[0001] The present invention relates to a toner for full color development where a plurality
of toners are overlapped on an image on a copying sheet. More particularly, the present
invention relates to a toner for full color development, in which the development
characteristics and transfer characteristics are substantially equal in the toners
to be overlapped.
[0002] Furthermore, the present invention relates to magenta, cyan and yellow toners among
toners for full color development. More particularly, the present invention relates
to these toners having such an excellent transparency that when these toners are mingled
on an image on a transfer sheet, the toners can show the intended colors sharply.
[0003] In the fields of the electrophotography and electrostatic printing, toners are used
for visualizing electrostatic latent images formed on image carriers. In these toners,
a resin having desirable electroscopic and binding properties, for example a styrene
resin or a polyester resin, is used as the resin medium, and carbon black or other
organic or inorganic coloring pigments are used as the coloring agents.
[0004] Full color development in which magenta, cyan, yellow and black color toners are
overlapped to form an image has been recently proposed and worked.
[0005] In this full color development, a multiple-color original is exposed to light through
a color-separating filter. This operation is repeated a number of times using cyan,
yellow and magenta color developers and a black toner, and toner images are thus overlapped
to obtain a multiple-color image. Organic pigments are used as coloring agents for
cyan, yellow and magenta toners used for this full color development, and carbon black
is used for a black toner.
[0006] Fig. 7 is a diagram illustrating the developing and transfer zones of an image-forming
apparatus for obtaining a full color image. In this apparatus, an electrostatic latent
image formed on a photosensitive drum 1 by an appropriate means is visualized by a
developer in any of the developing devices 3a, 3b, 3c and 3d of a developing unit
2 and is then transferred by a transfer charger 5 onto a transfer material held on
a transfer drum 4 by a gripper 6, from which electricity is removed by an electricity-removing
charger 7. Furthermore, a toner image developed by a developer in another developing
device of the devices 3a, 3b, 3c and 3d is transferred onto the transfer material
by the transfer charger, and third and fourth color images are similarly transferred.
Thus, a predetermined number of color images are transferred onto the transfer material
held on the transfer drum 4, and the transfer material is delivered to a fixing step
(not shown) to form a multiple-color image. In general, in the above-mentioned transfer
step, an operation of transferring a toner of a different color onto a toner layer
transferred on a transfer material is carried out. At this operation, it sometimes
happens that the charge of the toner already transferred on the transfer material
reduces the working transfer electric field at the transfer of the subsequent toner,
and therefore an image having a desired hue cannot be reproduced. For obviating this
disadvantage, there is sometimes adopted a method in which the transfer voltage is
gradually elevated at the transfer step or the transfer voltage is elevated at the
transfer of the third and subsequent toners when the toner layer becomes thick.
[0007] However, since the behavior of toners at the practical transfer step is delicate
and complicated, even if a predetermined transfer voltage is applied and the value
of the transfer voltage is elevated in the later stage, scattering of the toners or
insufficient transfer often occurs because the color toners have different characteristics
(such as charging characteristics and electric characteristics), and satisfactory
results cannot be obtained in the formation of a toner image of a desirable hue.
[0008] JP-A-1-32981 proposes a method in which the quantity of the charge of a toner to
be developed and transferred is made larger than the absolute value of the already
developed and transferred toner to compensate for the reduction of the working transfer
electric field and stabilize the transfer operation. According to this method, if
it is intended to adopt common development conditions (the charge characteristics
of the photosensitive material, the development bias voltage and the sliding contact
state between the photosensitive material and the developer carrier), since toners
are extremely different in the charge characteristics, development unevenness (insufficient
density of the solid portion, thicknening of line and dot images and formation of
toner dusts in the peripheral portion of the image area) is caused or scatterring
of toners is caused in the machine, and a shear in the hue and fogging are often observed
in the formed image.
[0009] It is important that color toners should be excellent not only in spectral reflection
characteristics but also in spectral transmission characteristics, and if this requirement
is not satisfied, an image having a hue similar to the inherent color cannot be obtained.
When a full color image is formed by overlapping a plurality of color toners, it is
especially important that a transparency should be given to the toners. If color toners
having poor transparency are used, the colors of the toners interfere with one another
and the formed image becomes dark, and it often happens that an image of a desired
color cannot be obtained.
[0010] As the means for overcoming the foregoing defects, there have been proposed a method
in which a specific fluorine-containing acrylic resin is used as a binder resin medium
(JP-A-62-273569) and a method in which an oil-soluble dye such as C.I. Solvent Yellow
60 is incorporated into a yellow toner (JP-A-62-273572).
[0011] However, even if these methods are adopted, the original image hue cannot be sharply
reproduced by mingling the colors, and it often happens that the formed image becomes
obscure and the characteristics of colors are not effectively utilized. Therefore,
the problem cannot be solved by these methods.
[0012] EP-A-275,636 discloses full color development processes using four differently colored
toners. In the toners 30% by number or less of the particles have a volume-average
particle size of less than 6.35 microns and 9% by weight or less of the particles
have a size above 20.2 microns.
[0013] The present invention seeks to provide a toner for full color development which has
a very high light-transmitting property, and an improved light-transmitting property
such that hues of respective toners overlapped at the color mingling step are sharply
manifested.
[0014] The present invention also seeks to provide toners having development characteristics
and transfer characteristics which are substantially conformable to one another by
diminishing the differences of electric characteristics among the respective toners,
in particular so that full color development having excellent image reproducibility
becomes possible without reduction of the chroma or unevenness of the density in the
formed image.
[0015] In accordance with one aspect of the present invention, there is provided a high
transparency toner for full color development comprising a binder resin having an
electroconductivity of 1.0 x 10⁻⁹ to 5.0 x 10⁻⁹ (s/cm) and magenta coloring agent
particles dispersed in the binder resin, the particle size distribution of the coloring
agent being such that when the toner is formed into a layer having a thickness of
0.9 »m there are fewer than 40 dispersed coloring agent particles having a size of
10 to 12.5 »m² and fewer than 20 dispersed coloring agent particles having a size
of 12.5 to 15.0 »m² per 780,000 »m² of surface of the toner layer.
[0016] In accordance with another aspect of the present invention, there is provided a high
transparency toner for full color development comprising a binder resin having an
electroconductivity of 1·0 x 10⁻⁹ to 5·0 x 10⁻⁹ (s/cm) and cyan coloring agent particles
dispersed in the binder resin, the particle size distribution of the coloring agent
being such that when the toner is formed into a layer having a thickness of 0.9 »m
there are fewer than 80 dispersed coloring agent particles having a size of 10 to
12.5 »m² and fewer than 50 dispersed coloring agent particles having a size of 12.5
to 15.0 »m² per 780.000 »m² of surface of the toner layer.
[0017] In accordance with still another aspect of the present invention, there is provided
high transparency toner for full color development comprising a binder resin having
an electroconductivity of 1·0 x 10⁻⁹ to 5·0 x 10⁻⁹ (s/cm) and yellow coloring agent
particles dispersed in the binder resin, the particle size distribution of the coloring
agent being such that when the toner is formed into a layer having a thickness of
0.9 »m there are fewer than 15 dispersed coloring agent particles having a size of
10 to 12.5 »m² and fewer than 10 dispersed coloring agent particles having a size
of 12.5 to 15.0 »m² per 780,000 »m² of surface of the toner layer.
[0018] Fig. 1 is a characteristic curve illustrating the transmission of a conventional
toner comprising a magenta coloring agent.
[0019] Fig. 2 is a characteristic curve illustrating the transmission of a toner of the
present invention comprising a magenta coloring agent.
[0020] Fig. 3 is a characteristic curve illustrating the transmission of a conventional
toner comprising a cyan coloring agent.
[0021] Fig. 4 is a characteristic curve illustrating the transmission of a toner of the
present invention comprising a cyan coloring agent.
[0022] Fig. 5 is a characteristic curve illustrating the transmission of a conventional
toner comprising a yellow coloring agent.
[0023] Fig. 6 is a characteristic curve illustrating the transmission of a toner of the
present invention comprising a yellow coloring agent.
[0024] Fig. 7 is a diagram illustrating the principle of a full color development apparatus.
[0025] Factors having an influence on the transparency of the toner include the characteristics
of the binder resin for example optical characteristics such as spectral reflecting
and spectral transmitting properties, and the uniformity of the shape. However, it
has hardly before been considered that the state of dispersion of the coloring agent
in the binder resin has a significant influence on the transparency of the toner.
We have now examined this dispersion and as a result have now completed the present
invention.
[0026] More specifically, we have found that if the binder resin is kneaded with the coloring
agent until a specific dispersion state of the coloring agent is attained and the
coloring agent is uniformly dispersed in the form of predetermined fine particles,
a color toner having an excellent light-transmitting property in the visible region,
as not observed in conventional toners, can be obtained. The preferred dispersion
state of a coloring agent and a preferred amount of the dispersed coloring agent for
each of full color development toners to be overlapped, especially magenta, cyan and
yellow toners, were examined. As a result, we have now completed the present invention.
[0027] A conventional organic coloring agent has a primary particle diameter of about 0.1
to 0.2 »m in the as-prepared state, but since particles are readily agglomerated in
the drying step, the secondary particle size is in a broad range of from several »m
to several »m. In conventional toners, a coloring agent having such a particle size
is mainly dispersed in a resin.
[0028] In contrast, in the toner of the present invention, the amounts of particles having
a size of 10 to 12.5 »m² and particles having a size of 12.5 to 15.0 »m are limited
below certain levels. These particles, the presence of which is restricted, correspond
mainly to secondary particles. The toner in which the particles are restricted has
an excellent light-transmitting property in the visible region except in the wavelength
absorption region of the coloring agent. We have also found that the allowable numbers
of coloring agent particles having a size of 10 to 12.5 »m² and coloring agent particles
having a size of 12.5 to 15.5 »m in the resin differ for magenta, cyan and yellow
toners.
[0029] Fig. 1 shows the results of the examination of the transmission T (%) of a conventional
toner comprising a magenta coloring agent at a wavelength in the visible region, and
Fig. 2 shows the results of the examination of the transmission T (%) of a toner having
a magenta coloring agent appropriately dispersed in a resin according to the present
invention, at a wavelength in the visible region. As is seen from Figs. 1 and 2, these
magenta toners show substantially the same absorption values at a wavelength of about
500 to 600 nm, but in other areas of the visible region (wavelengths shorter than
500 nm and longer than 600 nm), they do not absorb light but transmit it. Furthermore,
in the above region the conventional toner has a poor light-transmitting property.
In contrast, the magenta toner of the present invention exerts the same action as
that of the conventional toner in the inherent absorption region of the coloring agent,
but the toner of the present invention has an excellent light-transmitting property
in other visible regions. Accordingly, the toner of the present invention is suitably
used as a toner for full color development and provides an image having excellent
reproducibility.
[0030] In the magenta toner of the present invention, it is important that when the toner
is formed into a layer having a thickness of 0.9 »m as a measurement sample, there
are fewer than 40, especially fewer than 30, dispersed coloring agent particles having
a size of 10 to 12.5 »m² and fewer than 20, especially fewer than 10, dispersed coloring
agent particles having a size of 12.5 to 15.0 »m² per 780,000 »m² of surface of the
toner layer. If the number of coloring agent particles is within the above-mentioned
range, a sufficient light-transmitting property can be obtained, but if the number
of particles exceeds the above-mentioned range, the light-transmitting property is
degraded. The reason why the transparency of the toner is improved by restricting
the presence of coloring agent particles having such a large size has not been elucidated,
but it is believed that many coloring agent particles having a primary particle size
are present in the binder, they are uniformly dispersed and polymeric films of the
resin wet-adhere to the entire surfaces of the coloring agent particles.
[0031] In the above-mentioned magenta toner, a quinacridone pigment is preferably used as
the coloring agent. The quinacridone pigment has a good dispersibility in a resin,
and the above-mentioned requirements of the numbers of particles having the above-mentioned
particle sizes may be satisfied. Thus, the quinacridone pigment has a good dispersibility
in a binder resin, and a toner comprising the quinacridone pigment has uniform electric
characteristics and excellent light-transmitting and spectral characteristics.
[0032] Fig. 3 shows the results of the examination of the transmission T (%) of a conventional
toner comprising a cyan coloring agent at a wavelength in the visible region, and
Fig. 4 shows the results of the examination of the transmission T (%) of a toner having
a cyan coloring agent appropriately dispersed in a resin according to the present
invention, at a wavelength in the visible region. As is seen from Figs. 3 and 4, these
cyan toners show substantially the same absorption values at a wavelength of about
600 to 700 nm, but in the wavelength region of about 500 nm, they do not absorb light
but transmit it. Furthermore in the above region the conventional toner has a poor
light-transmitting property. In contrast, the cyan toner of the present invention
exerts the same action as that of the conventional toner in the inherent absorption
region of the coloring agent, but the toner of the present invention has an excellent
light-transmitting property in other visible regions. Accordingly, the toner of the
present invention is suitably used as a toner for full color development and provides
an image having excellent reproducibility.
[0033] In the cyan toner of the present invention, it is important that when the toner is
formed into a layer having a thickness of 0.9 »m as a measurement sample, there are
fewer than 80, especially fewer than 70, dispersed coloring agent particles having
a size of 10 to 12.5 »m² and fewer than 50, especially fewer than 40, dispersed coloring
agent particles having a size of 12.5 to 15.0 »m² per 780,000 »m² of surface of the
toner layer. If the number of coloring agent particles is within the above-mentioned
range, a sufficient light-transmitting property can be obtained, but if the number
of particles exceeds the above-mentioned range, the light-transmitting property is
degraded.
[0034] In the above-mentioned cyan toner, a copper phthalocyanine pigment is preferably
used as the coloring agent. The copper phthalocyanine pigment has a good dispersibility
in a resin, and the above-mentioned requirements of the numbers of particles having
the above-mentioned particle sizes may be satisfied. Thus, the copper phthalocyanine
pigment has a good dispersibility in a binder resin, and a toner comprising the copper
phthalocyanine pigment has uniform electric characteristics and excellent light-transmitting
characteristics.
[0035] Fig. 5 shows the results of the examination of the absorption wavelengths of a conventional
toner comprising a yellow coloring agent in the visible region, and Fig. 6 shows the
results of the examination of the absorption wavelengths of a toner having a yellow
coloring agent appropriately dispersed in a resin according to the present invention,
in the visible region. As is seen from Figs. 5 and 6, these yellow toners show substantially
the same absorption values at a wavelength of about 400 nm, but in other areas of
the visible region (wavelengths longer than 500 nm), they do not absorb light but
transmit it. Furthermore in the above region, the conventional toner has a poor light-transmitting
property. In contrast, the yellow toner of the present invention exerts the same action
as that of the conventional toner in the inherent absorption region of the coloring
agent, but the toner of the present invention has an excellent light-transmitting
property in other visible regions. Accordingly, the toner of the present invention
is suitably used as a toner for full color development and provides an image having
excellent reproducibility.
[0036] In the yellow toner of the present invention, it is important that when the toner
is formed into a layer having a thickness of 0.9 »m as a measurement sample, there
are fewer than 15, especially fewer than 10, dispersed coloring agent particles having
a size of 10 to 12.5 »m² and fever than 10, especially fever than 5, dispersed coloring
agent particles having a size of 12.5 to 15.0 »m² per 780,000 »m² of surface of the
toner layer. If the number of coloring agent particles is within the above-mentioned
range, a sufficient light-transmitting property can be obtained, but if the number
of particles exceeds the above-mentioned range, the light-transmitting property is
degraded.
[0037] In the above-mentioned yellow toner, a benzidine pigment is preferably used as the
coloring agent. The benzidine pigment has a good dispersibility in a resin, and the
above-mentioned requirements of the numbers of particles having the above-mentioned
particle sizes may be satisfied. Thus, the benzidine pigment has a good dispersibility
in a binder resin, and a toner comprising the benzidine pigment has uniform electric
characteristics and excellent light-transmitting characteristics.
[0038] In the present invention, it is important that the electroconductivity of the binder
resin is from 1.0 x 10⁻⁹ to 5.0 x 10⁻⁹ (s/cm), and it is especially preferred that
the electroconductivity is 1.0 x 10⁻⁹ to 3.0 x 10⁻⁹ (s/cm). If the electroconductivity
of the binder resin is less than the above-mentioned range, a great difference of
the electroconductivity is produced among toners to be overlapped, and also great
differences are produced in the development and transfer characteristics. For example,
as shown in Experiment 4-5 (Table 4) hereinafter, if a binder resin having a low electroconductivity
of 8.9 x 10⁻¹⁰ s/cm is used, carbon black raises up the electroconductivity of the
entire toner to 1.5 x 10⁻⁹ s/cm, while other toners such as cyan, magenta and yellow
toners show an electroconductivity of an order of 10 x 10⁻¹⁰ s/cm, and coloring agents
fail to show such a prominent increase of the electroconductivity as attained by carbon
black. Therefore, differences of the electrocoductivity are produced among the overlapped
toners.
[0039] In contrast, if a binder resin having an electroconductivity within the above-mentioned
range is used, no difference of the electroconductivity is found among the magenta,
cyan and yellow toners of the present invention, for example as shown in Experiments
4-1 and 4-2 concerning the magenta toner. If full color development is carried out
using toners, among which there is no difference of electroconductivity, the development
and transfer characteristics are substantially the same and excellent image reproducibility
is attained. On the other hand, if the electroconductivity of the binder resin is
greater than the above-mentioned range, even if charges are applied to toners, escape
of the charges is delayed and the charging state becomes unstable.
[0040] If the binder resin has an electroconductivity within the above-mentioned range,
the toner of the present invention has satisfactory electric characteristics, and
the resin of the toner of the present invention may be the same as or different from
binder resins of other toners used simultaneously with the toner of the present invention.
Incidentally, it is important that each of the binder resins of other toners should
satisfy the above-mentioned requirements of the electroconductivity.
[0041] In the present invention, it also is important that the melting point of the binder
resin should preferably be 80 to 130°C, more preferably 90 to 110°C. If the melting
point of the binder resin is within the above-mentioned range, an excellent coloring
property is attained if respective toners are overlapped. If the melting point of
the binder resin is above the above-mentioned range, the coloring property is degraded,
and if the melting point of the binder resin is below the above-mentioned range, an
offset phenomenon is sometimes caused.
[0042] The toner of the present invention will now be further described in detail.
[0043] The toner of the present invention is a toner for full color development, where the
toner is overlapped on other toners differing in color on an image on a transfer sheet.
The present invention is directed to a toner forming a basic color in full color development.
Basic toners for full color development include four toners, that is, magenta, cyan,
yellow and black toners. In full color development, these toners are developed in
order in the overlapped state, and the hue and image quality of an original are reproduced.
Each of these toners comprises a coloring agent and, if desired, a charge-controlling
agent in a binder resin. A known toner can be further incorporated in or added to
the toner.
[0044] A known resin can be used as the binder resin in the present invention, but it is
important that the resin used as the binder resin should have an electroconductivity
of 1.0 x 10⁻⁹ to 5.0 x 10⁻⁹ (s/cm), preferably 1.0 x 10⁻⁹ to 3.0 x 10⁻⁹ (s/cm), as
pointed out hereinbefore. Moreover, a resin having an excellent light-transmitting
property is preferably used. It also is important that the binder resin preferably
has a melting point of 80 to 130°C, more preferably 90 to 110°C.
[0045] As the resin having such characteristics, polyester, polystyrene, polyacrylic, polyamide
and polyolefin resins can be used singly or in the form of mixtures of two or more
of them.
[0046] In specific examples of the polyester resin, an aromatic dicarboxylic acid or a fatty
acid may be the acid component. As examples of the acid component, there can be mentioned
terephthalic acid, isophthalic acid, naphthalene-dicarboxylic acid, maleic acid, fumaric
acid, succinic acid, adipic acid, sebacic acid and cyclohexane-dicarboxylic acid.
Terephthalic acid is mainly used. As the diol component, there can be mentioned, for
example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, cyclohexane
dimethanol, hexylene glycol, triethylene glycol, glycerol, mannitol and pentaerythritol.
[0047] Specific examples of the styrene resin include polymers obtained by polymerizing
monomers such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene,
m-chlorostyrene, p-chlorostyrene, ethylstyrene and divinylstyrene singly or in combination.
[0048] As the acrylic resin, there can be used, for example, polymers obtained by polymerizing
monomers such as ethyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethyl-hexyl
methacrylate, acrylic acid and methacrylic acid singly or in combination. As the comonomer
other than the above-mentioned monomers, there can be used ethylenically unsaturated
acid and anhydrides thereof, such as maleic anhydride, fumaric acid, maleic acid,
crotonic acid and itaconic acid.
[0049] Polymers comprising, for example, vinyl-n-butyl ether, vinylphenyl ether or vinylcyclohexanyl
ether can be used a the vinyl ether resin.
[0050] Known resins derived from a diamine and a dicarboxylic acid and resins formed by
polymerizing a lactam, such as nylon 6, can be used as the polyamide resin.
[0051] Polymers formed by polymerizing, for example, ethylene, propylene, butene-1, pentene-1
or methylpentene-1 can be mentioned as the olefin resin.
[0052] The foregoing resins can be used singly, or two or more can be combined so that the
above-mentioned electroconductivity is attained, and the resulting mixtures can be
used as the binder resin.
[0053] In the present invention , in view of the electroconductivity, light-transmitting
property and melt viscosity characteristics, a polyester resin is preferably used.
[0054] The coloring agent to be contained in the coloring resin is roughly divided magenta,
cyan and yellow pigments. Preferably, the coloring agent is incorporated in the binder
resin in an amount of 1 to 20% by weight based on the binder resin.
[0055] As the magenta coloring agent, there can be mentioned C.I. Pigment Red 81, C.I. Pigment
Red 122, C.I. Pigment Red 57, C.I. Solvent Red 49, C.I. Solvent Red 19, C.I. Solvent
Red 52, C.I. Basic Red 10 and C.I. Disperse Red 15.
[0056] A quinacridone pigment is especially preferably used as the magenta coloring agent
because the quinacridone pigment has good dipersibility in the binder resin. The quinacridone
pigment is represented by the formula:

wherein R₁ and R₂ represent an imino group or a carbonyl group, and R₃ and R₄ represent
a hydrogen atom, an alkyl group or a halogen atom.
[0057] As the cyan coloring agent, there can be mentioned C.I. Pigment Blue 15, C.I. Pigment
Blue 16, C.I. Solvent Blue 25, C.I. Solvent Blue 55, C.I. Solvent Blue 70, C.I. Direct
Blue 86 and C.I. direct Blue 25.
[0058] A copper phthalocyanine pigment is preferably used as the cyan coloring agent because
the copper phthalocyanine pigment has good dispersibility in the binder resin. The
copper phthalocyanine pigment is represented by the formula:

wherein the benzene nuclei can be substituted with an alkyl group or a halogen atom.
[0059] As the yellow coloring agent, there can be mentioned nitro pigments such as Naphthol
Yellow, azo pigments such as Hansa Yellow 5G, Hansa Yellow 3G, Hansa Yellow G, Benzidine
Yellow GR, Benzidine Yellow G and Vulcan Yellow 5G, inorganic pigments such as yellow
iron oxide and yellow ochre, and oil-soluble dyes listed in Color Index, such as C.I.
Solvent Yellow 2, C.I. Solvent Yellow 6, C.I. Solvent Yellow 14, C.I. Solvent Yellow
15, C.I. Solvent Yellow 16, C.I. Solvent Yellow 19 and C.I. Solvent Yellow 21.
[0060] Among these yellow coloring agents, an organic dye or pigment is preferably used
from the viewpoint of the dispersibility in the binder resin. A benzidine pigment
is especially preferably used because the dispersibility in the binder resin is very
good and the pigment is dispersed in the form of very fine particles, and a yellow
toner having excellent electric characteristics can be provided.
[0061] A charge-controlling agent can be incorporated into the binder resin for controlling
the charging of the toner. A known charge-controlling agent can be used in the present
invention. For example, there can be mentioned oil-soluble dyes such as Nigrosine
Base (C.I. 50415), Oil Black (C.I. 26150) and Spiron Black, metal salts of naphthenic
acid, metal soaps, metal-containing azo dyes, pyrimidine compounds and metal chelates
of alkylsalicylic acids. A zinc salt or zinc complex of salicylic acid and a zinc
salt or zinc complex of an alkylsalicylic acid are preferably used as the charge-controlling
agent. It is preferred that the charge-controlling agent be incorporated in the binder
resin in an amount of 0.5 to 5.0% by weight based on the binder resin.
[0062] The toner for full color development, prepared from the foregoing components, preferably
has a particle size such that the median diameter based on the volume, measured by
a Coulter Counter, is 5 to 20 »m, especially 8 to 15 »m. The flowability of the toner
can be improved by sprinkling inorganic fine particles such as hydrophobic silica
fine particles or organic fine particles composed of, for example, a polymer on the
surface of the toner.
[0063] It is preferred that when the transmission T (%) at 550 nm of the magenta toner is
lower than 2%, the transmission T (%) at 440 nm of the toner be at least 40%, especially
at least 45%.
[0064] It is preferred that when the transmission T (%) at 600 nm of the cyan toner is lower
than 2%, the transmission T (%) at 490 nm of the toner be at least 70%, especially
at least 75%.
[0065] It is preferred that when the transmission T (%) at 400 nm of the yellow toner is
lower than 2%, the transmission T (%) at 550 nm of the toner be at least 75%, especially
at least 80%.
[0066] In the case where the above-mentioned toner is used as a two-component type developer
by mixing it with a magnetic carrier, any known magnetic carriers used in this field
can be used, but ferrite particles capable of forming a soft magnetic brush are generally
preferred.
[0067] As is apparent from the foregoing description, according to the present invention,
by limiting the numbers of particles having a size of 10 to 12.5 »m² and particles
having a size of 12.5 to 15.0 »m² among the coloring agent particles dispersed in
the binder resin to below certain values, the light-transmitting property can be improved
for any of the magenta, cyan and yellow toners. Accordingly, these toners having an
improved light-transmitting property are preferably used for the full color development
where the toners are used in the overlapped state.
[0068] Furthermore, according to the present invention, by using a resin having an electroconductivity
of 1.0 x 10⁻⁹ to 5.0 x 10⁻⁹ (s/cm) as the binder resin of the toner, the differences
of electric characteristics among toners used in the overlapped state for the full
color development can be diminished. If the differences of electric characteristics
among the toners can be diminished, the development conditions for full color development
can be made substantially the same among the toners. Therefore, the difference of
the transfer quantity among the toners can be reduced and full color treatment can
be performed with an excellent image reproducibility.
[0069] The present invention will now be further described in the following Examples.
(Experiment 1)
Experiment 1-1
(1) Preparation of Magenta Toner
[0070] A polyester resin as the binder resin, a quinacridone pigment as the coloring agent
and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 5 to 15 »m.
[0071] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in an area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 30 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 10.
[0072] As shown in Table 1, the transmission T (%) of the obtained toner at 550 nm was 2%
and the transmission T (%) at 440 nm was 48%. The relation between the wavelength
and the transmission is shown in Fig. 2.
[0073] The above toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(2) Preparation of Cyan Toner
[0074] The same binder resin as used for the magenta toner was used, and a copper phthalocyanine
pigment was used as the coloring agent. These components were kneaded so that when
the toner was formed into a layer having a thickness of 0.9 »m, in the area of 780,000
»m² of the formed surface of the toner, the number of coloring agent particles having
a size of 10.00 to 12.5 »m² was 60 and the number of coloring agent particles having
a size of 12.5 to 15.0 »m² was 35.
[0075] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(3) Preparation of Yellow Toner
[0076] The same binder resin as used for the magenta toner was used, and a benzidine pigment
was used as the coloring agent. These components were kneaded so that when the toner
was formed into a layer having a thickness of 0.9 »m, in the area of 780,000 »m² of
the formed surface of the toner, the number of coloring agent particles having a size
of 10.00 to 12.5 »m² was 10 and the number of coloring agent particles having a size
of 12.5 to 15.0 »m² was 5.
[0077] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
[0078] Toners (1) through (3) were subjected to full color development under the same conditions
shown in Table 1 and were overlapped on a transfer material. The formed image was
evaluated. The results of the evaluation are shown in Table 1.
Experiments 1-2 through 1-5
(1) Preparation of Magenta Toner
[0079] In the same manner as described in Experiment 1-1, a toner having a particle size
of 5 to 15 »m was prepared, and the number of coloring agent particles and the transmission
of the toner were as shown in Table 1.
[0080] The obtained toner was formed in a two-component developer in the same manner as
described in Experiment 1-1.
[0081] The same cyan and yellow toners as used in Experiment 1-1 were used.
[0082] The image formed by using these toners was evaluated in the same manner as described
in Experiment 1-1. The results of the evaluation are shown in Table 1.
Experiment 1-6
(1) Preparation of Magenta Toner
[0083] A polyester resin as the binder resin, a quinacridone pigment as the coloring agent
and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 5 to 15 »m.
[0084] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 120 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 80.
[0085] The transmission T (%) of the obtained toner at 550 nm was 1.5% and the transmission
T (%) at 440 nm was 20%. The relation between the wavelength and the transmission
is shown in Fig. 1.
[0086] The image formed by using this magenta toner and the same cyan and yellow toners
as used in Experiment 1-1 was evaluated in the same manner as described in Experiment
1-1. The obtained image was dark and had extremely poor transparency and sharpness.

(Experiment 2)
Experiment 2-1
(1) Preparation of Cyan Toner
[0087] A polyester resin as the binder resin, a copper phthalocyanine pigment as the coloring
agent and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 8 to 15 »m.
[0088] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 60 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 35.
[0089] As shown in Table 2, the transmission T (%) of the obtained toner at 600 nm was 1.0%
and the transmission T (%) at 490 nm was 76%. The relation between the wavelength
and the transmission is shown in Fig. 4.
[0090] The above toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(2) Preparation of Yellow Toner
[0091] The same binder resin as used for the cyan toner was used, and a benzidine pigment
was used as the coloring agent. These components were kneaded so that when the toner
was formed into a layer having a thickness of 0.9 »m, in the area of 780,000 »m² of
the formed surface of the toner, the number of coloring agent particles having a size
of 10.00 to 12.5 »m² was 10 and the number of coloring agent particles having a size
of 12.5 to 15.0 »m² was 5.
[0092] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(3) Preparation of Magenta Toner
[0093] The same binder resin as used for the cyan toner was used, and a quinacridone pigment
was used as the coloring agent. These components were kneaded so that when the toner
was formed into a layer having a thickness of 0.9 »m, in the area of 780,000 »m² of
the formed surface of the toner, the number of coloring agent particles having a size
of 10.00 to 12.5 »m² was 30 and the number of coloring agent particles having a size
of 12.5 to 15.0 »m² was 10.
[0094] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
[0095] Toners (1) through (3) were subjected to full color development under same conditions
shown in Table 2 and were overlapped on a transfer material. The formed image was
evaluated. The results of the evaluation are shown in Table 2.
Experiments 2-2 through 2-3
(1) Preparation of Cyan Toner
[0096] In the same manner as described in Experiment 2-1, a toner having a particle size
of 8 to 15 »m was prepared, and the number of coloring agent particles and the transmission
of the toner were as shown in Table 2.
[0097] The obtained toner was formed in a two-component developer in the same manner as
described in Experiment 2-1.
[0098] The same magenta and yellow toners as used in Experiment 2-1 were used.
[0099] The image formed by full color development using these toners was evaluated in the
same manner as described in Experiment 2-1. The results of the evaluation are shown
in Table 2.
Experiment 2-4
(1) Preparation of Cyan Toner
[0100] A polyester resin as the binder resin, a copper phthalocyanine pigment as the coloring
agent and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 8 to 15 »m.
[0101] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 110 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 80.
[0102] The transmission T (%) of the obtained toner at 600 nm was 0.5% and the transmission
T (%) at 490 nm was 64%. The relation between the wavelength and the transmission
is shown in Fig. 3.
[0103] The image formed by using this cyan toner and the same magenta and yellow toners
as used in Experiment 2-1 was evaluated in the same manner as described in Experiment
2-1. The obtained image was dark and had extremely poor transparency and sharpness.
Experiment 2-5
(1) Preparation of Cyan Toner
[0104] A cyan toner was prepared in the same manner as described in Experiment 2-4 except
that kneading was carried out so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 78 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 53.
[0105] This cyan toner and the same magenta and yellow toners as used in Experiment 2-1
were subjected to full color development and were overlapped on a transfer material
to form an image. The formed image was evaluated. The image had poor sharpness.

(Experiment 3)
Experiment 3-1
(1) Preparation of Yellow Toner
[0106] A polyester resin as the binder resin, a benzidine pigment as the coloring agent
and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 5 to 15 »m.
[0107] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 10 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 6.
[0108] As shown in Table 3, the transmission T (%) of the obtained toner at 400 nm was 2%
and the transmission T (%) at 550 nm was 80%. The relation between the wavelength
and the transmission is shown in Fig. 6.
[0109] The above toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(2) Preparation of Magenta Toner
[0110] The same binder resin as used for the yellow toner was used, and a quinacridone pigment
was used as the coloring agent. These components were kneaded so that when the toner
was formed into a layer having a thickness of 0.9 »m, in the area of 780,000 »m² of
the formed surface of the toner, the number of coloring agent particles having a size
of 10.00 to 12.5 »m² was 30 and the number of coloring agent particles having a size
of 12.5 to 15.0 »m² was 10.
[0111] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
(3) Preparation of Cyan Toner
[0112] The same binder resin as used for the yellow toner was used, and a copper phthalocyanine
pigment was used as the coloring agent. These components were kneaded so that when
the toner was formed into a layer having a thickness of 0.9 »m, in the area of 780,000
»m² of the formed surface of the toner, the number of coloring agent particles having
a size of 10.00 to 12.5 »m² was 60 and the number of coloring agent particles having
a size of 12.5 to 15.0 »m² was 35.
[0113] The toner was mixed with a known magnetic ferrite carrier to form a two-component
developer.
[0114] Toners (1) through (3) were subjected to full color development under same conditions
shown in Table 3 and were overlapped on a transfer material. The formed image was
evaluated. The results of the evaluation are shown in Table 3.
Experiments 3-2 through 3-4
(1) Preparation of Yellow Toner
[0115] In the same manner as described in Experiment 3-1, a toner having a particle size
of 5 to 15 »m was prepared, and the number of coloring agent particles and the transmission
of the toner were as shown in Table 3.
[0116] The obtained toner was formed in a two-component developer in the same manner as
described in Experiment 3-1.
[0117] The same magenta and cyan toners as used in Experiment 3-1 were used.
[0118] The image formed by full color development using these toners was evaluated in the
same manner as described in Experiment 3-1. The results of the evaluation of the image
of the toners overlapped on a transfer material are shown in Table 3.
Experiment 3-5
(1) Preparation of Yellow Toner
[0119] A polyester resin as the binder resin, a benzidine pigment as the coloring agent
and, optionally, a charge-controlling agent were sufficiently kneaded, pulverized
and classified to obtain a toner having a particle size of 5 to 15 »m.
[0120] This kneading was conducted so that when the toner was formed into a layer having
a thickness of 0.9 »m, in the area of 780,000 »m² of the formed surface of the toner,
the number of coloring agent particles having a size of 10.0 to 12.5 »m² was 30 and
the number of coloring agent particles having a size of 12.5 to 15.0 »m² was 25.
[0121] The transmission T (%) of the obtained toner at 400 nm was 2.0% and the transmission
T (%) at 550 nm was 62%. The relation between the wavelength and the transmission
is shown in Fig. 5.
[0122] The image formed by full color development using this yellow toner and the same magenta
and cyan toners as used in Experiment 3-1 was evaluated in the same manner as described
in Experiment 3-1. The obtained image had an unevendensity and poor the sharpness.

(Experiment 4)
Experiment 4-1
[0123] A toner having an average particle size of 10 »m and an electroconductivity of 2.5
x 10⁻⁹ (s/cm) was prepared by kneading 100 parts by weight of a polyester resin having
an electroconductivity of 2.5 x 10⁻⁹ (s/cm) and a melting point of 90° as the binder
resin and 4.0 parts by weight of a quinacridone pigment as the coloring agent so that
when the obtained toner was formed in a layer having a thickness of 0.9 »m, in the
area of 780,000 »m² of the formed surface of the toner, the number of dipsersed particles
having a size of 10 to 12.5 »m² was 29 and the number of dispersed particles having
a size of 12.5 to 15.0 »m² was 8.
[0124] A toner having an average particle size of 10 um and an electroconductivity of 2.6
x 10⁻⁹ (s/cm) was prepared by kneading 100 parts by weight of the same binder resin
as used above and 3.0 parts by weight of a benzidine pigment as a yellow coloring
agent so that when the obtained toner was formed into a layer having a thickness of
0.9 »m, in the area of 780,000 »m² of the formed surface of the toner, the number
of pigment particles having a size of 10.0 to 12.5 »m² was 10 and the number of particles
having a size of 12.5 to 15.0 »m² was 5.
[0125] A toner having an average particle size of 10 »m and an electroconductivity of 2.5
x 10⁻⁹ (s/cm) was prepared by kneading 100 parts by weight of the same binder resin
as described above and 4.0 parts by weight of a copper phthalocyanine as a cyan coloring
pigment so that when the obtained toner was formed in a layer having a thickness of
9 »m, in the area of 780,000 »m² of the formed surface of the toner, the number of
dispersed pigment particles having a size of 10.0 to 12.5 »m² was 58 and the number
of dispersed pigment particles was 36.
[0126] A black toner having an electroconductivity of 2.7 x 10⁻⁹ (s/cm) was prepared by
using 100 parts by weight of the binder resin and 4 parts by weight of carbon black
according to customary procedures.
[0127] The foregoing toners were independently mixed with a known ferrite carrier to prepare
respective color developers. These developers were subjected to full color development
under same developing conditions and were overlapped on a transfer material to obtain
a full color image. With respect to each developed toner, the toner transfer efficiency
was determined by using an A-4 original having an image area ratio of 20%. The obtained
results are shown in Table 4.
Experiments 4-2 through 4-5
[0128] The experiments were carried out in the same manner as described in Experiment 4-1
except that the electroconductivity and melting temperature of the binder resin, the
magenta coloring agent and the dispersion states of the coloring agents in the toners
were changed as shown in Table 4. The obtained results are shown in Table 4.
[0129] From the results obtained in Experiments 4-1 and 4-2, it is seen that in the magenta
toner of the present invention, the developing and transfer characteristics can be
made almost equal to those of other color toners and that this magenta toner has excellent
transparency and coloring properties. Therefore a sharp full color image can be provided
without any density unevenness.

(Experiment 5)
Experiments 5-1 through 5-5
[0130] Experiments were carried out in the same manner as described in Experiment 4-1 except
that the electroconductivity and melting point of the binder resin, the cyan coloring
agent and the dispersion states of the coloring agents in the toners were changed
as shown in Table 5. The obtained full color images were evaluated. The obtained results
are shown in Table 5.

(Experiment 6)
Experiments 6-1 through 6-5
[0131] Various toners were prepared in the same manner as described in Experiment 5-1 except
that the electrocoductivity and melting point of the binder resin, the cyan coloring
agent and the dispersion states of the coloring agents in the toners were changed
as shown in Table 6, and images formed by full color development using these toners
were evaluated. The obtained results are shown in Table 6.
[0132] From the results obtained in Experiments 5-1 and 5-2, it is seen that in the cyan
toner of the present invention, the developing and transfer characteristics can be
made substantially equal to those of other color toners and that this cyan toner has
excellent transparency and coloring properties. Therefore, a sharp full color image
can be provided without any density unevenness.
[0133] From the results obtained in Experiments 6-1 and 6-2, it is seen that in the yellow
toner of the present invention, the developing and transfer characteristics can be
made substantially equal to those of other color toners and that this cyan toner has
excellent transparency and coloring properties. Therefore, a sharp full color image
can be provided without any density unevenness.
