U.S. patent number 3,639,243 [Application Number 04/682,512] was granted by the patent office on 1972-02-01 for liquid developer electrophotography.
This patent grant is currently assigned to Kabushiki Kaisha Ricoh. Invention is credited to Hazime Machida, Zenjiro Okuno.
United States Patent |
3,639,243 |
Okuno , et al. |
February 1, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
LIQUID DEVELOPER ELECTROPHOTOGRAPHY
Abstract
A liquid developer for electrophotography, which is prepared by
dispersing, in a suitable carrier liquid, either independently or
together with a surface active agent, a toner which is obtained by
the so-called graft-copolymerization technique by a direct chemical
bonding between a pigment and unsaturated compounds having a
dispersing effect and a large electric charge polarity controlling
ability, or more specifically, unsaturated compounds capable of
chemically bonding to pigment, resulting in a large and distinct
electric charge polarity of said toner in the carrier liquid and
also capable of facilitating the dispersion of said particles in
said carrier liquid which consists of a paraffinic hydrocarbon
(including both isoparaffinic and paraffinic hydrocarbons) having a
relatively high-electric resistance and a low-dielectric
constant.
Inventors: |
Okuno; Zenjiro (Tokyo,
JA), Machida; Hazime (Tokyo, JA) |
Assignee: |
Kabushiki Kaisha Ricoh (Tokyo,
JA)
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Family
ID: |
26417249 |
Appl.
No.: |
04/682,512 |
Filed: |
November 13, 1967 |
Foreign Application Priority Data
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Nov 21, 1966 [JA] |
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41/76102 |
Nov 21, 1966 [JA] |
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41/76103 |
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Current U.S.
Class: |
430/114; 430/115;
523/205 |
Current CPC
Class: |
G03G
9/133 (20130101); C08F 2/44 (20130101) |
Current International
Class: |
C08F
2/44 (20060101); G03G 9/12 (20060101); G03G
9/13 (20060101); G03g 009/04 () |
Field of
Search: |
;252/62.1 ;117/37LX
;106/308 ;260/41 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
|
|
859,292 |
|
Jan 1961 |
|
GB |
|
937,971 |
|
Sep 1963 |
|
GB |
|
869,391 |
|
May 1961 |
|
GB |
|
859,292 |
|
Jan 1961 |
|
GB |
|
768,293 |
|
Feb 1957 |
|
GB |
|
723,584 |
|
Dec 1965 |
|
CA |
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Brammer; J. P.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A liquid developer for electrophotography, comprising a toner of
a single pigment having a n=ring in its chemical structure selected
from the group consisting of carbon black and aniline black and a
graft-polymer bonded to said benzenoid ring of said pigment by a
reaction of graft-copolymerization between one each of an
unsaturated compound expressed by formula (a), another unsaturated
compound expressed by formula (b) and said pigment:
wherein R.sub.1 is selected from the group consisting of --C.sub.n
H.sub.2n.sub.+ 1 wherein n= 1 to 3, a phenyl radical, a tosyl
radical, and H; Y is selected from the group consisting of (1)
--COOC.sub.n H.sub.2n.sub.+ 1 wherein 4.ltoreq.n.ltoreq. 20, (2)
--OCOC.sub.n H.sub.2n.sub.+ 1 wherein 1.ltoreq.n.ltoreq. 20, and
(3) --C.sub.n H.sub.2n.sub.+ 1, wherein 1.ltoreq.n20 (each
expression C.sub.n H.sub.2n.sub.+ 1 denoting an alkyl radical); X
is selected from the group consisting of
wherein n== 2 to 4 and R.sub.III are selected from the group
consisting of H, alkyl radicals having one to four carbon atoms, a
phenyl radical and a tosyl radical, (2) --COOH, (3) --OH, (4) --CN,
(5) --NH.sub.2,
wherein R is selected from the group consisting of H and an alkyl
radical of one to three carbon atoms,
wherein R is selected from the group consisting of H and an alkyl
radical of one to three carbon atoms; and a carrier liquid
consisting of a paraffinic hydrocarbon, said toner being dispersed
in said carrier liquid.
2. A liquid developer for electrophotography according to claim 1,
wherein said toner is dispersed in said carrier liquid together
with only a small amount of at least one surface active agent
selected from the group consisting of stearic acid, palmitic acid,
naphthenic acid and aluminum, cadmium, cobalt, nickel, manganese,
chromium and copper salts of an acid selected from the group
consisting of stearic acid, palmitic acid and naphthenic acid.
3. A liquid developer for electrophotography according to claim 1,
wherein said toner consists of a product of a
graft-copolymerization reaction between said pigment and a mixture
consisting of said unsaturated compound expressed by said formula
(a) and said another unsaturated compound expressed by said formula
(b), said mixture being of an (a) to (b) mol ratio wherein the
ratio of (b) is not in excess of 4 to 6 mols of (a).
4. A liquid developer for electrophotography according to claim 1,
wherein said toner consists of a product of a reaction obtained
from a mixture consisting of said unsaturated compound expressed by
said general formula (a) and said another unsaturated compound
expressed by said general formula (b), said mixture being added
with said pigment in an amount ranging from 25 to 50 percent by
weight of the total weight of said mixture.
5. The method of forming a liquid developer for electrophotography
according to claim 1, comprising forming a mixture of a member of
the group consisting of laurylmethacrylate and isoctylmethacrylate,
and a member of the group consisting of
.beta.-dimethylaminoethylmethacrylate, acrylonitrile, acrylic acid
and hydroxymethacrylate in the molal ratio of 6 mols of the former
to not more than 4 mols of the latter, adding a pigment from the
group consisting of aniline black and carbon black to the mixture
in the amount of 25 to 50 percent by weight of the total weight of
the mixture, a catalytic amount of polymerization initiator, and a
hydrocarbon solvent, heating the mixture in the range of about
100.degree. to 120.degree. C. for a sufficient time to obtain a
pigment graft-copolymer, milling said copolymer and dispersing the
milled copolymer in a hydrocarbon solvent.
Description
BACKGROUND OF THE INVENTION
The present invention is concerned with a liquid developer for use
in the wet-developing process of electrophotography.
Various liquid developers for electrophotography have been
proposed. These conventional developing agents, however, consist of
a pigment-dispersing agent, an electric charge polarity controlling
agent such as rosin, alkyd resin and asphalt, and a carrier liquid
consisting of a paraffinic hydrocarbon or the like which includes
isoparaffinic hydrocarbons and paraffinic hydrocarbons or the like.
Because these commonly used liquid developers employ, as the
dispersing and electric charge polarity controlling agents, natural
substances such as rosin and asphalt which are by nature not
uniform in quality, it has been difficult to prepare developers
which were uniform in their developing ability and quality. In
addition, the conventional developers had the shortcomings that the
dispersing ability of the particles of the developer deteriorated
to a great extent during a short period of time, and that repeated
use of the developer led to a marked attrition of the initial large
electric charge, and a marked based distinct polarity controlling
action which was exerted on the fine particles of pigment,
resulting in a small electric charge, in distinct polarity of the
fine particles of pigment. Furthermore, the deteriorated dispersing
ability of the particles of the developer caused these particles to
aggregate together and sediment, resulting in an extreme reduction
in the developing ability of the developer. These many defects of
the developers of the prior art may be explained as follows. Fine
particles of pigment retain their excellent dispersing ability as
well as their distinct polarity for some time after the developing
agent is made, because, during such period, a dispersing agent and
an electric charge controlling agent both remain sticking, with
relative firmness, to the fine particles of pigment, but these
agents which have for some time been adsorbed firmly to the fine
particles of pigment will gradually begin to detach from the
particles as time goes by.
SUMMARY OF THE INVENTION
The present invention relates to a liquid developer for
electrophotography, which is free from the aforesaid shortcomings
of a liquid developer of the prior art. More specifically, the
present invention contemplates the provision of a liquid developer
for electrophotography which is excellent in both developing
ability and stability, by first subjecting the two types of
unsaturated compounds expressed by the below-mentioned general
formulas (a) and (b) to graft-copolymerization with fine particles
of pigment, and then dispersing the resulting reaction product, as
particles, in a suitable carrier liquid for the liquid developer,
either independently or together with a surface active agent.
General formulas:
wherein R.sub.1 is selected from the group consisting radicals of
the formula --C.sub.n H.sub.2n.sub.+ 1 (an alkyl radical wherein n=
1-3), phenyl radicals, tosyl radicals and hydrogen; Y is the
radical --COOR.sub.II (wherein R.sub.II is selected from the group
consisting of radicals expressed by formulas --C.sub.n
H.sub.2n.sub.+ 1 (wherein 4.ltoreq.n.ltoreq.20), --OCOC.sub.n
H.sub.2n.sub.+ 1 (wherein 1.ltoreq.n.ltoreq.20)) and --C.sub.n
H.sub.2n.sub.+ 1 (an .alpha.-alkyl radical wherein
1.ltoreq.n.ltoreq.20); X is selected from the group consisting
of
(wherein n= 2-4, and R.sub.III is selected from the group
consisting of hydrogen, alkyl radicals having one to four carbon
atoms, phenyl radicals and tosyl radicals), --COOH, --OH, --CN,
--NH.sub.2, --CONR.sub.2 (wherein R is selected from the group
consisting of hydrogen and --C.sub.n H.sub.2n.sub.+ 1 (wherein
1.ltoreq.n3) and
from
(wherein B is selected from the group consisting of hydrogen and
C.sub.n H.sub.2n.sub.+ 1 (wherein 1.ltoreq.n.ltoreq.3))
The pigments which are used in the present invention preferably are
substances such as carbon black and aniline black CC.I. No. 50440)
which have a benzenoid ring in their chemical structures. The
functional radicals which are represented by Y in the aforesaid
general formula (a) of the unsaturated compounds are selected from
among those which effectively improve the dispersing ability of the
toner graft-copolymer in the hydrocarbon dispersion medium, and
which have an intensive chemical affinity to said dispersion
medium.
In the group of unsaturated compounds having the general formula
(b), on the other hand, those functional radicals which are
represented by X are selected from among those radicals that can
effectively control the polarity of the electric charge borne by
the particles of the liquid developer. The dispersing ability and
the stability of the particles of the liquid developer can be
improved further by the use of a product of reaction, namely, a
product obtained from a graft-copolymerization between particles of
pigment and a mixture of the two groups (a) and (b) of unsaturated
compounds said mixture being such as to have an (a) to (b) mol
ratio wherein the ratio of (b) is not in excess of 4 against 6 mols
of (a). With respect to the compounds of group (b) however, the use
of --COOR.sub.II as the functional radical which is represented by
Y, will extremely improve the dispersing ability as well as the
developing ability of the particles of the liquid developer.
In case the toner graft-copolymers consisting of fine particles of
pigment and a mixture of the aforesaid unsaturated compounds of the
(a) (a) and (b) are dispersed alone in dispersion media, said
toners, in many cases, will be impressed with a negative electric
charge. The present invention, however, further provides a liquid
developer such that the electric charge to be impressed on the
toner is controlled so as to be distinctly positive.
The surface active agents which are used in the present invention
consist of higher aliphatic acids such as stearic acid, palmitic
acid and naphthenic acid, and also metal soaps which are the salts
of the aforesaid higher aliphatic acids and metals selected from
the group consisting of aluminum, cadmium, cobalt, nickel,
manganese, chromium and copper. These surface active substances
have an ability, when placed in the developing liquid, to reverse
the polarity of the large electric charge impressed on the
particles of the developer to an extremely distinct positive charge
and also to hold the electric charge polarity controlling function
of the particles of the liquid developer stable for an extended
period of time.
As has been described, the present invention provides liquid
developers for electrophotography, which are uniform in quality and
which are of a predetermined uniform ability and whose electric
charge regulating agent and dispersing agent intended for the
pigments both consist of synthetic substances instead of using any
small amount of naturally occurring rosin or asphalt which have
been commonly used in a liquid developer of the prior art. Because
the fine particles of pigment are graft-copolymerized with the
large electric charge polarity controlling agent and also with the
dispersing agent, there is produced an extremely firm bonding
between these components, so that there is noted no appreciable
deterioration in the dispersing as well as the developing abilities
of the developing agent even after a repeated use of the latter
continuously for a prolonged period of time. In addition, the
liquid developer of the present invention which incorporates a
surface active agent allows the particles of the liquid developer
to be impressed with a very distinct electric charge polarity
controlling due to the action of the surface active agent, and
therefore, those copying materials which are developed by the use
of such liquid developer provide prints which carry
well-contrasted, clear images.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
To 0.9 mol of laurylmethacrylate was added 0.1 mol of
.beta.-dimethylaminoethylmethacrylate. Then, 25 percent by weight
of carbon black and 0.8 percent by weight of azobisisobutylonitrile
(polymerization initiator), both percentages relative to the total
weight of said mixture, and also toluene equal in amount to the
total weight of the aforesaid monomers were added to said mixture.
The resulting mixture was subjected to reaction at
100.degree.-110.degree. C. for 10 hours, with the result that a
carbon black graft-copolymer was obtained. This graft-copolymer was
then kneaded in a ball mill for 20 hours. One g. of this kneaded
graft-copolymer was dispersed in 500 cc. of an isoparaffinic
hydrocarbon (ISOPAR-H, a product of Esso Standard Oil, Inc.), and
thus, a liquid developer for electrophotography was obtained.
A positive original was placed on the photoconductive layer of an
electrophotographic copying material already impressed with a
negative electric charge by the application of corona discharge,
and after exposing to light, the copying material was developed by
the use of the aforesaid liquid developer of the present invention.
The result was that a very clear negative print of the image was
obtained. After repeated use of this liquid developer for an
extended period of time, there was noted no appreciable
deterioration in the developing ability of said liquid
developer.
EXAMPLE 2
To 0.9 mol of laurylmethacrylate was added 0.1 mol of
acrylonitrile. Then, 25 percent by weight of carbon black and 0.6
percent by weight of azobisisobutylonitrile, both percentages
relative to the total weight of said mixture, and also toluene in
an amount equal to half of the total weight of the aforesaid
monomers were added to said mixture. The resulting mixture was
subjected to reaction at 110.degree. C. for 15 hours, with the
result that a carbon black graft-copolymer was obtained. A small
amount of an isoparaffinic hydrocarbon (ISOPAR-H) was added to this
copolymer, followed by kneading in a ball mill for 20 hours. One g.
of the kneaded copolymer was dispersed in 500 cc. of an
isoparaffinic hydrocarbon identical to the aforesaid one, and thus
a liquid developer for electrophotography was obtained.
A positive original was placed on the photoconductive layer of an
electrophotography copying material already impressed with a
negative electric charge by the application of corona discharge,
and after exposure to light, the copying material was developed by
the use of the aforesaid liquid developer of the present invention.
The result was that a clear positive print of the image was
obtained. After repeated use of this liquid developer for an
extended period of time, no appreciable deterioration of the
developing ability was noted.
EXAMPLE 3
To 0.9 mol of laurylmethacrylate was added 0.05 mol of acrylic
acid. Then, 33 percent by weight of aniline black and 0.8 percent
by weight of azobisisobutylonitrile, both percentages relative to
the total weight of said mixture, and also toluene in an amount
equal to the total weight of the aforesaid monomers were added to
said mixture. The resulting mixture was subjected to reaction at
120.degree. C. for 10 hours, with the result that a graft-copolymer
was obtained. This graft-copolymer was kneaded in a ball mill for
16 hours. One g. of this kneaded copolymer was dispersed in 500 cc.
of an isoparaffinic hydrocarbon (ISOPAR-H), and thus, a liquid
developer for electrophotography was obtained.
After exposing to light electrophotography copying materials
already impressed with a negative electric charge by the
application of corona discharge, in a manner similar to that
described in examples 1 and 2, the copying materials were developed
by the use of the aforesaid liquid developer of the present
invention. The result was that very clear positive prints of the
image were obtained. After repeated use of this liquid developer
for an extended period of time, no appreciable deterioration of the
developing ability was noted.
EXAMPLE 4
To 0.95 mol of laurylmethacrylate was added 0.05 mol. of acrylic
acid. Then, 25 percent by weight of carbon black and 0.7-0.8
percent by weight of azobisisobutylonitrile (polymerization
initiator), both percentages relative to the total weight of said
mixture, and toluene equal in an amount to the total weight of the
aforesaid monomers were added to said mixture. The resulting
mixture was subjected to reaction at 70.degree. C. for 8 hours,
with the result that a carbon black graft-copolymer was obtained.
One g. of this copolymer was dispersed in 500 cc. of an
isoparaffinc hydrocarbon (ISOPAR-H), and furthermore, 2 cc. of 0.5
percent manganese naphthenate solution was added thereto, and thus
a liquid developer for electrophotography was obtained.
A positive original was placed on the photoconductive layer already
impressed with a negative electric charge, and after exposure to
actinic light, development was performed by the use of the
aforesaid liquid developer of the present invention. The result was
that a very clear positive print of the image was obtained. After
repeated use of the liquid developer for a prolonged period, no
reduction in the dispersing ability of the particles of the liquid
developer, nor any deterioration of the developing ability of the
liquid developer was noted.
EXAMPLE 5
To 0.9 mol of laurylmethacrylate was added 0.1 mol of
hydroxymethacrylate. Then, 33 percent by weight of carbon black and
0.7-0.8 percent by weight of azobisisobutylonitrile, both
percentages relative to the total weight of said mixture, and also
toluene in an amount equal to the total weight of the aforesaid
monomers were added to the mixture Thereafter, in a manner similar
to that described in example 4, a carbon black graft-copolymer was
obtained. One g. of this copolymer was dispersed in 500 cc. of an
isoparaffinic hydrocarbon (ISOPAR-H), and furthermore, 0.5 cc. of
0.5 percent cobalt naphthenate solution was added thereto, and
thus, a liquid developer for electrophotography was obtained. After
developing a copying material similar to that used in example 4 by
the use of the aforesaid liquid developer, a very clear positive
print of the image was obtained. After repeated use of this liquid
developer for a prolonged period, no reduction in the dispersing
ability of the particles of the developer nor any deterioration of
the developing ability was noted.
EXAMPLE 6
0.03 mol of .beta.-dimethylaminoethylmethacrylate was admixed with
0.97 mol of isooctylmethacrylate. Then, 50 percent by weight of
carbon black and 0.8 percent by weight of azobisisobutylonitrile,
both percentages relative to the total weight of said mixture, and
toluene in an amount equal to the total weight of the aforesaid
monomers were added to the mixture. Thereafter, in a manner similar
to that described in connection with example 4, a carbon black
graft-copolymer was obtained. One g. of this copolymer was
dispersed in 500 cc. of an isoparaffinic hydrocarbon (ISOPAR-H),
and furthermore, 3 cc. of 1 percent aluminum stearate solution was
added thereto, and thus, a liquid developer for electrophotography
was obtained. By developing a copying material similar to that in
example 4 with the aforesaid liquid developer, a very clear
positive print of the image was obtained. After repeated use of
this liquid developer for an extended period of time, no reduction
in the dispersing ability of the particles of the liquid developer
nor any deterioration of the developing ability of the liquid
developer was noted.
* * * * *