U.S. patent number 3,623,986 [Application Number 04/748,237] was granted by the patent office on 1971-11-30 for liquid developer for use in electrophotography.
This patent grant is currently assigned to Kabushiki Kaisha Ricoh. Invention is credited to Hazime Machida, Zenjiro Okuno.
United States Patent |
3,623,986 |
Machida , et al. |
November 30, 1971 |
LIQUID DEVELOPER FOR USE IN ELECTROPHOTOGRAPHY
Abstract
A liquid developer for use in electrophotography and being of
the type in which a toner is dispersed in a carrier liquid, said
carrier liquid consisting of an organic solvent having a high
electric resistance of at least 10.sup.10 .OMEGA.cm. and a low
dielectric constant of a maximum of 3, said toner being selected
from the group of toners of the following types (a),(b),(c) and
(d): A. Toners of the type in which pigment particles are coated,
by the kneading technique, with a homopolymer of a monomer selected
from the group consisting of polymeric monomers having an epoxy
radical (-0-) and polymeric monomers having a carbinol radical, B.
toners of the type that said homopolymer is graftcopolymerized to
said pigment particles, C. toners of the type in which the pigment
particles are coated, by the kneading technique, with a copolymer
in which is contained, by copolymerization, a monomer selected from
the aforesaid group of polymeric monomers, and D. toners of the
type in which said copolymer is graftcopolymerized to the pigment
particles.
Inventors: |
Machida; Hazime (Tokyo,
JA), Okuno; Zenjiro (Tokyo, JA) |
Assignee: |
Kabushiki Kaisha Ricoh (Tokyo,
JA)
|
Family
ID: |
12840856 |
Appl.
No.: |
04/748,237 |
Filed: |
July 29, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Aug 4, 1967 [JA] |
|
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42/49787 |
|
Current U.S.
Class: |
430/114; 430/115;
523/205; 430/904 |
Current CPC
Class: |
G03G
9/133 (20130101); C08F 292/00 (20130101); Y10S
430/105 (20130101) |
Current International
Class: |
C08F
292/00 (20060101); G03G 9/12 (20060101); G03G
9/13 (20060101); G03g 009/04 () |
Field of
Search: |
;252/62.1 ;260/33.6
;117/37LX |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lesmes; George F.
Assistant Examiner: Brammer; J. P.
Claims
What is claimed is:
1. A liquid developer for use in electrophotography consisting
essentially of a liquid hydrocarbon having a high electric
resistance of at least 10.sup.10 .OMEGA.cm and a low dielectric
constant of a maximum of 3 and a toner dispersed in said liquid
hydrocarbon, said toner consisting essentially of particles of a
pigment selected from the group consisting of Carbon Black (C.I.
No. 77,266) and Spirit Black (C.I. No. 50,440) and a coating-layer
coated on said particles, said coating-layer consisting essentially
of a polymer selected from the group consisting of:
a. homopolymers of a monomer selected from the group consisting of
glycidyl methacrylate, 2,3-epoxypropyl acrylate,
allyl-2,3-epoxypropyl maleate, allyl-2,3-epoxybutyrate,
hydroxyethyl methacrylate, allylalcohol,
2-ethyl-2-hydroxylethylaminoethyl acrylate, diethyl-vinylethynyl
carbinol, .beta.-hydroxylbutyl acrylate, methyl-phenyl-vinylethynyl
carbinol, methyl-ethyl-vinylethynyl carbinol,
n-dipropyl-vinylethynyl carbinol and n-propyl-vinylethynyl
carbinol; and
b. copolymers of at least 15 mol percent of a monomer selected from
said group of monomers named in (a) and the balance consisting of
at least one monomer selected from the group consisting of butyl
methacrylate, lauryl methacrylate, styrene, aminostyrene,
hydroxystyrene, chlorostyrene, methylstyrene, acrylamide,
dibutylacryl-amide, dimethylacrylamide, .alpha.-methyl-acrylamide,
2-n-butylbutadiene, 1,3-cyclohexadiene, 2-n-amylbutadiene-1,3,
anhydrous maleic acid, crotonic acid, acrylonitrile and
.alpha.-ethyl acrylonitrile.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is concerned with a liquid developer for use
in electrophotography and of the type in which a toner is dispersed
in a carrier liquid and the toner has a positive charge, said
carrier liquid consisting of an organic solvent having a relatively
high electric resistance and a low dielectric constant, said toner
comprising pigment particles and a polymer selected from the group
consisting of homopolymers obtained from the polymerization of
monomers having specific radicals and the group consisting of
copolymers obtained from the copolymerization of those monomers
having specific radicals and other types of monomers, said polymer
being either graft copolymerized to or coated on said pigment
particles.
2. Description of the Prior Art
Liquid developers for use in electrophotography are, in general,
prepared by kneading a mixture of pigment particles, a polarity
regulating agent, a dispersing agent and a fixing agent, and
dispersing the kneaded mixture in a solvent consisting of a
paraffinic or an isoparaffinic hydrocarbon. More specifically, it
has been an indispensible requirement of the liquid developers of
the prior art that the pigment particles which constitute the basic
material of the toner are coated with the aforesaid various agents,
i.e., a polarity regulating agent which is adapted to impress the
toner with a distinct positive or negative electric charge to cause
the deposition, by electrophoresis, of the toner onto the area of
the electrostatic latent image which is formed on the
photoconductive layer of the electrophotographic copying material,
a fixing agent which is adapted to insure the adhesion of the toner
on the surface of said photoconductive layer, and a dispersing
agent which is adapted to have the toner stably dispersed in the
carrier liquid. It has been the practice to use, as the polarity
regulating agents and the fixing agents, those materials such as
naturally occurring rosin, asphalt, synthetic resins and lauryl
methacrylate-dimethylaminoethyl methacrylate copolymers, and also
to use, jointly with the aforesaid materials, surface active
agents, such as metal soap, in order to impart a distinct polarity
to the toner and to improve the dispersibility of the toner in the
carrier liquid. It is also known to affect the regulation of the
polarity of the toners by the combined use of two or more kinds of
pigments. In spite of the past efforts which have been paid to
improve the ability of the toners as desired, however, the
following drawback of the toners has not been successfully solved
to date.
Specifically, the aforesaid drawback of the toners was represented
by the fact that, when the liquid developers of the prior art were
stored for an extended period of time or when the same liquid
developers were used repeatedly, it occurred that the polarity
(meaning the positive or negative electric charge) of the toners
became indistinct so as to result in a deterioration of the
developing ability of the toners. The evidence of the deterioration
of the developing ability of the toners was detected by observing
the lowered concentration of the toner in the liquid developer due
to the repeated use thereof and caused by the elevated
concentration of the additional agents such as the surface active
agent in the liquid developer, and in some cases, the deterioration
was detected by observing the sedimentation of the particles of the
toner in the bottom of the layer of the liquid. When the liquid
developer is converted to either one of the aforesaid conditions,
not only will the copied image which is formed on the surface of
the photoconductive layer of the electrophotographic copying
material lose clarity, but also there will occur a dark solid
background on the copying material and an insufficient fixation of
the toner, and the copy will not meet the practical
requirements.
As has been described above, it has been extremely difficult for
the liquid developers of the prior art to retain, for an extended
period of time, the initial satisfactory developing ability which
was possessed by them at the time they were prepared.
SUMMARY OF THE INVENTION
It is, therefore, the object of the present invention to provide a
liquid developer for use in electrophotography which has overcome
the aforesaid drawbacks of the liquid developers of the prior art
and which, above all, is extremely stable and does not cause any
deterioration of the developing ability during its repeated
use.
We have discovered the following facts that, when a toner which is
prepared either (1) by conducting the graft copolymerization of a
homopolymer of a polymeric monomer having an epoxy radical or a
carbinol radical or the graft copolymerization of a copolymer which
contains the aforesaid polymeric monomer to pigment particles, or
(2) by coating the pigment particles with said polymeric monomer or
with said copolymer by kneading the mixture of said pigment
particles and said polymeric monomer or said copolymer, is
dispersed in a carrier liquid consisting of a hydrocarbon, the
resulting toner will bear a distinct positive electric charge, that
the resulting toner exhibits a satisfactory dispersibility and a
satisfactory developing ability without the combined use of other
additives, and further that these desirable properties of the toner
do not deteriorate after the storage of the liquid developer
containing said toner for an extended period of time and during the
repeated use of such a liquid developer. It has been found also by
us that the liquid developer containing the aforesaid graft
copolymerized toner and the liquid developer containing the
aforesaid coated toner both possess a substantially equal
developing ability.
The present invention has been worked out based on the aforesaid
knowledge.
The carrier liquid which is used with the toner in the present
invention can be the carrier liquids which have been employed in
general in electrophotography. It is to be noted, however, that,
since the polarity regulating agents (resins) and the other
additives which were used in the liquid developers of the prior art
were selected, with preference, from among those having a low
solubility in the carrier liquids, it is desirable, in the present
invention, to use those polymeric monomers having an epoxy radical
or a carbinol radical, in the form of a copolymer containing such a
substance as lauryl methacrylate as the counterpart constituent of
the copolymer. Those toners which are prepared either by graft
copolymerizing the aforesaid copolymers to pigment particles or by
coating the pigment particles with such copolymers by kneading the
mixture of the pigment particles and the copolymers, exhibit a much
better dispersibility in the aforesaid carrier liquids, as compared
with the dispersibility which is exhibited by the toners prepared
either by graft-copolymerizing homopolymers to pigment particles or
by coating the pigment particles with homopolymers by kneading the
mixture of these two constituent materials.
As the polymeric monomers having an epoxy radical which are
applicable to the present invention, those monomers such as
glycidyl methacrylate, 2,3-epoxypropyl acrylate,
allyl-2,3-epoxypropyl maleate, and allyl-2,3-epoxybutyrate are
suitable. Also, as the polymeric monomers having a carbinol radical
which are applicable to the present invention, those monomers such
as hydroxyethyl methacrylate, allylalcohol,
2-ethyl-2-hydroxylethyl-aminoethyl acrylate, diethyl-vinylethynyl
carbinol, .beta.-hydroxylbutyl acrylate, methyl-phenyl-vinylethynyl
carbinol, methyl-ethyl-vinylethynyl carbinol,
n-dipropyl-vinylethynyl carbinol and n-propyl-vinylethynyl carbinol
are suitable. Furthermore, as the monomers which are copolymerized
with one of the aforesaid polymeric monomers, those monomers
including alkyl methacrylate such as butyl methacrylate and lauryl
methacrylate, styrene, styrene derivatives such as aminostyrene,
hydroxystyrene, chlorostyrene and methylstyrene; acrylamide,
acrylamide derivatives and acrylic acid derivatives such as
dibutylacrylamide, dimethyl-acrylamide and
.alpha.-methyl-acrylamide; diene derivatives such as
2-n-butylbutadiene, 1,3-cyclohexadiene and 2-n-amylbutadiene-1,3,
dibasic acid such as anhydrous maleic acid and crotonic acid; and
acrylonitrile derivatives and methacrylonitrile derivatives such as
acrylonitrile and .alpha.-ethylacrylonitrile, are suitable.
In case a copolymer of the aforesaid type is used with the pigment
particles, the object of the present invention will be attained by
the employment of a two or more component copolymer in which is
contained a polymeric monomer having the aforesaid specific radical
in amount at least 15 percent by mole, as will be understood
clearly from the embodiments of the present invention which will be
described later.
As has been described, the present invention contemplates the
provision of a liquid developer for use in electrophotography which
is of an extremely simple structure such that a toner which is
comprised of a combination of only pigment particles and a polymer
is dispersed in a carrier liquid. It is to be noted, however, that,
in spite of such a simple structure of the liquid developer, the
toner bears a very distinct polarity and also that it has a
satisfactory dispersibility in the carrier liquid and that,
accordingly, when the liquid developer of the present invention is
used in the developing process, the copied images obtained are
satisfactory in both the clarity and the fixation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
To 0.2 mole of glycidyl methacrylate, 0.2 mole of butyl
methacrylate, 0.41 mole of styrene and 0.3 mole of lauryl
methacrylate was added 0.005 mole of azobisisobutyronitrile, and
there further was added 1 mole of toluene. The resulting mixture
was allowed to react in a nitrogen atmosphere at 90.degree. C. for
9 hours, and thus, a highly viscous copolymer was prepared. To 7
parts by weight of said copolymer were added 1 part by weight of
carbon-black (produced under the trade name of Asahi XC-550, by
Asahi Carbon, Ltd. of Japan) and 32 parts by weight of Naphtha No.
6 (trade name of a petroleum hydrocarbon, i.e., an aliphatic
hydrocarbon solvent containing 25 weight percent aromatics, flash
point 40.degree. C., specific gravity 0.789, produced by ESSO
Standard Oil Company of U.S.A.). The resulting mixture was kneaded
in a ball mill for 8 hours, and as a result, a highly concentrated
toner was prepared. Four grams of the concentrated toner thus
obtained was introduced in 1 liter of Isopar H (trade name of an
isoparaffinic hydrocarbon, flash point 123.degree. F.,
Kauri-Butanol value 27, specific gravity 0.7571, produced by ESSO
Standard Oil Company of U.S.A.). Thus, a liquid developer for use
in electrophotography of the type in which the toner consisted of
the pigment particles coated with the aforesaid copolymer and
having a polarity regulated to the positive charge was dispersed in
the carrier liquid was obtained.
Using a commercially available electrophotographic copying
material, an electrostatic latent image was given, this copying
material according to a known technique, and then the resulting
copying material was developed by immersing the latter in the
liquid developer of the present invention. The result was that a
very clear positive copied image was formed. Also, the liquid
developer of the present invention was left to stand for more than
6 months and furthermore, the liquid developer thus obtained was
subjected to repeated use for such an extended period of time.
However, neither of these liquid developers of the present
invention showed any appreciable deterioration of their developing
abilities.
EXAMPLE 2
To 7 parts by weight of a monomer-constituting liquid consisting
of:
styrene 0.2 mole lauryl methacrylate 0.2 mole hydroxyethyl
methacrylate 0.3 mole azobisisobutyronitrile 0.005 mole toluene 1.0
mole
was added 1 part by weight of carbon-black (produced under the
trade name of Statexdeness by Columbian Carbon Company of U.S.A.).
In a manner similar to that described in example 1, the resulting
mixture was allowed to react, and thus, a graft-copolymeric toner
wherein the copolymer is united with the pigment particles was
prepared. To 1 part by weight of this toner was added 4 parts by
weight of Naphtha No. 6, and the resulting mixture was kneaded in a
ball mill for 8 hours to disperse the components thoroughly
relative to each other. As a result, a highly concentrated toner
was obtained. Four grams of this concentrated toner was dispersed
in 1 liter of Naphtha No. 6, and thus a liquid developer for use in
electrophotography wherein the polarity of the toner was regulated
to the positive charge was obtained. Using this liquid developer,
an electrophotographic copying material which had been given an
electrostatic latent image by a known technique was developed. The
result was that a very clear positive copied image was formed. This
liquid developer was left to stand or subjected to repeated use for
a period of more than 6 months, but it showed no appreciable
deterioration of its developing ability in each of these tests.
EXAMPLE 3
A copolymer was prepared, in a manner similar to that described in
example 1, by the use of the copolymer-constituting liquid having
the following composition:
lauryl methacrylate 1.0 mole hydroxyethyl methacrylate 0.6 mole
azobisisobutyronitrile 0.005 mole toluene 1.0 mole
By blending this copolymer with carbon-black (produced under the
trade name of Mitsubishi No. 44, by Mitsubishi Chemical Industries,
Ltd. of Japan) and also with Naphtha No. 6, the resulting mixture
was kneaded thoroughly in a ball mill. Thus, a highly concentrated
toner was prepared. Four grams of this concentrated toner was
dispersed in 1 liter of Naphtha No. 6, and as a result, a liquid
developer for use in electrophotography wherein the polarity of the
toner was regulated to the positive charge was obtained. The liquid
developer thus obtained was applied to the development of the
electrophotographic copying material which was similar to that
described in example 1. The result was that a very clear positive
copied image was formed. The liquid developer thus obtained was
left to stand or subjected to repeated use for a period of more
than 4 months, but no appreciable deterioration of the developing
ability was noted in each of these tests.
EXAMPLE 4
A copolymer was prepared, in a manner similar to that described in
example 1, by the use of a copolymer-constituting liquid having the
following composition:
lauryl methacrylate 0.6 mole allyl alcohol 0.4 mole toluene 1.0
mole azobisisobutyronitrile 0.005 mole
7 parts by weight of this copolymer, 1 part by weight of Spirit
Black (a product of Orient Chemical Industries, Ltd. of Japan) and
32 parts by weight of Isopar H were kneaded together in a ball mill
for 8 hours, and thus, a highly concentrated toner was prepared.
Four grams of this concentrated toner was dispersed in 1 liter of
Isopar H, and as a result, a liquid developer for use in
electrophotography was obtained. The liquid developer thus obtained
was applied to the development of an electrophotographic copying
material similar to that described in example 1. The result was
that a very clear positive copied image was formed. This liquid
developer was left to stand or subjected to repeated use for a
period of more than 4 months, but no deterioration of the
developing ability was noted in each of these tests.
* * * * *