U.S. patent number 3,870,644 [Application Number 05/307,993] was granted by the patent office on 1975-03-11 for liquid developer for plural-color electrophotography.
This patent grant is currently assigned to Kabushiki Kaisha Ricoh. Invention is credited to Hazime Machida, Zenjiro Okuno.
United States Patent |
3,870,644 |
Machida , et al. |
March 11, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Liquid developer for plural-color electrophotography
Abstract
A set of liquid developers for plural-color electrophotography,
comprising carrier liquids and toners of four colors separately
dispersed in said carrier liquid for each color, said toners being
selected from the group consisting of: A. a toner consisting
substantially of coloring agents for four colors and finely divided
particles of colorless, transparent organic photoconductive
substance colored severally by said four coloring agents; B. a
toner consisting substantially of coloring agents for four colors,
finely divided particles of colorless, transparent organic
photoconductive substance colored severally by said four coloring
agents, and one coating agent coated on the surface of said colored
photoconductive substance and selected from the group consisting of
hitherto known coating resins for toner and such vinyl polymers as
are insoluble in said carrier liquid; and C. a toner consisting
substantially of coloring agents for four colors, finely divided
particles of colorless, transparent organic photoconductive
substance colored severally by said four coloring agents, and a
polymer coated on the surface of said colored photoconductive
substance and having an affinity with said carrier liquid.
Inventors: |
Machida; Hazime (Tokyo,
JA), Okuno; Zenjiro (Tokyo, JA) |
Assignee: |
Kabushiki Kaisha Ricoh (Tokyo,
JA)
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Family
ID: |
27278414 |
Appl.
No.: |
05/307,993 |
Filed: |
November 20, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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9971 |
Feb 9, 1970 |
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Foreign Application Priority Data
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Feb 10, 1969 [JA] |
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44-9277 |
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Current U.S.
Class: |
430/114;
430/45.2; 430/901 |
Current CPC
Class: |
G03G
9/135 (20130101); G03G 9/122 (20130101); G03G
9/131 (20130101); Y10S 430/101 (20130101) |
Current International
Class: |
G03G
9/12 (20060101); G03G 9/135 (20060101); G03G
9/13 (20060101); G03g 009/00 () |
Field of
Search: |
;252/62.1L
;96/1.2,1.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Nelson; P. A.
Attorney, Agent or Firm: Woodhams, Blanchard and Flynn
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This is a continuation-in-part of application Ser. No. 9 971, filed
Feb. 9, 1970 now abandoned.
Claims
What is claimed is:
1. In a set of liquid developers for plural-color
electrophotography, in which each developer comprises a toner
dispersed in a carrier liquid, said carrier liquid being a liquid
hydrocarbon having an electric resistance of at least
10.sup.9.OMEGA. .cm and a dielectric constant of not greater than
3, said set of liquid developers comprising separate liquid
developers respectively containing as the only toner present
therein
a. a magenta-color toner consisting essentially of finely divided
particles of photoconductive substance colored with a
magenta-coloring agent;
b. a cyan-color toner consisting essentially of finely divided
particles of photoconductive substance colored with a cyan-coloring
agent;
c. a black-color toner consisting essentially of finely divided
particles of photoconductive substances colored with a
black-coloring agent;
d. a yellow-color toner consisting essentially of finely divided
particles of photoconductive substance colored with a
yellow-coloring agent, the improvement which comprises: the
photoconductive substance in each of said toners is a colorless,
transparent photoconductive substance selected from the group
consisting of anthracene, imidazole, carbazole,
poly-3,6-dibromovinylcarbazole, poly-2,3-dichlorovinylcarbazole,
poly-2,4-dichlorovinylcarbazole, poly-3,6-dichlorovinylcarbazole,
poly-3-bromo-6-chlorovinylcarbazole, poly-3-bromovinylcarbazole,
poly-3-chlorovinylcarbazole, poly-N-vinylcarbazole,
polyvinyllanthracene, polyvinylcarbazole, polydimethylaminostyrene,
polyorthobromocarbazole, poly-2,3-dichlorovinylanthracene,
polyorthochlorovinylcarbazole, poly-2,4-dichlorocarbazole, and
poly-2-chlorovinylanthracene.
2. A set of liquid developers for plural-color electrophotography
according to claim 1, wherein said toners are respectively coated
with a coating agent selected from the group consisting of:
a polymer comprising at least one monomer selected from the group
consisting of vinyl monomers expressed by the below-mentioned
formula (1);
a polymer comprising at least one vinyl monomer selected from the
group consisting of monomers expressed by the below-mentioned
formula (2); and
a copolymer comprising at least one monomer selected from the group
consisting of vinyl monomers expressed by the below-mentioned
formula (1) and at least one monomer selected from the group
consisting of vinyl monomers expressed by the below-mentioned
formula (2); Formula (1) ##SPC7##
wherein, Y is selected from the group consisting of --COOH, --H and
--Cl;
X is selected from the group consisting of --C.sub.n H.sub.2n.sub.+
1 (1.ltoreq.n.ltoreq.4), --OCOC.sub.n H.sub.2n.sub.+ 1
(1.ltoreq.n.ltoreq.4), --OC.sub.n H.sub.2n.sub.+ 1
(1.ltoreq.n.ltoreq.4), --CN, --COOH, --Cl, --COCl, --COOR wherein R
is selected from the group consisting of ##SPC8## wherein L is
selected from the group consisting of --CH.sub.3, --NO.sub.2,
--NH.sub.2, --N(CH.sub.3).sub.2, --COOH, --COOCH.sub.3, --OH,
--OCH.sub.3, --Cl and Br ##SPC9##
--(CH.sub.2).sub.n ##SPC10##
and --(CH.sub.2).sub.n ##SPC11##
Ro is selected from the group consisting of --H and --CH.sub.3,
Formula (2) ##SPC12##
wherein, R is selected from the group consisting of --H and
--CH.sub.3 ;
R' is selected from the group consisting of alkyls having 5 to 20
carbon atoms, --OR" wherein R" is selected from the alkyls having 5
to 20 carbon atoms, and --COOR'" wherein R'" is selected from the
group consisting of cyclohexyl and alkyls having 5 to 20 carbon
atoms.
3. A set of liquid developers for plural-color electrophotography
according to claim 2, wherein said toners are respectively composed
of said coloring agent and products of the copolymerization
reaction of:
a. a monomer for forming said organic photoconductive substance
selected from the group consisting of 3,6-dibromovinylcarbazole,
2,3-dichlorovinylcarbazole, 2,4-dichlorovinylcarbazole,
3,6-dichlorovinylcarbazole, 3-bromo-6-chlorovinylcarbazole,
3-bromovinylcarbazole, 3-chlorovinylcarbazole, N-vinylcarbazole,
vinylanthracene, vinylcarbazole, dimethylaminostyrene,
orthobromocarbazole, 2,3-dichlorovinylanthracene,
orthochlorovinylcarbazole, 2,4-dichlorocarbazole and
2-chlorovinylanthracene; and
b. at least one monomer selected from the group consisting of
monomers expressed by said formula (1) and monomers expressed by
said formula (2), the products of said copolymerization reaction
being separately colored with said coloring agents for each
color.
4. A set of liquid developers for plural-color electrophotography
according to claim 1, wherein each said toner consists essentially
of 100 parts by weight of said photoconductive substance and 1 to
100 parts by weight of said coloring agent.
5. A set of liquid developers for plural-color electrophotography
according to claim 2, wherein each said toner consists essentially
of 100 parts by weight of said photoconductive substance and 1 to
100 parts by weight of said coloring agent, and the amount of said
coating agent coated on each said toner is in the range of from 0.1
to 10 parts by weight of said coating agent per one part by weight
of said toner.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a set of liquid developers for
electrophotography, and particularly a set of liquid developers for
use in reproducing a plural-color electrophotograph by a
wet-developing process.
2. Description of the Prior Art
The conventional liquid developers for plural-color
electrophotography have been prepared by processes in which pigment
particles in plural colors are coated for each color with a natural
resin or a synthetic resin for imparting a polarlity-controlling
property and a dispersibility to said particles and the thus coated
particles are separately dispersed as the toner in a carrier
liquid. And, in case of reproducing a plural-color image of an
original on an electrophotographic recording material by employing
a set of developers as above, there has been usually applied a
method wherein the impression of electrostatic charge, exposure and
development are repeated in turn thereby reproducing the color
images in the order of, say, black, yellow, magenta and cyan.
However, said developers in the prior art have a drawback in
reproducing a plural-color image of an original on a recording
material such that, in cases where the developers employed contain
toners consisting of the pigments or a resin coated thereon having
a high electrical resistivity, the electrical resistivity of the
first formed image-area becomes higher than that of the non-image
area, making it difficult to effect a uniform impression of
electrostatic charge on the surface of the recording material at
the time of the next impression of electrostatic charge to form
another color-image area different from the first one and resulting
in impairment of the color balance. In other words, the high
electrical resistivity of the image-area hampers the disappearance
of the electric charge of the area where a complete disappearance
of said electric charge is required after exposure, and, as a
result, on the occasion of the next dipping in another developer,
the toner adheres to the latter area too, thereby making it
difficult to reproduce a plural-color image of the original. On the
other hand, a similar phenomenon occurs also in case of reproducing
the color images in order as above by employing a set of developers
containing toners consisting of pigments or a resin coated thereon
having a low electrical resistivity. In other words, a uniform
impression of electrostatic charge on the recording material
subsequent to formation of the first image-area thereon becomes
impossible as in the foregoing case and there takes place a
disappearance of the electric charge of the area where a residual
charge is required after exposure or decrease in electric potential
thereof, and, as a result, on the occasion of the next dipping in
another developer, the toner fails to adhere to said area, thereby
making it difficult to reproduce a desired plural-color image of
the original.
Inasmuch the plural-color electrophotography is supposed to
reproduce the color-images of an original by means of superposing
toners for plural colors in order as above, certain portions of a
once formed image-area must be adhered to toners for other colors
thereon, and, accordingly, the materials of said toners should be
also possessed of satisfactory electrostatic characteristics.
Thus, the U.S. Pat. No. 3,060,020 Specification provides a method
for reproducing the multi-color images electrographically using the
developer powders prepared by mixing a photoconductive zinc oxide
powder together with a thermoplastic material and coloring agents
for each color. In case of utilizing such developer powders as
liquid developer there was entailed a drawback that developer
powders, which dispersibility in carrier liquid is inferior,
precipitate after a long period of preservation, thereby the
function as developer being lost. The images formed onto an
electrophotographic copying material using liquid developers
dispersed said developer powders in a carrier liquid had also a
drawback that they are readily separated from a photoconductive
layer owing to its bad adhesiveness to said layer.
In case of effecting color reproduction using such liquid
developers, furthermore, it was found that impression and
disappearance of electric charge can be made as desired, but in
superposing toners for plural colors only the color of the
last-adhered toner is predominant and the color tone of the
first-adhered toner decreases, entailing dissatisfaction in
reproductivity of color tone.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a set of liquid
developers for plural-color electrophotography which make up for
the shortcomings of conventional developers as described in the
foregoing.
The developers under the present invention are applicable to both
the electrostatic recording material employed for a method wherein
an electrostatic latent image is formed on a recording material by
means of an impression of electrostatic charge on said recording
material and exposure subsequent thereto and the thus formed latent
image is then made into a plural-color visible image through
wet-process development and the electrostatic recording material
employed for a method wherein an electrostatic latent image
corresponding to an original image is directly formed on a
recording material and then made into a plural-color visible image
through wet-process development.
As for the colored particles to be employed for the material of the
toners in the present invention, finely divided particles of
colorless, transparent organic photoconductive substances having a
high electrical resistivity and provided with a desired color are
applicable. And, as for said colorless, transparent organic
photoconductive substances, the suitable one includes, for
instance, anthracene, imidazole, carbazole,
poly-3,6-dibromovinylcarbazole, poly-2,3-dichlorovinylcarbazole,
poly-2,4-dichlorovinylcarbazole, poly-3,6-dichlorovinylcarbazole,
poly-3-bromo-6-chlorovinylcarbazole, poly-3-bromovinylcarbazole,
poly-3-chlorovinylcarbazole, poly-N-vinylcarbazole and
polyvinylanthracene, etc.
As for the coloring agent for providing these photoconductive
substances with desired colors, either of the inorganic substance
and the organic substance will do, and all of those colored
substances called pigments and those colored substances called
coloring matters are applicable. And, the coloring agents having
transparency are advantageously employed in the present invention.
For example, as for the coloring agent for black color, Cyanine
Black BX (a manufacture of Sumitomo Kagaku K. K.), Spilon Black (a
manufacture of Hodogaya Chemical Industries Ltd., as hereinafter
referred to as H Co.), Spirit Black (a manufacture of Orient
Chemical Industries Ltd., as hereinafter referred to as O Co.),
etc. are applicable. As for the coloring agent for magenta color,
Spilon Red (C.I. Solvent Red 8; a manufacture of H Co.), Spilon
Orange (C.I. Solvent Orange 5; a manufacture of H Co.), Benzidine
Orange (C.I. No. 21110; a manufacture of Sanyo Color Works Ltd., as
hereinafter referred to as S Co.), Brilliant Carmine 6B (C.I. No.
15850; a manufacture of S Co.), Scarlet KR (C.I. No. 15865; a
manufacture of S Co.), Fast Red (C.I. No. 15865; a manufacture of
Dainichi Seika K. K. as hereinafter referred to as D Co.), Monolite
Fast Red (a manufacture of Imperial Chemical Industries Ltd.,
England as herein after referred to as I Co.), etc. are applicable.
As for the coloring agent for yellow color, Spilon Yellow (C.I.
Solvent Yellow 19; a manufacture of H Co.), Benzidine Yellow GNN
(C.I. No. 21100; a manufacture of S Co.), Benzidine Yellow 471
(C.I. No. 21095; a manufacture of D Co.), Monolite Fast Yellow IOG
(a manufacture of I Co.), etc. are applicable. As for the coloring
agent for cyan color, Victoria Blue (C.I. No. 44045; a manufacture
of H Co.), Methylene Blue (C.I. No. 52015; a manufacture of H Co.),
Oil Blue (C.I. No. 61555; a manufacture of O Co.), Alkali Blue
(C.I. No. 42750; a manufacture of O Co.), Sky Blue (a manufacture
of S Co.), Cyanine Blue FG (a manufacture of S Co.), Cyanine Blue
NSG (C.I. No. 74250; a manufacture of D Co.), Lignol Blue NCB (a
manufacture of Toyo Ink Industries Ltd.), Monastral Fast Blue G (a
manufacture of I Co.), Vali Fast Blue (C.I. No. 74350; a
manufacture of O Co.), etc. are applicable. As for the coloring
agent for green color, Phthalocyanine Green L. L (a manufacture of
S Co.), Phthalocyanine Green LX (C.I. No. 42040; a manufacture of S
Co.), Seika Light Green Lake No. 4554 (C.I. No. 42040; a
manufacture of D Co.), Chromofine Green G (C.I. No. 74260; a
manufacture of D Co.), etc. are applicable. As for the coloring
agent for other colors than the foregoing, Spilon Violet (C.I.
Solvent Violet 2; a manufacture of H Co. for purple color) is
applicable.
In the present invention, the toners to be applied comprise the
aforesaid highly insulating organic photoconductive substance and
coloring agent employed as the toner base and according to the
following combinations (a), (b) and (c):
a. a toner consisting substantially of a colorless, transparent
organic photoconductive substance and a coloring agent.
b. a toner consisting substantially of a colorless, transparent
organic photoconductive substance, a coloring agent and a hitherto
known resin for use in coating the toner or at least one polymer
selected from the group consisting of compounds expressed by the
below-mentioned general formula (1); and
c. a toner consisting substantially of a colorless, transparent
organic photoconductive substance, a coloring agent and a polymer
which principle component is at least one member of the group
consisting of compounds expressed by the below-mentioned general
formula (2).
In other words, such developers as prepared by dispersing either
one of the toners of said combination in a carrier liquid are
included in the present invention.
To begin with, in case of preparing a toner under (a), the coloring
agent is first dissolved or dispersed in an appropriate solvent,
next a photoconductive substance is dissolved or dispersed therein,
and the resultant dispersion is dried and pulverized. In this case,
it is desirable to either select a combination of such
photoconductive substance and coloring agent as are mutually
soluble from among the abovementioned photoconductive substances
and coloring agents or select a solvent in which both the
photoconductive substance and the coloring agent are soluble.
Therefore, such particles as obtained by drying and pulverization
of a dispersion prepared by combining either one of such
photoconductive substances as polyvinyl anthracene,
poly-2,3-dichlorovinyl carbazole, poly-2,4-dichlorovinyl carbazole
and polyvinyl carbazole with either one of the oil-soluble coloring
agents such as Methylene Blue (a manufacture of H Co.), Victoria
Blue (a manufacture of H Co.) and Spilon Red (a manufacture of H
Co.) and dissolving the thus combined photoconductive substance and
coloring agent in either one of monochlorobenzene, dichlorobenzene
and benzene, which are all capable of dissolving both of said
photoconductive substance and coloring agent, are suitable as the
toner in the present invention. Further, in case where a polymeric
photoconductive substance such as N-vinylcarbazole is employed,
through effecting suspension polymerization by adding a coloring
agent for a desired color at the time of polymerization of said
substance, there can be obtained a toner which is provided with
said color much more securely and particularly suitable for the
developer of the present invention.
The monomer or monomers applicable for producing a colored organic
photoconductive substance such as aforesaid colored
poly-N-vinylcarbazole are at least one monomer selected from the
group consisting of N-vinylcarbazole, vinylanthracene,
dimethylaminostyrene, 3-bromo-6-chlorovinylcarbazole,
orthobromocarbazole, 3,6-dibromovinylcarbazole,
2,3-dichlorovinylanthracene, orthochlorovinylcarbazole,
2,4-dichlorocarbazole and 2-chlorovinylanthracene. The foregoing
toners display a distinct electric charge within the
below-mentioned carrier liquids, and, besides, the dispersibility
thereof has proved satisfactory.
As for the toner under (b) above, it is prepared by employing the
toner under (a) as its base and combining therewith a hitherto
known resin for use in coating the toner or a polymer comprising at
least one member of the group consisting of compounds expressed by
the following general formula (1), thereby much more improving the
fixability of toner toward an electrostatic recording material, the
electrification property of toner and the dispersibility of toner.
General Formula (1) ##SPC1##
wherein, Y represents a radical selected from the group consisting
of --COOH, --H and --Cl;
X represents a radical selected from the group consisting of
--C.sub.n H.sub.2n.sub.+1 (1.ltoreq.n.ltoreq.4), --OCOC.sub.n
H.sub.2n.sub.+1 (1.ltoreq.n.ltoreq.4), --OC.sub.n H.sub.2n.sub.+1
(1.ltoreq.n.ltoreq.4), --CN, --COOH, --Cl, --COCl, --COOR [wherein
R is selected from the ##SPC2##
[wherein L is selected from the group consisting of --CH.sub.3,
--NO.sub.2, --NH.sub.2, --N(CH.sub.3).sub.2, --COOH, --COOCH.sub.3,
--OH, --OCH.sub.3, --Cl and --Br], ##SPC3##
(wherein L is identical with said L), --(CH.sub.2).sub.n
##SPC4##
(wherein, L is identical with said L, and n=1-4) and
--(CH.sub.2).sub.n ##SPC5##
(wherein, L is identical with said L, and n=1-4); Ro represents a
radical selected from the group consisting of --H and --
--CH.sub.3.
To give concrete examples of such coating resin or polymer, the
former includes hitherto known coating agents such as alkyd resin
STAYDELITE resin, rosin, linseed oil and phenolmodificated resin,
and as for the latter, there can be enumerated varieties of
substances, such as styrene butadiene copolymer, polybutyl
methacrylate, polyoctyl methacrylate, polylauryl methacrylate,
polycyclohexyl methacrylate, poly-n-hexyl vinyl ether, polyvinyl
butylate, polystearyl vinyl ether, poly-n-amyl vinyl ether,
styrene-butyl methacrylate copolymer, styrene-lauryl methacrylate
copolymer, hydroxyl ethyl methacrylate-hexyl methacrylate
copolymer, glycidyl methacrylate-vinyl stearate copolymer,
methacrylate-aminostyrenelauryl methacrylate copolymer,
paracyclohexyl methacrylatenitrostyrene-octylacrylate copolymer,
octadecyl methacrylateacrylamide copolymer, etc.
In case of preparing a toner under (b), there can be applied either
of the following two methods: a method wherein appropriate toner
particles and a coating resin or a polymer are kneaded in the
presence of a small quantity of solvent, thereby causing said
coating resin or polymer to coat the surface of said particles; and
a method wherein a photoconductive substance, a coloring agent and
a coating resin or polymer are mixed within a solvent and a mixture
resulting therefrom is subjected to either spray-drying or
pulverization after drying to make it into particles having a
grain-size of about 1 - 5.mu..
In case of preparing a toner under (c), a polymer consisting of at
least one vinyl monomer selected from the group consisting of
compounds expressed by the following general formula (2) is coated
on the toner under (a). General Formula (2) ##SPC6##
wherein, R represents a radical selected from the group consisting
of --H and --CH.sub.3 ;
R' represents a radical selected from the group consisting of alkyl
radicals having 5 to 20 carbon atoms, --OR" (wherein R" represents
a radical selected from alkyl radicals having 5 to 20 carbon atoms)
and --COOR'" (wherein R'" represents a radical selected from the
group consisting of cyclohexyl radical and alkyl radicals having 5
to 20 carbon atoms).
Further, in case of preparing a toner having a composition under
(c), such a compound as expressed by the aforementioned general
formula (1) may be employed at the same time.
In case of preparing a toner by employing a vinyl monomer expressed
by the general formula (1) or a vinyl compound expressed by the
general formulas (1) and (2), a polymer consisting of at least one
vinyl compound expressed by the general formula (1) or consisting
of at least one vinyl compound expressed by the general formula (1)
along with at least one vinyl compound expressed by the general
formula (2) is first prepared and thus prepared polymer is treated
in the same way as the coating resin in case of preparing a toner
under (b), whereby the desired toner is obtained. Further, it will
do to carry out polymerization upon adding a photoconductive
substance and a coloring agent when preparing said polymer.
Moreover, through either polymerization upon adding a monomer which
is to form a photoconductive substance consisting of a polymer,
such as N-vinyl carbazole, vinyl anthracene, dimethylaminostyrene,
orthobromovinyl carbazole, 2,3-chlorovinyl anthracene,
orthochlorovinyl carbazole, 2,4-dichlorovinyl carbazole,
3,6-dichlorovinylcarbazole, 2-chlorovinyl anthracene,
3,6-dibromovinylcarbazole and 3-bromo-6-chlorovinylcarbazole, to a
vinyl compound expressed by said general formulas, or suspension
polymerization upon adding a coloring agent in addition to the
foregoing monomer, there can be obtained a toner consisting of a
polymer chemically bonded to a photoconductive substance and
contributing to the polarity-controllability as well as
dispersibility thereof.
The present invention relates to a set of liquid developers for
plural-color electrophotography wherein the toners have been
separately dispersed in a carrier liquid for each color. As for the
carrier liquid to be employed, any of the liquid hydrocarbons of
normal paraffin family, isoparaffin family, olefin family and
Naphtha No. 6 family hitherto known as the carrier liquid for
developers for use in the wet-process developing method or said
liquid hydrocarbons containing an aromatic hydrocarbon as well is
applicable, and these hydrocarbons are all possessed of an
electrical resistivity not less than 10.sup.9.OMEGA. .cm and a
dielectric constant not greater than 3. To give concrete examples
of hydrocarbons having said properties, there are manufactures of
ESSO Standard Oil Co. sold under tradenames of Naphtha No. 6,
Solvesso 100, Isopar H, Isopar G and Isopar L along with a
manufacture of Mobile Oil Co. sold under the tradename of Pegasol
AS-100. And, it will do to employ these manufactures either
individually or upon mixing two or more thereof.
In order to form a colored image on an electrophotographic copying
material by the use of the set of four color developer liquids
according to the present invention, the following developing
process is applicable:
a. Negative charge from corona discharge is impressed onto the
entire surface of a photoconductive layer of the copying material,
said layer being formed by dispersing zinc oxide in a resinous
binder, and this is followed by the exposing of the photoconductive
layer, through a colored original and a blue filter which is laid
underneath of said original, to light. The resultant copying
material having an electrostatic latent image is then subjected to
the first development by the immersion of said copying material
into a developer liquid containing dispersed therein yellow
toners;
b. After drying the resultant copying material having a yellow
image, the photoconductive layer of said coyping material is again
impressed with negative charge. Thereafter, the copying material is
exposed, through the same colored original and a green filter laid
underneath thereof, to light. Then, the exposed copying material is
subjected to the second development by the immersion of said
copying material into a developer liquid containing dispersed
therein magenta toners;
c. The resultant copying material having a yellow image and a
magenta image is dried, and then this copying material is once
again impressed with negative charge and exposed, through the same
colored original and a red filter laid underneath thereof, to
light, and then subjected to the third development by the immersion
of said copying material into a developer liquid containing
dispersed therein cyan toners;
d. Thereafter, the resultant copying material is dried and
impressed with negative charge according to the same procedure as
described above, and, subsequently, exposure is effected, through
the same colored original without using a filter, to light. The
exposed copying material is then subjected to the fourth
development by the immersion of said copying material into a
developer liquid containing dispersed therein black toners.
When reproducing a colored original through the above-mentioned
process, the toners contained in the developer have a colorless,
transparent organic photoconductive substance as base material, and
therefore when interposing toners for multi colors for the purpose
of reproducing the colored original the electric charge impressed
on the copying material after formation of images thereon is
permitted to be uniform in both image and non-image areas and when
exposing the copying material to light the disappearance of
electric charge impressed on the desired area can be effected
rapidly and completely, whereby it is made possible to fix desired
toners for multi colors in turn onto desired areas of the copying
material and furthermore transparency of said toners prevents the
colors of last superposed toners from being predominant in the
toner-superposed area.
Because of their containing toners consisting of a colorless,
transparent organic photoconductive substance having a high
electrical resistivity as the toner base, the above-described
developers under the present invention are capable of rendering the
electrification property of an image-area and a non-image area
uniform when impressed with electrostatic charge subsequent to
formation of the image on a recording material on the occasion of
superposing colors for reproducing a plural-color image, and also
capable of causing the electric charge on a desired portion of a
recording material to disappear rapidly and completely in case
where a recording material impressed with electrostatic charge is
subjected to exposure, so that it is possible to cause a toner for
a desired color to fix onto a desired portion of said recording
material in order. Thus, a plural-color original can be faithfully
reproduced without impairing the color-balance.
In applying a set of four color developer liquids of our invention
to the respective developments, colors in each development may be
employed in various color sequence as shown in the undermentioned
Table 1.
Table 1
__________________________________________________________________________
Development Developer liquid No. Sequence 1 2 3 4 5 6 7 8
__________________________________________________________________________
First yellow magenta magenta cyan cyan black black black Second
cyan yellow cyan magenta yellow yellow cyan magenta Third magenta
cyan yellow yellow magenta magenta magenta cyan Fourth black black
black black black cyan yellow yellow
__________________________________________________________________________
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
A solution was prepared by adding 1 kg of N-vinyl carbazole to 10
kg of a buffer solution (viz., a solution prepared by dissolving
2.88g to caustic soda, 11.18g of potassium chloride and 9.28g of
boric acid in 6 litres of distilled water) and dissolving therein
by heating at 70.degree.C. Then, to said solution was added another
solution prepared by dissolving 20g of Victoria Blue in 100 ml of
monochlorobenzene, and the mixture was thoroughly stirred. To a
solution thus prepared was added still another solution prepared by
dissolving 2.5g of azobisisobutylonitrile (viz., a reaction
initiator) in 50 ml of monochlorobenzene, and, while stirring at a
high speed, 5g of bentonite was added as well. Subsequently, while
stirring, the resultant mixed solution was heated up to a
temperature of about 90.degree.C, and, by means of maintaining said
temperature for four hours, said solution was caused to effect
suspension polymerization, whereby there was prepared
photoconductive particles colored in blue. Then, these particles
were washed in water, cleansed with methanol and dried. The dried
particles were further treated with monochlorobenzene, and
thereafter were resuspended within n-hexane and dried, thereby
producing finely divided particles of cyan color. By dispersing
about 10g of thus produced particles in 1,000 ml of Naphtha No. 6,
there was obtained a developer containing a cyan-color toner.
On the other hand, in accordance with the method of preparing a
developer as set forth above, a developer containing black-color
toner, a developer containing yellow-color toner and a developer
containing magenta-color toner were also prepared by employing
Spirit Black, Spilon Yellow and Spilon Red, respectively, in lieu
of Victoria Blue employed in preparing the foregoing cyan-color
toner.
By employing a set of liquid developers for plural-color
electrophotography comprising black, yellow, magenta and cyan
colors prepared as above, and applying conventional processes to a
commercialized electrophotographic copying paper (viz., a copying
paper having a photoconductive layer formed by binding zinc oxide
on a supporting paper with a resinous binder), a plural-color image
was reproduced. To be precise, namely, negative charge was first
impressed on the photoconductive layer of the copying paper, then
the photoconductive layer was exposed to light through a colored
original and a blue filter which is laid underneath of said
original and thereafter the copying material was dipped into the
liquid developer containing dispersed therein yellow-color toner to
thereby reproduce a yellow-color image on the copying paper.
Magenta and cyan-color images were reproduced respectively on the
copying paper by the following steps, i.e., impression of electric
charge, exposure to light through a green filter, dipping into a
developer containing magenta-color toner, additional impression of
electric charge, exposure to light through a red filter, and
dipping into a developer containing cyan-color toner. Then, a
black-color image was reproduced on the copying paper by impressing
negative electrostatic charge on the photoconductive layer of the
copying paper having yellow, magenta and cyan color images,
thereafter exposing the copying paper to white light through a
color original using no filter and dipping said copying paper into
a developer containing black-color toner. Clear-colored copied
images were thus obtained which reproduced original images with
high fidelity.
EXAMPLE 2
0.1 kg of a mixture, prepared by kneading-- poly-2, 4-dichlorovinyl
carbazole 1 kg, chlorobenzene 5 kg and Spilon Yellow 100 g,
was resuspended within 15 kg of n-hexane, whereby finely divided
particles of yellow-color were obtained. Then, by dispersing 50g of
thus obtained particles in 1,000 ml of Isopar H, a developer
containing a yellow-color toner was prepared.
On the other hand, by employing the same composition as above
except for employment of Cyanine Black BX as a coloring agent for
black-color, Vali Fast Blue as a coloring agent for cyan-color and
Fast Red as a coloring agent for magenta-color, respectively, in
lieu of said Spilon Yellow, there were prepared developers
respectively containing black-color toner, cyan-color toner and
magenta-color toner.
When a set of liquid developers for plural-color electrophotograpy
thus obtained was applied for copying a colored original onto an
electrophotographic copying paper by the use of the developers in
the order of black-yellow-magenta-cyan, there was obtained a
clear-cut colored image which faithfully reproduced said
original.
The efficiency of a set of liquid developers for pluralcolor
electrophotography thus prepared proved equal to that of developers
in Example 1.
EXAMPLE 3
A mixture, prepared by kneading-- polyvinyl anthracene powder 1 kg,
polystyrene-butadiene resin 0.5 kg, Brilliant Carmine 6B 50 g and
toluene 3 kg
was subjected to spray-drying with a spray-dryer, whereby finely
divided particles of magenta-color having a grain-size of about
1.mu. were obtained. By dispersing 20g of said particles in 1,000
ml of Naphtha No. 6/Solvesso 100 (mixing ratio: 6/4), a developer
containing a magenta-color toner was prepared.
On the other hand, by employing the same composition except for
employment of Spilon Black as a coloring agent for black-color,
Lignol Blue NCB as a coloring agent for cyan-color and Monolite
Fast Yellow IOG as a coloring agent for yellow-color, respectively,
in lieu of said Brilliant Carmine 6B, there were prepared
developers containing black-color toner, cyan-color toner and
yellow-color toner, respectively.
Further, for the purpose of testing a performance of the liquid
developers according to the invention, a set of control liquid
developers was prepared in accordance with the same procedure as
described above except that 1 kg of zinc oxide powder was used in
place of the polyvinyl anthracene powder referred to in the above
preparation of the respective liquid developers of the present
invention.
Comparative tests were carried out by the methods described below
to compare the aforesaid liquid developers as regards their toners
dispersion stability in the carrier liquid, fixing ability to a
photoconductive layer of copying paper and reproducibility of a
color tone of a colored original.
1. Dispersion Stability:
The magenta-color toner containing developer according to our
invention was poured into a measuring sedimentation tube 10 mm in
diameter and 300 mm in length till the surface of said toner comes
up to 300 mm. The same was left stand respectively for 7 days, one
month and three months to measure at each termination the
graduation to which the uppermost surface of the sedimented toner
came up.
It is to be noted that the larger the value of graduation, the more
superior the dispersion stability. The same measurement was
effected concerning the control developer containing a
magenta-color toner. Thus obtained dispersion stability test
results will be shown in Table-2.
Table 2 ______________________________________ after after one
after three 7 days month months
______________________________________ Developer according 250 mm
200 mm 150 mm to our example Control developer 140 mm 50 mm 40 mm
______________________________________ 2. Fixing Ability:
By using the same liquid developer according to the invention as
used in the aforesaid test-(1), an electrophotographic copying
paper (which is a copying paper for use in the electrophotographic
copying machine sold under the trademark Electron Recopy BS-1
manufactured by Kabushiki Kaisha RICOH) and Electron Recopy BS-1,
copied image consisting of magenta toner was formed on the copying
paper.
The toner concentration of the copied image was measured by a
densitometer manufactured and sold under the trade name of Narumi
NSG-III type of Narumi Shokai Kabushiki Kaisha, both before and
after 50 and 300 erasing strokes respectively were applied to the
image using a reciprocating erasion tester. The erasion tester was
provided with an eraser named "LION" (manufactured by Fukui
Kabushiki Kaisha) having a sectional area of 10 mm .times. 10 mm.
The tester is designed for rubbing the image with the eraser
reciprocally 100 times per minute under a load of 600 g. From the
test results, the undermentioned value was calculated:
Image concentration after erasure/Image concentration before
erasure .times. 100
Then, by the same method as described above, the copied image
formed with the control liquid developer containing magenta color
toner was tested in like fashion and the same calculation was
made.
The fixing ability (adhesiveness) of the toner to the
photoconductive layer is directly proportional to the thus
calculated value. The test results are given in Table-3.
Table 3 ______________________________________ Fixing Ability (%)
After 50 After 300 erasure erasure
______________________________________ Image formed with the
developer of our 70 45 invention Image formed with the control
developer 35 20 ______________________________________
As is clear from the results in Tables-2 and -3, the developer
according to our invention is recognized superior in both
dispersion stability and adhesiveness to photoconductive layer in
comparison with control developer using zinc oxide.
3. Reproducibility of Color Tone:
Next, using, as original, a color step tablet having colors of
black, blue, green, red, cyan, magenta, yellow and white
(transparent), and as developer, a set of developers according to
our invention and a set of control developers, color images were
reproduced on marketed electrophotographic copying papers according
to the same procedure disclosed in Example 2 to survey a difference
in color tone between images reproduced in both cases of using our
developer and control one. Thus obtained results were as mentioned
below.
Negative electrostatic charge was impressed on a photoconductive
layer of a copying paper, then same was exposed to white light
through said plural-color original, and dipped into a developer
containing black color toner to thereby form a copied black color
image area. A copied black color image was similarly reproduced
using a control developer containg black color toner. So far as
said copied black color image areas are concerned, there could find
no difference between our invention and the control example. Next,
electrostatic charge was impressed on the copying paper having the
thus copied color image, then same was exposed to light through a
blue filter interposed between the plural-color original and said
copying paper and dipped into a developer containing yellow color
toner to thereby form a copied yellow color image area. The yellow
color toner was, in both cases of our invention and the control
example, adhered to the copied black color image area and to areas
of the copying paper corresponding to red and yellow color areas of
the original. In the copied black color image area there was
recognized that the yellow color toner adhered onto the black color
toner and the adhered amount was substantially same in degree
between our invention and the control example. When making
comparison in color tone between both copied black image areas, it
was recognized that the copied black color image area of the
control example was more predominant in yellow than ours.
Next, electrostatic charge was impressed on the copying paper
having thus formed copied black and yellow color image areas, then
same was exposed to light through a green filter interposed between
the plural-color original and said copying paper and dipped into a
developer containing magenta color toner to thereby form a copied
magenta color image area. The magenta color toner adhered to the
copied black color image area and to areas of the copying paper
corresponding to blue, red and magenta color areas of the original
in both the control example and our invention. In the copied black
and red color image areas there was recognized that the magenta
color toner adhered onto the yellow color toner which formed the
copied yellow color image area, but the adhered amount was
substantially same in degree in both the control example and our
invention. In observing the color tone of the respective image
areas, it was recognized that the copied black color image area of
the control example was more predominant in red than ours, and that
the copied red color image area of the control example was more
predominant in magenta than ours. Then, electrostatic charge was
impressed on the copying paper having thus formed the respective
copied image areas, same was exposed to light through a red filter
interposed between the plural-color original and said copying paper
and dipped into a developer containing cyan color toner to thereby
form a copied cyan image area.
The cyan toner adhered to the copied black color image area and to
areas of the copying paper corresponding to blue, green and cyan
color areas of the original. It was recognized that in the black
and blue color areas the cyan color toner adhered onto the magenta
color toner which formed the copied magenta color image area and in
the green color area the cyan color toner adhered onto the yellow
color toner which formed the copied yellow color image area, but
the adhered amount was substantially same in degree in both our
invention and the control example. When comparing the present
invention with the control example in respect of the color tone of
the respective color image areas there was recognized that the
copied black color image area of the control example was cyanic
black, while that of our invention almost deep-black, and that the
copied blue and green color image areas of the control example were
all predominant in cyan color as compared with those of our
invention.
As described above, comparing the present invention with the
control example it was recognized that the amounts of adhered
toners in the respective color image areas was almost equal in both
cases, but in the color-imposed portions of the control example the
color of the uppermost toner was predominant and that of the
undermost toner decreased, especially the four-color imposed
portion thereof was not colored in deep-black but most predominant
in blue color. Contrary to this, in the copied color image
according to our invention it was recognized that the color of the
uppermost toner did not become unnaturally predominant and that of
the undermost toner was displayed with no decrease, thereby
permitting obtainment of a copied color image extremely superior in
reproductivity of color tone from the original color image.
This phenomenon may be analyzed as hereinafter, that is, in an
inorganic photoconductive substance such as a zinc oxide powder,
which lacks transparency, the color of the under portion of the
formed image is decreased by the toner for the color of the upper
portion thereof, while in an organic photoconductive powder, which
is transparent, such does never take place, thereby producing
superior color tone reproducibility.
For the purpose of obtaining a set of liquid developers for
plural-color electrophotography, it is desirable in the present
invention to fix the mixing ratio of a coloring agent to an organic
photoconductive substance in toner in the range of from 1 to 100
parts by weight of said agent against 100 parts by weight of said
substance. And concerning the coating agent it is preferable to
coat 1 part by weight of toner having a composition as described
above with 0.1 to 10 parts by weight of the coating agent.
EXAMPLE 4
A mixture, prepared by mixing-- Anthracene 3 kg, styrene 1 kg,
butyl acrylate 2 kg and benzoyl peroxide 10 g,
was heated at a temperature ranging from 90.degree.C to
100.degree.C in an atmosphere of nitrogen gas, thereby effecting
polymerization reaction. A mixture prepared by kneading upon adding
10g of phthalocyanine blue and 100 g of toluene to 100 g of the
products from said polymerization was subjected to spray-drying
with a spray-dryer, whereby, a cyan-color toner having a grain-size
of about 1.mu. was prepared.
On the other hand, in accordance with the foregoing method of
preparing a toner, a black-color toner, a yellow-color toner and a
magenta-color toner were respectively prepared by employing Spilon
Black, Benzidine Yellow GNN and Scarlet KR, respectively, in lueu
of the foregoing phthalocyanine blue. Subsequently, about 15g each
of these four color toners was separately dispersed in 1,000 ml
each of Naphtha No. 6, whereby a set of liquid developers for
plural-color electrophotography were prepared.
Further, by applying such combinations of materials as shown in the
following Table 4 and in accordance with the method of preparing
developers of the present example, two sets of liquid developers
for plural-color electrophotography were prepared.
Table 4 ______________________________________ Material for Toner
Devel- Photocon- Vinyl Reaction Coloring Carrier oper ductive
Compound Initiator Agent Liquid No. Substance
______________________________________ vinyl styrene Methylene
Naphtha anthracene (0.75 Blue No. 6 (3 kg) kg) Cyanine Naphtha
azobis- Black BX No. 6 1 Lauryl isobutylo- metha- nitrile Brilliant
crylate (10 g) Carmine Naphtha (1.25 6B No. 6 kg) Benzidine Yellow
Naphtha 471 No. 6 vinyl butyl Brilliant Naphtha anthracene metha-
Carmine No.6/ (3 kg) crylate 6B Solvesso (1 kg) 100 6/4 azobis-
Spilon Naphtha isobutylo- Black No.6/ nitrile Solvesso 2 metha-
(4.5 g) 100 6/4 crylic acid Spilon Naphtha (0.3 Yellow No.6/ kg)
Solvesso 100 6/4 Cyanine Naphtha Blue No.6/ Solvesso 100 6/4
______________________________________
It is noted in this connection that, in case where the toner for
each color in the present example was prepared without employing a
spray-dryer but prepared through the process comprising the steps
that the coloring agent was added and mixed with the products from
polymerization reaction, the solvent was removed thereafter, and
said polymerization-reaction products thus treated were pulverized,
the toner thus obtained was equal to that obtained through
spray-drying.
Each set of developers prepared as above was employed for
reproducing a plural-color image under the same operation as
described in Example 1, and, as a result, there was obtained a
satisfactory plural-color image from any and every set thereof.
EXAMPLE 5
A mixture consisting of-- orthochlorovinyl carbazole 1.5 kg, vinyl
toluene 0.5 kg, octylmethacrylate 1.0 kg, azobisisobutylonitrile
6.5 kg, dichlorobenzene 100 ml, Methylene Blue 14 g and buffer
solution (having the same 18 kg composition as in Example 1)
was caused to effect suspension polymerization through the same
polymerizing operation as in Example 4. Then, 20 g of a cyan-color
toner thus obtained was dispersed in 1,000 ml of Naphtha No. 6 as a
carrier liquid, whereby a cyan-color developer was obtained.
On the other hand, by employing coloring agents for black-color
(Spilon; Spirit Black), coloring agents for yellow-color (Benzidine
Yellow GNN; Benzidine Yellow 471) and coloring agents for
magenta-color (Fast Red; Benzidine Orange) respectively in lieu of
Methylene Blue among the foregoing materials for toner and in
accordance with the foregoing method of preparing a toner, a
black-color toner, a yellow-color toner and a magenta-color toner
were respectively prepared. Further, the respective toner was
separately dispersed in 1,000 ml of carrier liquid for each color,
whereby liquid developers for plural-color electrophotography were
obtained.
For the purpose of testing a performance of the liquid developer
according to the invention, a control liquid developer was prepared
in accordance with the same procedure as described above except
that 1.5 kg of zinc oxide powder was used in place of the
orthochlorovinyl carbazole referred to in the above preparation of
the liquid developer containing a cyan-color toner of the present
invention.
Comparative tests were carried out in accordance with the same
methods as described in tests-(1) and -(2) in Example 3. The test
results of the dispersion stability in the carrier liquid and the
fixing ability to a photoconductive layer of copying paper are
given respectively in Table-5 and Table-6.
In the comparative tests, the liquid developer containing
cyan-color toner according to our invention was employed for
comparison with the control liquid developer containing cyan-color
toner using zinc oxid.
Table 5 (Dispersion stability)
______________________________________ After 7 After one After
three days month months ______________________________________
Developer according to our invention 300 mm 300 mm 250 mm Control
developer 200 mm 75 mm 50 mm
______________________________________
Table 6 ______________________________________ Fixing Ability (%)
After 50 After 300 erasure erasure
______________________________________ Image formed with the
developer of our invention 90 70 Image formed with the control
developer 50 35 ______________________________________
As is clear from the results in Tables-5 and -6, the developer
according to our invention is recognized superior in both
dispersion stability and adhesiveness to photoconductive layer in
comparison with control developer using zinc oxide.
* * * * *