charge control agents and fluidity-imparting agents added to the toner,
Any of the materials that make up the developer, such as improving the binder that is the body
Many studies have been made to achieve excellent triboelectric charging.       [0015]   For example, as a technology for adding a charge auxiliary agent such as chargeable fine particles to toner,
JP-A-52-32256 and JP-A-56-64352 disclose toner and the opposite polarity.
Resin fine powder and a fluorine-containing compound disclosed in JP-A-61-160760.
A technique has been proposed to obtain stable triboelectricity by adding each to a developer.
Even today, many charge assisting agents are being developed.       [0016]   Further, various techniques have been devised as a method for adding the charging auxiliary as described above. An example
For example, the electrostatic force between the toner particles and the charging auxiliary or the van der Waals force
Generally, a method of adhering to the surface of toner particles is used.
It is. However, in this method, the additive is uniformly dispersed on the surface of the toner particles.
It is not easy, and additives are not adhered to the toner particles and aggregate with each other,
It is difficult to avoid the presence of so-called free additives. This trend Becomes more remarkable as the specific electrical resistance of the charging aid increases and the particle size decreases.
. In such a case, the performance of the toner is affected. For example, the triboelectric charge is unstable
The image density is not constant, and the image has a lot of fog.       [0017]   Or, when performing continuous copying, etc., the content of the charging aid changes, and the image quality at the initial stage is maintained.
It had problems such as not being able to hold.       [0018]   Another method of addition is to add the binder resin and colorant during the production of the toner.
There is a method of adding a charging auxiliary. However, it is easy to make the charge control agent uniform
And that substantially contributes to the chargeability are those near the toner particle surface.
In addition, since the charge assisting agent and the charge controlling agent present inside the particles do not contribute to the charging property,
It is not easy to control the amount of the charge auxiliary added and the amount of dispersion on the surface. Again
Even in the toner obtained by such a method, the amount of triboelectric charge of the toner is unstable, and
Charge assisting agents, such as those that satisfy the developer characteristics cannot be easily obtained.
The fact is that the use of only has not been able to achieve a satisfactory quality.       [0019]   In recent years, the demand for higher definition and higher image quality of copying machines has been increasing in the market.
In the technical field, attempts to achieve high image quality color by reducing the particle size of toner
However, as the particle size becomes smaller, the surface area per unit weight increases,
Where the amount of charged electricity tends to be large, and where image density is low or durability may be deteriorated
It is. In addition, due to the large amount of charge of the toner, the adhesion between the toners is strong,
Fluidity decreases, causing problems in toner replenishment stability and tribo addition to replenished toner
Come.       [0020]   In the case of color toners, conductive substances such as magnetic substances and carbon black are included.
Because there is no charge, there is no part that leaks charge, and generally the amount of charged electricity tends to increase
. This tendency is particularly noticeable when using a polyester binder with high charging performance.
More prominent.       [0021]   Further, especially in a color toner, the following properties are strongly desired.
. (1) The toner needs to have good fixability. (2) The toner must have good hue and spectral reflection characteristics and sufficient saturation.
No.       [0022]   From this point of view, many binder resins have been studied, but the
No toner satisfying all the characteristics has been developed. Today, in the art,
Polyester resins are often used as binder resins for color.
In general, toners made of tellurium-based resins are easily affected by temperature and humidity, and charge amount under low humidity
Stable even in a wide range of environments due to problems such as excessive charge and insufficient charge under high humidity
There is an urgent need to develop a color toner having a reduced charge amount.       [0023]   Color toners such as yellow, magenta or cyan toners
Leaks triboelectric charge because it does not contain conductive substances such as
There is no portion in the toner, and the frictional charge of the toner generally tends to increase.
This is especially true when polyester binders with high triboelectricity
Notable when used as a resin.       [0024]   In a color toner for forming a full-color image, as shown below,
Characteristics are strongly desired. (1) To ensure that the fixed toner does not hinder color reproduction due to irregular reflection of light,
At the time of fixing, the toner particles are almost in a state of almost complete melting, and the shape can not be distinguished
It is necessary to transform to (2) Make sure that the upper toner layer does not disturb the color tone of the lower toner layer having a different color tone.
In addition, the color toner must have transparency. (3) Each color toner has balanced hue and spectral reflection characteristics and sufficient saturation
Must have.       [0025]   Today, polyester resins are widely used as binder resins for full-color toners.
ing. As described above, toner containing polyester resin generally has temperature and humidity.
It is liable to be affected by the
Problems that are likely to occur, and have a stable charge amount in a wide range of environments.
Development of toners and developers is expected.       [0026]     [Problems to be solved by the invention]   An object of the present invention is to provide a toner for developing an electrostatic image, which solves the above-mentioned problems.
It is to be.       [0027]   The object of the present invention is not easily influenced by the environment such as temperature and humidity, and a stable triboelectric charging property is always provided.
To provide a toner for developing an electrostatic image.       [0028]   An object of the present invention is to be able to form a clear image without fog and to have excellent durability stability.
To provide a toner for developing electrostatic images.       [0029]   SUMMARY OF THE INVENTION An object of the present invention is to provide an electrostatic image forming apparatus capable of forming a clear color OHP image without turbidity.
An object of the present invention is to provide a color toner for an image.       [0030]     Means and Action for Solving the Problems   Specifically, the present invention has at least a colorant-containing resin particle and an external additive.
In the electrostatic image developing toner, the colorant-containing resin particles have a weight average particle diameter (D_Four) 5
10 to 10 μm, and the external additiveHydrophobic titanium oxide fine powder, the hydrophobic titanium oxide
Fine powder is subjected to hydrophobic treatment with a silane coupling agent in an aqueous medium.
AndHaving an average particle size of 0.01 to 0.2 μm, having a hydrophobicity of 20 to 98%,
The light transmittance for a light wavelength of 400 nm is 40% or more.SparseAqueous anatase-type acid
The present invention relates to a toner for developing an electrostatic image, which is a fine powder of titanium oxide.       [0031]   The present inventor has proposed that the electrostatic charge image developing toner (especially, non-magnetic color toner) As a result of intensive studies on stabilization, the above-mentioned silane coupling agent was used as an external additive.
Hydrophobic anatase-type titanium oxide fine particles treated with
Has been found to be extremely effective in terms of imparting, environmental stability, etc., and has reached the present invention.
Things.       [0032]   This is difficult to achieve with the commonly known hydrophobic silica as a flow improver
It was what was.       [0033]   The reason is that silica fine particles themselves have strong negative charge
This is because the titanium fine particles are almost neutrally chargeable. Hydrophobic oxidation than before
It has been proposed to add titanium fine particles, but titanium oxide fine particles
The activity was smaller than that of silica, and the hydrophobization was not always sufficiently performed. Ma
In addition, when a large amount of treating agent is used or a highly viscous treating agent is used,
Is certainly increased, but coalescence of particles occurs, and the fluidity-imparting ability decreases.
In addition, compatibility between charging stabilization and imparting fluidity has not always been achieved.       [0034]   The use of anatase-type titanium oxide fine particles is disclosed in, for example,
As disclosed in Japanese Patent Publication No. 112052, anatase-type titanium oxide fine particles
Product specific resistance value is 10⁷As small as Ωcm, if used as it is under high humidity
Of triboelectric charge is fast and is not necessarily satisfactory in stabilizing the toner charge.
Instead, there was a need for improvement.       [0035]   Further, JP-A-59-5225 discloses an example in which a hydrophobic titanium oxide is contained in a toner.
No. 5 discloses a toner containing titanium oxide treated with an alkyl trialkoxysilane.
Has been proposed, but the addition of titanium oxide certainly makes toner electrophotographic
The surface activity of titanium oxide is originally small, but the coalescence at the processing stage
Due to particles and uneven hydrophobicity, full color image formation is not always
It was not satisfactory when applied to color toners.       [0036]   The present inventors have conducted intensive studies on the stability of the chargeability of the toner and found that
0.01-0.2 μm, hydrophobicity 20-98%, light for 400 nm light wavelength
Hydrophobic anatase-type acid treated with a silane coupling agent having a transmittance of 40% or more
Toner containing fine titanium oxide powder as an external additive stabilizes charging and imparts fluidity
It was found to be extremely effective in terms of giving.       [0037]   Anatase-type titanium oxide fine particles are produced using titanium chloride as a raw material.
Can be.       [0038]   Untreated anatase-type titanium oxide fine particles have hydrophilicity,
Hydrophobic anatase-type acid having a degree of 20-98% (preferably 20-80%)
Titanium iodide particles need to make hydrophilic anatase-type titanium oxide particles hydrophobic.
is there.       [0039]   As a preferable method for hydrophobizing the anatase type titanium oxide fine particles, an aqueous medium
In the body, anatase-type titanium oxide fine particles are dispersed while being dispersed to a primary particle size.
There is a method of surface treatment while hydrolyzing the coupling agent.
Titanium oxide fine particles are less likely to coalesce and treated more hydrophobic than in the gas phase.
The repulsion between the titanium oxide fine particles by the treatment works, and the anatase type titanium oxide
Fine particles are surface-treated in a state of substantially primary particles.       [0040]   For treating the titanium oxide surface while hydrolyzing the coupling agent in an aqueous medium
The method uses coupling that generates gas like chlorosilanes and silazanes.
It is not necessary to use an agent, and furthermore, titanium oxide particles
Highly viscous coupling agents, which are easy to unite and difficult to process well, can be used.
The effect of hydrophobization is enormous.       [0041]   As the coupling agent that can be used in the present invention, for example, a silane coupling agent
And a titanium coupling agent. More preferably used is silane Coupling agent, general formula     R_mSiY_n [Wherein, R represents an alkoxy group, m represents an integer of 1 to 3, and Y represents an alkyl group.
, A vinyl group, a glycidoxy group, a hydrocarbon group such as a methacryl group, n is 1 to
Indicates an integer of 3. ] It is shown by. For example, vinyltrimethoxysilane, vinyltriethoxy
Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetate
Xysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyl
Rutrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane
, Trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyl
Rutrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecy
Lutrimethoxysilane and the like can be mentioned.       [0042]   In particular, the formula C_pH_{2P + 1}-Si- (OC_qH_{2q + 1})_ThreeWherein p is an integer of 3 to 12
And q represents an integer of 1 to 3].
Hydrophobic treatment of anatase-type titanium oxide fine particles in aqueous medium using pulling agent
Good to do.       [0043]   When p in the above formula is smaller than 3, the hydrophobic treatment becomes easy, but the hydrophobicity is reduced.
When it is difficult to sufficiently impart it, and when p is greater than 12, the hydrophobicity is sufficiently increased.
However, coalescence between the titanium oxide particles increases, and the fluidity-imparting ability tends to decrease.       [0044]   Further, when q is larger than 3, the reactivity of the silane coupling agent decreases and the hydrophobicity is increased.
Is not sufficiently performed.       [0045]   In particular, p in the formula represents an integer of 3 to 12 (more preferably, an integer of 3 to 8), and q
Represents an integer of 1 to 3 (more preferably an integer of 1 or 2)
It is preferable to use a xysilane coupling agent.       [0046]   The treatment amount is 1 to 50 parts by weight, preferably 100 parts by weight of titanium oxide.
3 to 40 parts by weight, and the degree of hydrophobicity is 20 to 98%, preferably 20 to 80%,
Preferably, it should be 40-80%.       [0047]   If the degree of hydrophobicity is less than 20%, the charge amount is significantly reduced due to long-term storage under high humidity.
A mechanism for promoting triboelectric charging on the hardware side is required, and the developing device becomes complicated.
When the degree of hydrophobicity exceeds 98%, anatase-type titanium oxide with low volume resistivity is produced.
Even when used, it is difficult to control the triboelectric charging of titanium oxide itself, resulting in low
It becomes easy for the toner to charge up under moisture.       [0048]   Further, the average particle diameter of the titanium oxide fine powder having hydrophobicity is set at 0.1 from the viewpoint of imparting fluidity.
01-0.2μ is good. If the average particle size is larger than 0.2 μm, the flowability is poor.
The frictional electrification of the toner tends to be non-uniform, resulting in toner scattering and fog.
I will. On the other hand, when the average particle size is smaller than 0.01 μm, the colorant-containing resin particles
It is easy to be embedded in the surface, toner deterioration tends to occur quickly, and durability is low.
Easy to drop. This tendency is due to the sharp melt
This is particularly remarkable in the color toner of the nature.       [0049]   The primary average particle diameter of the titanium oxide in the present invention is 120,000 times that of a transmission electron microscope.
From the micrograph, average the primary particle size of 1000 particles.       [0050]   Further, in the present invention, the treated titanium oxide fine powder has an optical length of 400 nm.
Light transmittance of 40% or more in OHP film
Preferred for forming an image.       [0051]   The hydrophobicized titanium oxide fine powder used in the present invention has a primary particle diameter of 0.2 to
Although it is as small as 0.01 μm, it is indispensable if it is actually contained in the toner.
It is not necessarily dispersed in primary particles, but may be present in secondary particles.
Can be. Therefore, no matter how small the primary particle size, the behavior of secondary particles If the effective diameter is large, the effect of the present invention is reduced. However, in the visible range
The higher the light transmittance at the lower limit wavelength of 400 nm, the smaller the secondary particle diameter.
In addition, good results such as the ability to impart fluidity and the sharpness of the projected image of the OHP can be obtained.       [0052]   On the other hand, titanium oxide fine powder, which has poor transmission of visible light,
OHP film with a full-color image
When projected, the projected image is blurred, and a clear full-color projected image is obtained.
Becomes difficult.       [0053]   The crystal form of titanium oxide has a lattice constant (a) of 3.78 Å by X-ray diffraction.
Trom, anatase type whose lattice constant (b) is 9.49 angstroms
To verify that.       [0054]   As a method for obtaining hydrophobic titanium oxide fine particles, volatile titanium alkoxy
After low-temperature oxidation of titanium oxide and the like to obtain spherical titanium oxide fine particles,
Although there is a method of obtaining spherical titanium oxide, the starting material is expensive,
In view of the fact that is complex, the hydrophobic anatase titanium oxide used in the present invention
Fine powder can be easily produced, which is advantageous in cost.       [0055]   In the present invention, the aqueous medium is a medium containing water as a main component. concrete
In water, water itself, water with a small amount of surfactant added,
Examples thereof include those in which a pH adjuster is added and those in which an organic solvent is added to water. Surface activity
As the surfactant, a nonionic surfactant such as polyvinyl alcohol is preferable.
. The surfactant is preferably added in an amount of 0.1 to 5% by weight based on water. pH adjuster and
Examples thereof include inorganic acids such as hydrochloric acid.       [0056]   The titanium oxide fine powder is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the aqueous medium.
It is preferable to add and mix and treat with a hydrophobizing agent.       [0057]   The stirring is performed, for example, by using a mixer having stirring blades (specifically, an attritor, a TK
Titanium oxide fine powder in an aqueous medium with a high shear mixing device such as a mixer.
It is better to carry out enough to become the next particle.       [0058]   Titanium oxide fine powder hydrophobized with a silane coupling agent in an aqueous medium
In order not to coalesce the hydrophobic titanium oxide particles with the silane coupling agent in the
Further, surface treatment may be performed. The functional groups of titanium oxide remaining in the treatment in aqueous medium
The purpose is to further seal with a silane coupling agent.
Reactivity is very high once it has been treated in an aqueous system. This is because
Although it is not clear yet, since it has been treated organically in aqueous systems,
Familiarity between the non-reactive group of the coupling agent and the lipophilic group of the titanium oxide fine particles
Is good, and the reaction efficiency is increased.       [0059]   The silane coupling agent used for hydrophobic treatment in the gas phase is a general formula     R_mSiY_n [Wherein, R represents an alkoxy group or a chlorine atom, m represents an integer of 1 to 3,
Y represents a hydrocarbon group such as an alkyl group, a vinyl group, a glycidoxy group, and a methacryl group;
And n represents an integer of 1 to 3. ] Are shown. For example, typically, dimethyldichlorosilane,
Limethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane
, Allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltri
Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyl
Riacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane, etc.
I can give it.       [0060]   The titanium oxide fine powder is treated with a silane coupling agent,
Silane coupling that evaporates into a cloud-like form of finely divided tan powder by stirring etc.
Dry treatment can be performed to react the agent. Silane coupling agent is fine powder 1
1 to 20 parts by weight, more preferably 3 to 10 parts by weight, per 100 parts by weight. Is good.   The hydrophobic anatase type titanium oxide fine powder is contained in the toner in an amount of 0.02 to 3% by weight.
It is preferred that       [0061]   Also, the particle size of the toner is reduced (for example, 5 to 10 μm, preferably
To 9 μm), the titanium oxide of the present invention is also suitable. Reduce toner particle size
As a result, the surface area per weight increases, and excessive charging due to rubbing tends to occur. this
The effect of titanium oxide fine particles, which can control charging and impart fluidity, is great.       [0062]   In the present invention, the external additive has a polarity opposite to that of the colorant-containing resin particles, and
A region having a diameter of 0.5 to 0.02 μm, preferably 0.2 to 0.02 μm and a particle diameter of 0.
Adding organic resin particles each having a distribution peak in the range of 3 to 0.8 μm
Is also preferred.       [0063]   The reason is that the charge-up of the toner used in the present invention is caused by the above-mentioned organic tree.
This is because they are neutralized by the fat particles.       [0064]   Further, by adding the organic resin particles, the rise of the charge of the toner is reduced.
Accelerated and very stable charging properties are achieved from the beginning.       [0065]   The reason for this is not yet clear, but is presumed as follows. That is, organic
At the beginning of the rubbing of the toner particles with the charging member such as a carrier, the resin particles contain a colorant-containing resin.
The particles are strongly attracted to the charging member rather than the oil particles, and are charged. Therefore,
The rising of the charge of the colorant-containing resin particles having the opposite polarity is promoted. Meanwhile, once stand up
After peeling, on the contrary, it is more strongly attracted to the colorant-containing resin particles than the charging member,
The function of neutralizing excessive charging works.
Since the rising and saturation charge level can be maintained good and stable in various environments
is there.       [0066]   In order to make the above operation more effective, the organic resin particles have a particle size of 20 to 20.
Have peaks in each of the 0 μm region and the 300-800 μm particle size region
Is preferred. The proportion of the larger peak is preferably 2 to 20% by weight.
More preferably, the content is 3 to 13% by weight. If the average particle size is smaller than the above range, the organic resin particles
The particles adhere too strongly to the colorant-containing resin particles or become embedded, and
Fruits disappear. On the other hand, if it is larger than the above range, the dispersion becomes uneven or
The effect will be lost by separating.       [0067]   In the present invention, in order to ensure its performance and to have a stable negative charging property
Is preferably provided in an amount of 0.1 to 5.0% by weight based on the colorant-containing resin particles.
.       [0068]   Further, even when the diameter of the toner is reduced, the organic resin particles of the present invention are suitable.       [0069]   That is, when the diameter of the toner is reduced, the number of contact points between the toner and the carrier increases, and
Asphalt is likely to occur, and the number of points of contact between toner
Locking is more likely to occur. On the other hand, 0.2 to 0.0
Spherical organic resin particles with an appropriate size of 2μ are good spacers and good results
Effect. For the toner blocking, change the material of the opposite polarity resin particles to the toner resin.
Use of a material having a higher Tg is more effective.       [0070]   There are some examples of adding resin particles of the opposite polarity to the toner.
In JP-A-4-45135 and JP-B-52-32256, toner particles are used.
The addition of small colorless resin particles has been proposed.       [0071]   However, in these examples, the toner and the opposite polarity resin particles behave separately,
During development, the toner adheres to the latent image area, while the opposite polarity resin particles adhere to the background area.
It is said that.       [0072]   In other words, the opposite polarity resin particles function to promote charging of the toner.
Become. However, in the present invention, the opposite polarity resin particles which are sufficiently small
Finally, the toner is strongly adhered to the toner, and is developed as a unit.
The resin particles on the relatively coarse side of 300 to 800 mμ
It is different from the above-mentioned invention because it is characterized by improving
.       [0073]   More recently, silica and organic resin particles have been disclosed in JP-A-1-113767.
Have been proposed, which reduce the adhesion between the drum and toner.
It is used to weaken. However, in the present invention, the drum
In the configuration with the function of weakening the adhesive force on the side, the cleaning characteristics are further enhanced
Used for the purpose, that is, the purpose of moderately removing foreign substances on the drum
The present invention is different from the above-described invention because of its features.       [0074]   For the purpose of not lowering the charge of the toner, see Japanese Patent Publication No. 2-3172 and the like.
In addition, although a system to be used has been proposed, in the present invention, the charging is rather likely to be excessive.
Magnetic color toner is used positively to lower the charge.
It is an invention.       [0075]   The monomers constituting the opposite polarity resin particles used in the present invention are not particularly limited.
However, it is necessary to make a selection in consideration of the charge amount of the toner and the like. Used in the present invention
Specific examples of the monomer having addition polymerizability that can be represented by the following monomers
be able to.       [0076]   That is, styrene and its derivatives, for example, methylstyrene, dimethylstyrene,
Trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene
, Propyl styrene, butyl styrene, hexyl styrene, heptyl styrene,
Alkylstyrenes such as octylstyrene, fluorostyrene, chlorostyrene,
Halogenated styrenes such as bromostyrene, dibromostyrene and iodostyrene And nitrostyrene, acetylstyrene, methoxystyrene and the like.
You.       [0077]   Further, addition-polymerizable unsaturated carboxylic acids, that is, acrylic acid, methacrylic acid, α-
Tylacrylic acid, crotonic acid, α-methyl crotonic acid, α-ethyl crotonic acid,
Addition-polymerizable unsaturated aliphatic monomers such as isocrotonic acid, tiglic acid, and ungeric acid
Carboxylic acid, or maleic acid, fumaric acid, itaconic acid, citraconic acid, mesacon
Addition-polymerizable unsaturated aliphatic dicarboxylic acids such as acid, glutaconic acid and dihydromuconic acid
Acids.       [0078]   In addition, metal salts of these carboxylic acids can also be used.
The conversion can be performed after the completion of the polymerization.       [0079]   Further, the addition-polymerizable unsaturated carboxylic acid and alkyl alcohol, halogenated alcohol may be used.
Alkyl alcohol, alkoxyalkyl alcohol, aralkyl alcohol,
And esterified products with alcohols such as alkenyl alcohol. And
Examples of the alcohols include methyl alcohol, ethyl alcohol, and propyl alcohol.
Alcohol, butyl alcohol, amyl alcohol, hexyl alcohol,
Butyl alcohol, octyl alcohol, nonyl alcohol, dodecyl alcohol
Alkyl alcohols such as toluene, tetradecyl alcohol and hexadecyl alcohol
Halogenated alkyl alcohols obtained by partially halogenating these alkyl alcohols
Methoxyethyl alcohol, ethoxyethyl alcohol, ethoxyethoxy
Siethyl alcohol, methoxypropyl alcohol, ethoxypropyl alcohol
Alkoxyalkyl alcohols such as benzyl alcohol, phenylethyl
Alcohol, aralkyl alcohol such as phenylpropyl alcohol; allyl
Alkenyl alcohols such as alcohol and crotonyl alcohol can be mentioned.       [0080]   Amides and nitriles derived from the addition-polymerizable unsaturated carboxylic acids; Aliphatic monoolefins such as ethylene, propylene, butene and isobutylene; salts
Vinyl chloride, vinyl bromide, vinyl iodide, 1,2-dichloroethylene, 1,2-di
Bromoethylene, 1,2-diiodoethylene, isopropenyl chloride, isopromide
Lopenyl, allyl chloride, allyl bromide, vinylidene chloride, vinyl fluoride, vinylyl fluoride
Halogenated aliphatic olefins such as den; 1,3-butadiene, 1,3-pentane
Diene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene
Conjugated diene such as ene, 2,4-hexadiene, 3-methyl-2,4-hexadiene
Ene-based aliphatic diolefins are exemplified.       [0081]   Vinyl acetates, vinyl ethers; vinyl carbazole, vinyl pyridine
And nitrogen-containing vinyl compounds such as vinylpyrrolidone.       [0082]   Those obtained by polymerizing one or more of these monomers can be used.       [0083]   The reverse polarity resin particles used in the present invention are limited to using only one kind.
However, a plurality of types can be used in combination.       [0084]   In addition, the method for producing the opposite polarity resin particles used in the present invention includes a spray dryer.
A method, suspension polymerization method, emulsion polymerization method, soap-free polymerization method, seed polymerization method, mechanical pulverization
Any method can be used as long as it can produce spherical fine particles, such as a method. This
The most suitable among them is that there is no residual emulsifier, so the chargeability of the toner
A soap-free polymerization method that does not hinder the environmental change of the specific electrical resistance without inhibiting
However, the present invention is not limited to this.       [0085]   In order to have two peaks in the distribution of resin particles, two types of resin particles are used.
May be dry-blended or wet-blended and then dried.
Later, when drying from the emulsion state, the primary particles are appropriately coalesced to form two peaks.
Is more preferably achieved. If necessary, heat or crush
You may.       [0086]   The opposite polarity resin particles may be subjected to a particle surface treatment as necessary. For surface treatment
Metals such as iron, nickel, cobalt, copper, zinc, gold, silver, etc.
Surface treatment with a jack or the like, or a metal acid such as the above metal, magnetic material, or conductive zinc oxide
To fix compounds by ion adsorption or external addition, pigments or dyes,
Is made by coating or externally adding an organic compound that can be triboelectrically charged, such as a polymer resin.
It may be carried.       [0087]   The molecular weight distribution of the opposite polarity resin particles is such that the peak molecular weight is in the range of 10,000 to 5,000,000.
And preferably in the range of 20,000 to 1,000,000. Peak minutes
When the number of particles is more than 5,000,000, the fixability of the color toner is adversely affected, and 10,000
If it is smaller than this, the magnetic particles are contaminated, and the blocking resistance is deteriorated.       [0088]   In the toner according to the present invention, in order to stabilize the charge characteristics of the colorant-containing resin particles,
You may mix | blend a charge control agent. At that time, it is colorless or pale without affecting the color tone of the toner.
Color charge control agents are preferred. As the negative charge control agent at that time, for example, alkyl substitution
Metal complexes of salicylic acid (e.g. chromium complexes of di-tert-butylsalicylic acid or
Is a zinc complex). Incorporating negative charge control agent into toner
0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the binder resin.
It is preferable to add 5 to 8 parts by weight.       [0089]   When a two-component developer is prepared by mixing the toner and the carrier according to the present invention,
Is 2 to 12% by weight, preferably 3 to 9% by weight, as the toner concentration in the developer.
Good results are usually obtained with a percentage by weight. If the toner concentration is less than 2% by weight, the image
The concentration tends to be low, and if it exceeds 10% by weight, fog and in-flight scattering increase,
It is easy to shorten the useful life of the developer.       [0090]   As the colorant used in the present invention, known dyes and pigments, for example, phthalocyanine
Lou, Indaslen Blue, Peacock Blue, Permanent Red, Rakere Pad, rhodamine lake, Hansa yellow, permanent yellow, benzidine
It can be used widely such as yellow. The content of the OHP film
12 parts by weight or less for 100 parts by weight of binder resin that is sensitive to permeability
Below, preferably 0.5 to 9 parts by weight.       [0091]   Additives may be added to the toner of the present invention as needed as long as the properties of the toner are not impaired.
Such additives may be, for example, Teflon, zinc stearate
, A lubricant such as polyvinylidene fluoride, or a fixing aid (eg, low molecular weight polyether)
Organic resin particles and the like.       [0092]   In producing the colorant-containing resin particles used in the toner of the present invention, a heat filter is used.
The components were well kneaded with a heat kneader such as an extruder, kneader or extruder.
Then, a method of obtaining by mechanical pulverization and classification; a material such as a colorant in the binder resin solution
A method of obtaining by dispersing and then spray-drying; or simply forming a binder resin.
After mixing the predetermined material with the monomer, the emulsified suspension is polymerized to contain the colorant.
A suspension polymerization method for obtaining resin particles can be applied.       [0093]   As a binder substance used in the colorant-containing resin particles of the present invention, a conventional electrophotographic toner is used.
Various types of material resins known as knuckle binder resins are used.       [0094]   For example, polystyrene, styrene / butadiene copolymer, styrene / acryl
Styrene copolymer such as copolymer, polyethylene, ethylene / vinyl acetate copolymer
Copolymers, ethylene-based copolymers such as ethylene-vinyl alcohol copolymers,
Resin, epoxy resin, acrylic phthalate resin, polyamide resin, poly
Ester resins, maleic acid resins and the like. In addition, any resin can be produced
Are not particularly limited.       [0095]   Among these resins, especially when a polyester resin with high negative chargeability is used
The effect of the present invention is enormous. That is, the polyester-based resin has an immediate fixability. It is suitable for color toners, but has a strong negative charging ability and tends to be excessively charged.
By using a polyester resin in the constitution of the present invention, the adverse effects are improved, and an excellent toner is obtained.
can get.       [0096]   In particular,       [0097] [Outside 1] (Where R₁And R_TwoRepresents an ethylene or propylene group, and x and y are each
It represents an integer of 1 or more, and the average value of x + y is 2 to 10. )
Diol component or phenol derivative or bisphenol substituted diol component
Carboxylic acid or its anhydride or its lower alkyl ester
Bonic acid component (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid,
Polycondensed with tallic acid, trimellitic acid, pyromellitic acid)
Resins are more preferred because they have sharp melting properties.       [0098]   When the toner of the present invention is used as a two-component developer using a carrier, a key is required.
Electrically insulating resin is used as the coating resin on the carrier surface.
It is appropriately selected depending on the core material. In the present invention, adhesion with the carrier core material surface
Acrylic acid (or acrylic acid ester) monomer to improve the properties
And at least one selected from methacrylic acid (or methacrylic acid ester) monomers
Also needs to contain one kind of monomer. Negative chargeability, especially as a toner material
When high-resin polyester resin particles are used, the purpose is to stabilize the toner charge.
Furthermore, it is preferable to use a copolymer with a styrene monomer,
It is preferable that the copolymer weight ratio be 5 to 70% by weight.       [0099]   The monomer for the coating resin of the carrier core material that can be used in the present invention includes styrene-based monomers.
Examples of the monomer include a styrene monomer, a chlorostyrene monomer, an α-
Styrene monomer, styrene-chlorostyrene monomer, etc.
Examples of the monomer include an acrylate monomer (methyl acrylate)
Monomer, ethyl acrylate monomer, butyl acrylate monomer, acrylic acid
Octyl monomer, phenyl acrylate monomer, 2-ethylhexyl acrylate
Monomer) and methacrylic acid ester monomer (methyl methacrylate
Nomer, ethyl methacrylate monomer, butyl methacrylate monomer, methacrylate
Phenyl luate monomer).       [0100]   As the carrier core material (magnetic particles) used in the present invention, for example, surface oxidation or
Unoxidized gold such as iron, nickel, copper, zinc, cobalt, manganese, chromium and rare earth
Metals and their alloys or oxides such as magnetic ferrite can be used. Again
There are no particular restrictions on the method of manufacturing the slab.       [0101]   Preferably, the metal composition ratio of copper, zinc and iron is 5-20: 5-20: 30-80.
(Weight ratio): at least 98% by weight of a magnetic ferrite carrier.       [0102]   Next, an image forming apparatus for performing non-magnetic one-component development using the toner of the present invention.
An example of the position will be described, but the present invention is not necessarily limited to this. Figure 1 shows the latent image
2 shows an apparatus for developing an electrostatic image formed on a holding member. Reference numeral 1 denotes a latent image holding member,
The image is formed by an electrophotographic process means or an electrostatic recording means (not shown). 2
Is a non-magnetic slide made of aluminum or stainless steel.
Consisting of Non-magnetic one-component color toner is stored in hopper 3 and supplied.
The developer is supplied onto the developer carrier by the roller 4. Note that the supply roller 4 is
The toner on the developer carrier is also stripped off. Supplied on the developer carrier
The toner is uniformly and thinly applied by the developer application blade 5. Developer application
The contact pressure between the blade and the developer carrier is 3 to 3 as a linear pressure in the sleeve generatrix direction.
250 g / cm, preferably 10 to 120 g / cm is effective. Contact pressure If it is less than 3 g / cm, it becomes difficult to apply the toner uniformly, and the charge amount of the toner
The cloth becomes broad, causing fogging and scattering. The contact pressure is 250g / c
m, a large pressure is applied to the toner, so that the toners aggregate or
Or it is not preferable because it is crushed. Contact pressure 3 to 250 g / cm
By preparing the toner, it is possible to loosen the aggregation unique to the small particle size toner.
Instantaneously rises in the charge amount. The developer application blade is
It is preferable to use a material of the triboelectric series suitable for charging the toner to the polarity.
New       [0103]   In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber
Etc. are preferred. Further, it may be coated with a polyamide resin or the like. Also conductive rubber
It is preferable to use such as it can prevent the toner from being excessively charged.       [0104]   In addition, the thin layer coating of the toner on the developer carrier by the blade proposed in the present invention is performed.
In a system that uses a toner, a toner layer on a developer carrier is required to obtain a sufficient image density.
Is smaller than the gap length between the developer carrying member and the latent image holding member, and the gap
It is necessary to apply an alternating electric field. That is, the bias power supply 6 shown in FIG.
The alternating electric field between the developer carrier and the latent image holding member or a DC electric field is superimposed on the alternating electric field.
By applying the developing bias, the toner is transferred from the developer carrier to the latent image carrier.
This facilitates the movement of the knurling and can obtain a better quality image.       [0105]   Hereinafter, the measuring method of the present invention will be described.       [0106] (1) Particle size measurement of colorant-containing resin particles and toner   The particle size distribution can be measured by individual methods.
This was performed using a Rölter counter.       [0107]   That is, as a measuring device, a Coulter counter TA-II type (Coulter counter
Interface (Nikkaki) that outputs the number average distribution and volume distribution using And CX-1 personal computer (manufactured by Canon).
A 1% NaCl aqueous solution is prepared using graded sodium chloride. The measurement method is
A surfactant, preferably an alkyl, is used as a dispersant in 100 to 150 ml of an aqueous electrolytic solution.
0.1 to 5 ml of rubenzenesulfonate, and 2 to 20 mg of the measurement sample
Add. The electrolyte in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser,
With the Coulter Counter TA-II, an aperture of 100 μm
Using a patcher, measure the volume and number of samples, and measure the volume distribution and number of 2 to 40 μm.
Distribution was calculated. Then, according to the present invention, the weight base determined from the volume distribution
Semi-weight average diameter (D4) (The median value of each channel is the representative value for each channel.
), The amount of coarse powder on a weight basis (16.0 μm or more) determined from the volume distribution,
The number-based fine powder number (5.04 μm or less) was determined.       [0108] (2) Hydrophobicity measurement   The degree of hydrophobicity of the titanium oxide fine powder having a hydrophobic surface is measured as follows.
You.       [0109]   By changing the mixing ratio of water and methanol variously, the total volume of water was 100 ml.
The mixed methanol solution is put into a 250 ml stoppered glass bottle.       [0110]   0.2 g of a sample was added, and 1 g was applied with a paint conditioner manufactured by Red Devil Co., Ltd.
After mixing for 0 minutes, mix methanol and water with the entire sample wetted.
The degree of hydrophobicity is measured as the percentage of methanol in the combined solution.       [0111] (3) Method of measuring transmittance   0.10g sample   Alkyd resin (Bekkosol 1323-60-EL manufactured by Dainippon Ink and Chemicals, Inc.)
  13.20g   Melamine resin (Super Beckamine J-820-60 manufactured by Dai Nippon Ink Co., Ltd.)
  3.30g   3.55 g thinner (Amirac thinner manufactured by Kansai Paint Co., Ltd.)   Glass media 50.00g a. The above material was collected in a 150 ml glass bottle with a stopper, and the product was
Disperse for 1 hour with a conditioner. b. After dispersion, apply to PET film sheet with 2 mil doctor blade
You. c. The coated film obtained in b is heated at 120 ° C. for 10 minutes and baked. (D). The coated film sheet obtained in c) was subjected to 32 by U-BEST 50 manufactured by JASCO.
The transmittance is measured in the range of 0 to 800 nm and compared.       [0112]   Also, the titanium oxide fine powder or the treated titanium oxide fine powder is solid content concentration of 0.1 wt.
% And dispersed in ethanol at 400% using UV2200 manufactured by Shimadzu Corporation.
May be measured.       [0113] (4) Method for measuring particle size of organic resin particles apparatus   Coulter counter N4 type as measuring device and ultrasonic generator for dispersion (
Tomy Seiko UD-200 type is used. Method   Put an appropriate amount of sample in 30 to 50 ml of distilled water to which a trace amount of surfactant has been added.
Disperse for about 2 to 5 minutes at an output of 2 to 6 using the ultrasonic generator. Disperse the sample
Transfer the suspended suspension to the cell, wait for air bubbles to escape, and set the measurement temperature to 50 ° C in advance.
Set to the above-mentioned coulter counter set in the above. To keep the sample at a constant temperature
After 10 to 20 minutes have elapsed, the measurement is started, and the volume average particle size distribution is determined.       [0114]     【Example】   Hereinafter, production examples and examples according to the present invention will be described. "Department" and "%"
Indicates "parts by weight" and "% by weight".       [0115]   Production Example 1   Anatase type hydrophilic titanium oxide fine powder (average particle size 0.05 μm, BET ratio table
Area 120m^Two/ G) 1 part was added to 100 parts of an aqueous medium consisting of water and sufficiently stirred.
After stirring, the silane coupling agent (n-C_FourH₉Si (OCH_Three)_Three) 0.2 parts aqueous medium
In addition to the body, thoroughly stirred so that the titanium oxide fine particles do not coalesce, and then filtered after stirring.
Dry, lightly crushed, the average particle size is 0.05μm, the degree of hydrophobicity
Is 70%, and the light transmittance for a light wavelength of 400 nm is 60%.
A type I treated titanium oxide fine powder I was obtained. The obtained treated titanium oxide fine powder I is
According to optical X-ray analysis, about 20% by weight (about 25 parts by weight of
(Silane coupling agent)
Was.       [0116]   Production Example 2   N-C as silane coupling agent₆H₁₃Si (OCH_Three)_ThreeUse 15 copies
Except that, in the same manner as in Production Example 1, anatase-type hydrophilic titanium oxide fine powder was treated with water.
Hydrophobizing treatment, the average particle size is 0.05 μm, the degree of hydrophobicity is 60%,
Anatase-type treated titanium oxide having a transmittance of 55% for a light wavelength of 400 nm
Fine powder II was obtained.       [0117]   Production Example 3   N-C as silane coupling agent_TenH_{twenty one}Si (OCH_Three)_ThreeUse 15 copies
Except that, in the same manner as in Production Example 1, anatase-type hydrophilic titanium oxide fine powder was treated with water.
Hydrophobizing treatment, the average particle size is 0.05 μm, the degree of hydrophobicity is 70%,
Anatase-type treated titanium oxide having a transmittance of 45% for a light wavelength of 400 nm
Fine powder III was obtained.       [0118]   Production Example 4   Anatase type hydrophilic titanium oxide fine powder (average particle size 0.05 μm, BET ratio table
Area 120m^Two/ G) in water and mixing and stirring in the water while n-C₆ H₁₃Si (OCH_Three)_ThreeIs oxidized to 20% by weight with respect to the titanium oxide fine powder.
Titanium particles are added and mixed so that they do not coalesce, and dried and crushed to obtain a hydrophobicity of 40%.
The average particle size is 0.05 μm, and the light transmittance for a light wavelength of 400 nm is 5 μm.
5% of anatase-type treated titanium oxide fine powder IV was obtained.       [0119]   Production Example 5   Use of phenyltrimethoxysilane as a silane coupling agent
Except that the anatase-type hydrophilic fine powder was hydrophobized in water in the same manner as in Production Example 4.
, An average particle size of 0.05 μm, a degree of hydrophobicity of 30%, and a light wave of 400 nm.
Anatase-type treated titanium oxide fine powder V having a light transmittance of 60% with respect to length was obtained.
Was.       [0120]   Production Example 6   The treated titanium oxide fine powder IV obtained in Production Example 4 was mixed with (CH_Three)_TwoSi (OC
H_Three)_Two5% by weight, the average particle size is 0.05 μm and the degree of hydrophobicity is 5
0%, and an anatase type having a light transmittance of 50% for a light wavelength of 400 nm.
To obtain titanium oxide fine powder VI.       [0121]   Comparative Production Example 1   CH as silane coupling agent_ThreeSi (OC_TwoH_Five)_ThreeExcept that you use
In the same manner as in Production Example 1, the average particle size was 0.05 μm, and the degree of hydrophobicity was 15%.
Treated titanium oxide fine powder V having a transmittance of 50% for a light wavelength of 400 nm
II was obtained.       [0122]   Comparative Production Example 2   Anatase type hydrophilic titanium oxide fine powder (average particle size 0.05 μm, BET specific surface
120m^Two/ G) is sintered by high-temperature heating to obtain rutile having an average particle size of 0.3 μm.
-Type hydrophilic titanium oxide fine powder was obtained. The obtained rutile-type hydrophilic titanium oxide fine powder is
Hydrophobization treatment was performed in the same manner as in Production Example 1, and the average particle size was 0.3 μm and the degree of hydrophobicity was 80%, and a rutile type process having a transmittance of 10% for a light wavelength of 400 nm.
A titanium oxide fine powder VIII was obtained.       [0123]   Comparative Production Example 3   Anatase type hydrophilic titanium oxide fine powder (average particle size 0.05 μm, BET ratio table
Area 120m^Two/ G) in the gas phase with n-C₆H₁₃Si (OCH_Three)_ThreeHydrophobic treatment
And has an average particle size of 0.06 μm, a hydrophobicity of 50%, and a light of 400 nm.
A treated titanium oxide fine powder IX having a light transmittance of 25% with respect to the wavelength was obtained.       [0124]   Comparative Production Example 4   Hydrophilic titanium oxide fine powder (average particle size 0.4 μm, BET specific surface area 12 m^Two/ G
), The average particle diameter was 0.4 μm,
A treated titanium oxide fine powder X having a degree of hydration of 50% was obtained.       [0125]   Comparative Production Example 5   Treated titanium oxide fine powder IV is mixed with 10% by weight of 500 centistokes dimethy
Further treated with polysiloxane to have an average particle size of 0.07 μm and a hydrophobicity of
85% and has a light transmittance of 30% for a light wavelength of 400 nm.
A fine tan powder XI was obtained.       [0126]   Comparative Production Example 6   30% by weight of n-C₁₆H₃₃Si (OCH_Three)_Threeso
Further processing gave an average particle size of 0.06 μm, a hydrophobicity of 90%,
Treated titanium oxide fine powder XII having a light transmittance of 32% for a light wavelength of 0 nm
Obtained.       [0127]   Comparative Production Example 7   N-C as silane coupling agent₁₆H₃₃Si (OCH_Three)_ThreeTo use
Except that the average particle diameter was 0.06 μm and the degree of hydrophobicity was the same as in Production Example 1. 75% and a light transmittance of 35% at a light wavelength of 400 nm.
Powder XIII was obtained.       [0128]   Example 1   Polyester resin obtained by condensation of propoxylated bisphenol and fumaric acid
  100 copies   Phthalocyanine facial department 4 copies   Chromium complex of di-tert-butylsalicylic acid 2 parts       [0129]   The above materials are sufficiently premixed with a Henschel mixer and melted with a twin screw extruder.
After kneading, cooling and coarsely pulverizing to about 1-2 mm using a hammer mill, then air
The product was pulverized with a jet-type pulverizer. Further classify the obtained finely pulverized product
2 to 10 μm so that the particle size distribution of the present invention is obtained, and the weight average particle size is 8.2 μm.
m colorant-containing resin particles were obtained.       [0130]   0.5 part of treated titanium oxide fine powder I was added to 100 parts of the colorant-containing resin particles.
And a cyan toner.       [0131]   5 parts of this cyan toner, 75% methyl methacrylate and butyl acrylate
Copolymer having a weight average molecular weight of 200,000 (weight average molecular weight 200,000)
Particle size 35% or less 4.2%, Particle size 35-40μm 9.5%, Particle size 74μm or more
0.2%) having a particle size distribution of 0.2%.
It was mixed with 95 parts of a 5% coated magnetic carrier to give a two-component developer.       [0132]   Using this developer, a commercially available plain paper color copier (color laser copier 500
(Manufactured by Canon Inc.), the development contrast was set to 300 V, and at 23 ° C./65%.
An image was drawn. The resulting image is a Macbeth RD918 type with SPI filter
And the reflection density was measured (the same applies to the subsequent image density measurement method). This The image density was as high as 1.52 and clear without any fog. Also, O
The HP projection image was also clear and clear. After that, 10,000 more copies
The density fluctuation during this time was as small as 0.1, and the fog and sharpness were the same as those in the initial stage.
And so on. Also, even under low temperature and low humidity (20 ° C, 10% RH),
When the trust was set to 300 V and image output was performed, the image density was as high as 1.47.
This suggests that the present invention was effective in controlling the amount of charge under low humidity.       [0133]   Further, even under high temperature and high humidity (30 ° C./80% RH), the development contrast is similarly reduced to 30%.
The image density was 1.54, which was very stable and good when the image was set at 0V.
Image was obtained.       [0134]   Each ring of 23 ° C / 60% RH, 20 ° C / 10% RH, 30 ° C / 80% RH
No abnormality was observed in the initial image after one month at the boundary.       [0135]   Example 2   Except for using the treated titanium oxide fine powder II, the procedure was the same as in Example 1.
An toner was prepared, and a two-component developer was prepared.
A take-out test was performed.       [0136]   Under a high temperature and high humidity environment (30 ° C./80% RH), the amount of triboelectricity of the toner
Although the image density slightly decreased and the image density slightly increased to 1.57 to 1.61, good results were obtained.
Was done.       [0137]   Example 3   Except for using the treated titanium oxide fine powder III,
A cyan toner was prepared, and a two-component developer was prepared.
I did the drawing.       [0138]   Under a low-temperature and low-humidity environment (20 ° C./10% RH), the image density is 1.40 to 1. Although it was slightly lower at 45, good results were obtained.       [0139]   Comparative Example 1   Except for using the treated titanium oxide fine powder VII prepared in Comparative Production Example 1
A cyan toner was prepared in the same manner as in Example 1, and a two-component developer was further prepared.
An image was formed in the same manner as in Example 1.       [0140]   Under a high temperature and high humidity environment (30 ° C./80% RH), the triboelectric charge of the cyan toner is low.
And the image density increases to 1.70 to 1.75, and fog appears in the non-image area.
Occurred.       [0141]   Comparative Example 2   Commercially available hydrophilic titanium oxide fine powder (P25, Nippon Aero
Manufactured by Jill Co .; average particle size: about 0.021 μm, BET specific surface area: about 50 m^Two/ G, sparse
A cyan toner was prepared in the same manner as in Example 1 except that the hydration degree was 0%.
And a two-component developer was prepared, and image formation was performed in the same manner as in Example 1.
Was.       [0142]   The fluidity of the cyan toner was poor, and the image quality of the toner image was significantly reduced. Also high
In a warm and humid environment (30 ° C./80% RH), the triboelectric charge of the cyan toner decreases.
, Toner scattering occurred in the copying machine.       [0143]   Comparative Example 3   Except for using the treated titanium oxide fine powder VIII prepared in Comparative Production Example 2.
Then, a cyan toner was prepared in the same manner as in Example 1, and a two-component developer was further prepared.
Then, image formation was performed in the same manner as in Example 1.       [0144]   The fluidity of the cyan toner decreased, and the image quality of the toner image decreased. OHP
When a cyan toner fixed image is formed on a film and projected, the OHP projected image is The whole was dark and poor.       [0145]   Comparative Example 4   Except for using the treated titanium oxide fine powder XIII prepared in Comparative Production Example 7
Then, a cyan toner was prepared in the same manner as in Example 1, and a two-component developer was further prepared.
Then, image formation was performed in the same manner as in Example 1.       [0146]   Under a low-temperature and low-humidity environment (20 ° C./10% RH), the image density is 1.30 to 1.40.
, And the reproducibility of the highlight part was also slightly reduced. In addition, the seal
Example: When an anti-toner fixed image was formed and projected, the sharpness of the OHP projected image was
The number was slightly lower than that of No. 1.       [0147]   Example 4   Use a commercially available color copying machine (color laser copying machine 500, manufactured by Canon)
Modified as shown in FIG. 1 and carried out in the same manner as in Example 1 except that no carrier was used.
When the image of 00 sheets was produced, the image density was 1.46 to 1.53 at 20 ° C./10% RH 1.50 to 1.55 at 23 ° C / 65% RH 1.52 to 1.58 at 30 ° C./80% RH And good results were obtained.       [0148]   Example 5   Instead of phthalocyanine facial, C.I. I. Pigment Yellow 17 3.5 parts
Was used to prepare a yellow color toner in the same manner as in Example 1. Example 1 and
A two-component developer was prepared in the same manner, and images were formed in the same manner as in Example 1.
An excellent yellow color toner image was obtained. Even in each environment, good yellow
A Lartner image was obtained.       [0149]   Example 6   Instead of phthalocyanine facial, C.I. I. Solvent Red 49 to 0.
8 parts and C.I. I. Pigment Red 122 and 4.2 parts of Example 1.
Similarly, a magenta color toner was prepared. Two-component development in the same manner as in Example 1.
A magenta color toner was prepared.
-An image was obtained. Good magenta color toner images were obtained in each environment.
Was.       [0150]   Example 7   A two-component developer containing the cyan color toner prepared in Example 1 and Example 5
A two-component developer containing the yellow color toner prepared in
Two-component developer containing magenta color toner and plain paper full color copier (
CLC500 (manufactured by Canon Inc.), and toner of each color was printed under the same conditions as in Example 1.
To obtain a full-color image with good color tone.
Was. Further, when images were formed in each environment, a good full-color image was obtained.       [0151]   Full color image using OHP film instead of plain paper as transfer material
When formed, a full-color fixed image with excellent translucency and excellent color
Could be formed on the film.       [0152]   Example 8   Polyester resin obtained by condensation of propoxylated bisphenol and fumaric acid
  100 parts by weight   4 parts by weight phthalocyanine facial   Chromium complex of di-tert-butylsalicylic acid 2 parts by weight       [0153]   The above materials are sufficiently premixed with a Henschel mixer and melted with a twin screw extruder.
After kneading, cooling and coarsely pulverizing to about 1-2 mm using a hammer mill, then air
The product was pulverized with a jet-type pulverizer. Further classify the obtained finely pulverized material 2 to 10 μm so that the particle size distribution of the present invention is obtained.
Colorant-containing resin particles were obtained.       [0154]   0.5 weight of the treated titanium oxide fine powder VI is added to 100 parts by weight of the colorant-containing resin particles.
Styrene / methacrylic acid having two peaks at 0.055μ and 0.5μ
Methyl luate resin particles were combined with 0.3 parts by weight to obtain a cyan toner.       [0155]   Mixing with resin-coated magnetic ferrite carrier as in Example 1, two components
System developer and prepare a commercially available plain paper color copier (color laser copier 500
(Manufactured by Canon Inc.), the development contrast was set to 300 V, and at 23 ° C / 65% RH
When the image was formed, the obtained image had a high density of 1.45 and was clear without any fog.
It was something. After that, another 10,000 copies were made.
The fluctuation was as small as 0.12, and the fog and sharpness were equivalent to those at the initial stage. Low
Under low temperature and humidity (20 ° C, 10% RH), set development contrast to 300V
Then, when an image was formed, the image density was as high as 1.41, and the present invention was carried out under a low humidity.
This suggests that the effect of controlling the charge amount was effective.       [0156]   Also, the development contrast is set to 300V under high temperature and high humidity (30 ° C / 80% RH).
The image density was 1.50, and the image density was very stable and good.
Was done.       [0157]   Each ring of 23 ° C / 60% RH, 20 ° C / 10% RH, 30 ° C / 80% RH
No abnormality was found in the initial image after one month at the boundary.       [0158]   Comparative Example 4   Same as Example 8 except that the treated titanium oxide fine powder IX was used in Example 8.
When fogging was observed at 30 ° C./80% RH, toner
Some scattering occurred. This is because it was first treated in the gas phase, not in an aqueous system,
Coalescence of the titanium oxides, resulting in impaired fluidity of the toner. You.       [0159]   Comparative Example 5   Same as Example 8 except that the treated titanium oxide fine powder X was used in Example 8.
When the image was formed, fog was observed at 30 ° C./80% RH, and the toner was scattered.
Also occurred slightly.       [0160]   Comparative Example 6   Same as Example 8 except that the treated titanium oxide fine powder XI was used in Example 8.
The image density was reduced by about 0.2 at 20 ° C./10% RH.
Fog was also noted.       [0161]   Comparative Example 7   Same as Example 8 except that the treated titanium oxide fine powder XII was used in Example 8.
When the image was extracted in the same manner, the titanium oxide fine particles were united at 20 ° C / 10% RH.
The image defect considered to be the cause occurred in the solid portion.       [0162]   Example 9   Same as Example 8 except that the treated titanium oxide fine powder III was used in Example 8.
When the image was formed in the same manner as described above, the image density was 0.05 to 0.1 at 30 ° C./80% RH.
1 higher, but slightly better in reproducing highlights with good results
Was done.       [0163]   Example 10   Same as Example 1 except that the treated titanium oxide fine powder IV was used in Example 8.
As a result, good results were obtained as in Example 2.       [0164]     【The invention's effect】   As described above, when the toner of the present invention is used, a high-quality Excellent color toner for OHP film that can provide toner image
A fixed image can be formed.

[Brief description of the drawings]     FIG.   FIG. 3 is an explanatory diagram showing an example of a developing device using a non-magnetic one-component developer.

Claims (1)

Claims: 1. A toner for developing an electrostatic charge image having at least colorant-containing resin particles and an external additive, wherein the colorant-containing resin particles have a weight average particle diameter (D ₄ ) of 5 to 10 μm.
m, the external additive is hydrophobic titanium oxide fine powder, and the hydrophobic titanium oxide fine powder
Has been subjected to hydrophobic treatment with a silane coupling agent in an aqueous medium,
It has an average particle size of 0.01 to 0.2 μm, a hydrophobicity of 20 to 98%, and 400 n
The toner for developing electrostatic images, wherein the light transmittance is hydrophobicity anatase type titanium oxide fine powder Ru der least 40% with respect to the wavelength of light m. 2. The electrostatic image developing toner according to claim 1, wherein the hydrophobic titanium oxide fine powder has a hydrophobicity of 20 to 80%. Wherein the hydrophobic titanium oxide fine powder, 0.02 to 3 wt% content has been has claim 1 or 2 of the toner for electrostatic image development in the toner. 4. A color toner comprising nonmagnetic colorant-containing color resin particles and an external additive, wherein the external additive is a hydrophobic titanium oxide surface-treated while hydrolyzing a silane coupling agent in an aqueous medium. 2. The toner for developing an electrostatic image according to claim 1, which is a fine powder. 5. The toner according to claim 4 , wherein the hydrophobic titanium oxide fine powder has an average particle size in the range of 0.2 to 0.02 μm and has a hydrophobicity of 20 to 80%. 6. The hydrophobic additive according to claim 1, wherein the external additive is a hydrophobic titanium oxide fine powder which is subjected to a surface treatment while hydrolyzing a silane coupling agent in an aqueous medium, and further surface-treated with a coupling agent in a gas phase. 4. An electrostatic image developing toner. 7. The electrostatic image developing device according to claim 1, wherein the external additive further contains organic resin particles having at least peaks at particle diameters of 0.02 to 0.2 μm and 0.3 to 0.8 μm. toner. 8. A hydrophobic titanium oxide fine powder which has been subjected to a surface treatment with an external additive while hydrolyzing a silane coupling agent in an aqueous system, and further subjected to a surface treatment with a coupling agent in a gaseous phase. 2. The toner for developing an electrostatic image according to claim 1, further comprising organic resin particles having at least peaks at 0.22 to 0.2 [mu] and 0.3 to 0.8 [mu].