Process of producing nonaqueous resin dispersion and liquid developer for electrostatic photography

A process of producing a nonaqueous resin dispersion, particularly useful for a liquid developer in electrostatic photographic, which comprises subjecting to photopolymerization a system containing at least a monomer (A) having one polymerizable double bond, which is soluble in a nonaqueous solvent but becomes insoluble upon polymerization thereof, and at least a dispersion stabilizing resin (P) which is a polymer having a weight average molecular weight of from 1.times.10.sup.4 to 1.times.10.sup.6 and containing a specific repeating unit represented by formula (I) in an amount of at least 50% by weight based on the weight of the polymer and has a specific functional group represented by formula (II) bonded to the side chain of the polymer and/or only one terminal of the main chain of the polymer, the photopolymerization reaction being carried out in the nonaqueous solvent by irradiating the system with ultraviolet rays having a wavelength of not longer than 400 n.m.: ##STR1##

FIELD OF THE INVENTION 
The present invention relates to a process of producing a nonaqueous resin 
dispersion useful for a liquid developer for electrostatic photography, a 
printing ink, a coating material, etc., and to a liquid developer for 
electrostatic photography prepared using the nonaqueous resin dispersion. 
BACKGROUND OF THE INVENTION 
Nonaqueous dispersed resin particles being used as a liquid developer for 
electrostatic photography, a printing ink, a coating material, etc., are 
the particles of a resin capable of fixing the coexisting pigment or dye 
as a film thereof and are required to be fine particles and stably 
dispersed. In particular, since the resin particles dispersed in a 
nonaqueous solvent having a high electric resistant give influences on 
image qualities of the developed images, the dispersed resin particles are 
required to have a good dispersibility. 
As a process of producing the nonaqueous dispersed resin particles, a 
so-called nonaqueous dispersion polymerization reaction wherein a monomer 
which is soluble in a nonaqueous dispersing solvent and becomes insoluble 
upon polymerization is granulated by a polymerization reaction in the 
nonaqueous dispersing solvent and in the presence of a dispersion 
stabilizing resin soluble in the solvent to provide a nonaqueous resin 
dispersion containing the particles, is known and various processes are 
proposed, for example, in K. E. J. Barrett, Dispersion Polymerization in 
Organic Dedia, published by John Wiley & Sons, 1975; Sooichi Muroi, Cho 
Biryushi Polymer no Saisentan Gijutu (Highest Technology of Super Fine 
Particle Polymer), Chapter 2, published by C M C K.K., 1991; etc. 
According to the nonaqueous dispersion polymerization reaction, the 
improvement of productivity such as saving of energy consumption, 
simplification of steps involved, etc., is attained and a particle 
dispersion having preferred characteristics such as fine particle sizes 
and a narrow particle distribution can be obtained as compared to a 
so-called mechanical process through kneading, grinding, and wet 
dispersion steps. 
However, when bonding of the soluble dispersion stabilizing resin and the 
insoluble dispersed resin particles is insufficient, the dispersion 
stabilizing resin tends to diffuse in the solution, whereby the dispersion 
stabilizing resin is released from the resin particles after storage or 
repeated use of the resin particle dispersion for a long period of time, 
causing precipitation, aggregation, and using such dispersed resin 
particles for a liquid developer, since the resin particles once 
aggregated and accumulated are reluctant to redisperse, the particles 
attach to everywhere of a developing machine, which results in staining of 
images and machine troubles of the developing machine such as clogging of 
a liquid-sending pump, etc. 
For overcoming these defects, a means of chemically bonding the soluble 
dispersion stabilizing resin and insoluble latex particles is proposed as 
disclosed in U.S. Pat. No. 3,990,980. 
That is, according to the disclosed process, dodecyl methacrylate is 
copolymerized with glycidyl methacrylate having a polymerizable double 
bond group to synthesize a random copolymer soluble in a nonaqueous 
solvent, esterifying the random copolymer by a high-molecular reaction 
with methacrylic acid to provide a dispersion stabilizing resin having 
introduced therein a methacryloyloxy group, and subjecting the dispersion 
stabilizing resin to a polymerizing gradulation reaction. 
However, in a liquid developer using the dispersed resin particles thus 
obtained by the foregoing process, the dispersion stability to the 
spontaneous precipitation of the dispersed resin particles is improved to 
some extent but the improvement is yet insufficient. When the liquid 
developer containing the dispersed resin particles is used for a 
developing apparatus, there is a problem that the liquid developer is 
insufficient in redispersion stability to put in practical use, such that 
the toners (dispersed resin particles) attached to each part of the 
developing apparatus are solidified in the form of film, which is not 
liable to redisperse and further causes machine troubles, staining of copy 
images, etc. 
Also, in the production process of resin particles described in the 
foregoing U.S. patent, for producing monodisperse particles having a 
narrow particle distribution, there is a great restriction on the 
combination of a dispersion stabilizing resin being used and a monomer 
being insolubilized, and in general, resin particles having a wide 
particle distribution containing a large amount of coarse particles or 
polydisperse resin particles having at least 2 mean particle sizes are 
formed. Also, in the production process, it is difficult to obtain 
monodisperse resin particles having a narrow particle distribution and a 
desired mean particle size, and large resin particles having particle 
sizes of at least 1 .mu.m and very fine resin particles having particle 
sizes of smaller than 0.1 .mu.m are formed. Furthermore, in the foregoing 
production process, there is a problem that the dispersion stabilizing 
resin being used must be produced by a complicated production process 
requiring a long period of time. 
For solving these problems, a process of using the dispersion stabilizing 
resin obtained by a process wherein in the polymer as described above, the 
polymerizable double bond group being bonded to the polymer of the 
dispersion stabilizing resin is bonded parting from the polymer main chain 
with at least 10 total atoms such that the copolymerization reactivity 
with the monomer which becomes the dispersed resin particles by being 
solubilized is not sterically hindered (e.g., U.S. Pat. No. 4,618,557 and 
JP-A-60-185962 ("JP-A" as used herein means an "unexamined published 
Japanese patent application")), a process of introducing the polymerizable 
double bond group to one end only of the polymer main chain of the soluble 
polymer (e.g., JP-A-1-282566), etc., is disclosed. 
As described above, it is important that in the nonaqueous dispersed resin 
particles having a good dispersion stability, the dispersion stabilizing 
resin is efficiently bonded to the component becoming an insoluble resin 
by causing a reaction in the polymerizing granulation reaction such that 
they are not separated even in a severe using condition. 
In the conventional known process as described above, the polymerizing 
granulation of a dispersion stabilizing resin and a monomer is carried out 
by adding thereto a polymerization initiator in a nonaqueous solvent. 
For example, in the case of a radical polymerization reaction using an 
azobis compound, a peroxide compound, etc., as is known, since the 
stability of the initiation radical and the growth radical is low, the 
elemental reactions (e.g., recombination, chain transfer, stop, hydrogen 
abstraction, etc.) of a polymer proceed complicatedly, which results in 
making it difficult to attain efficient bonding of a resin component for a 
dispersion stability and an insolubilized resin component or forming 
gelled materials by the progress of a polymerization reaction. 
Also, in an ionic polymerization reaction using a ionic polymerization 
initiator such as an alkyl metal compound, a Lewis acid, a Grignard 
reagent, etc., since the initiator and a growth living polymer react with 
an active hydrogen compound such as water, etc., to lose the initiating 
faculty, there is a problem that a severe purification of a solvent, 
monomers, etc., is required or the kind of the monomer forming resin 
particles is restricted. 
SUMMARY OF THE INVENTION 
The present invention has been made for solving the foregoing problems 
involved in the conventional nonaqueous resin dispersions. 
An object of the present invention is, therefore, to provide a novel 
process of producing a nonaqueous resin dispersion. 
Another object of the present invention is to provide a novel process of 
producing a nonaqueous resin dispersion excellent in a grafting efficiency 
of a dispersion stabilizing resin. 
Still another object of the present invention is to provide a novel 
production process of obtaining fine resin particles excellent in the 
dispersion stability and the redispersion stability and having a narrow 
particle size distribution. 
A further object of the present invention is to provide a liquid developer 
for electrostatic photography excellent in redispersion characteristics 
obtained by the foregoing dispersed resin particles. 
It has now been discovered that the above objects can be attained by the 
present invention as set forth hereinbelow. 
That is, according to an aspect of the present invention, there is provided 
a process of producing a nonaqueous resin dispersion, which comprises 
subjecting to photopolymerization a system containing at least a monomer 
(A) having one polymerizable double bond, which is soluble in a nonaqueous 
solvent but becomes insoluble upon polymerization thereof, and at least a 
dispersion stabilizing resin (P) which is a polymer having a weight 
average molecular weight of from 1.times.10.sup.4 to 1.times.10.sup.6 and 
containing a repeating unit represented by formula (I) in an amount of at 
least 50% by weight based on the weight of the polymer and has a 
functional group represented by formula (II) bonded to the side chain of 
the polymer and/or only one terminal of the main chain of the polymer, 
said photopolymerization reaction being carried out in the nonaqueous 
solvent by irradiating the system with ultraviolet rays having a 
wavelength of not longer than 400 n.m.: 
##STR2## 
wherein V.sup.0 represents --COO--, --OCO--, --(CH.sub.2).sub.r COO--, 
--(CH.sub.2).sub.r OCO--, --O--, --CONHCOO--, --CONHCONH--, --COND.sup.11 
--, SO.sub.2 ND.sup.11 --, or a phenylene group (wherein D.sup.11 
represents a hydrogen atom or a hydrocarbon group having from 1 to 22 
carbon atoms and r represents an integer of from 1 to 4); a.sup.1 and 
a.sup.2 which may be the same or different, each represents a hydrogen 
atom, a halogen atom, a cyano group, a hydrocarbon group, --COO--D.sup.12, 
or --COO--D.sup.12 through a hydrocarbon group (wherein D.sup.12 
represents a hydrocarbon group which may be substituted); and R.sup.0 
represents an aliphatic group having from 8 to 32 carbon atoms: 
##STR3## 
wherein Z.sup.0 represents --O--R.sup.1 or --NR.sup.2 (R.sup.3) (wherein 
R.sup.1 represents a monovalent organic residue the atom of which adjacent 
to the oxygen atom is a carbon atom and R.sup.2 and R.sup.3, which may be 
the same or different, each represents a hydrogen atom or the monovalent 
organic residue same as R.sup.1, with a proviso that R.sup.2 and R.sup.3 
are not simultaneously a hydrogen atom. 
According to a preferred embodiment of the process of producing a 
nonaqueous resin dispersion described above, the dispersion stabilizing 
resin (P) further contains as a copolymerization component at least one 
kind of monofunctional macromonomers (M) each having a weight average 
molecular weight of from 1.times.10.sup.3 to 2.times.10.sup.4 and having a 
polymerizable double bond group represented by formula (III) bonded to 
only one terminal of the main chain of the polymer having at least the 
repeating unit shown by formula (I) described above: 
##STR4## 
wherein b.sup.1, b.sup.2, and V.sup.1 have the same meanings as a.sup.1, 
a.sup.2, and V.sup.0 in formula (I) described above, respectively. 
According to another aspect of the present invention, there is provided a 
liquid developer for electrostatic photography composed of at least resin 
particles dispersed in a nonaqueous solvent having an electric resistance 
of at least 1.times.10.sup.9 .OMEGA..multidot.cm and a dielectric constant 
of not higher than 3.5, wherein said resin particles are the nonaqueous 
resin dispersion obtained by the production process described above.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention is a novel process of producing a nonaqueous resin 
dispersion wherein a resin particle dispersion is produced by carrying out 
a photopolymerization reaction in the coexistence of (i) at least one kind 
of the dispersion stabilizing resin (P) having the functional group shown 
by formula (II) described above and containing the repeating unit shown by 
formula (I) described above, and (ii) the monomer (A) having one 
polymerizable double bond group, which is soluble in a nonaqueous solvent 
but is insoluble when polymerized, in the nonaqueous solvent while 
initiating the photopolymerization by irradiation of ultraviolet rays 
having a wavelength of not longer than 400 n.m., and also is a liquid 
developer for electrostatic photography using the resin dispersion. 
The production process of the present invention is different from a 
conventional nonaqueous dispersion polymerization process involving 
polymerization using a polymerization initiator and has the feature 
residing in obtaining dispersed resin particles by a living radial 
polymerization reaction with the irradiation of ultraviolet rays using the 
resin (P) which is capable of stabilizing the dispersion of nonaqueous 
dispersed resin particles and initiating polymerization. The reaction 
proceeds according to a light-inferter process as described in, for 
example, Takashi Otsu et al., Makromol. Chem., Rapid. Commun., 3, 
133(1982), the reaction scheme of which is shown below: 
##STR5## 
As described above, in the reaction of the present invention, the 
polymerization is initiated at the resin (P) which is the dispersion 
stabilizing resin, the polymerization growing reaction proceeds livingly 
i.e., the reaction proceeds with a produced polymer having an active site 
(radical) at the terminal thereof for a relatingly long time, and the 
reaction is terminated merely by stopping the irradiation of ultraviolet 
rays. 
Also, the terminal group of the polymer in the reaction of the present 
invention is chemically utterly inert to other visible rays than 
ultraviolet rays or in a natural passage of time, and the stability of the 
polymer being used in this invention is good. Accordingly, the dispersed 
resin particles in the resin dispersion of the present invention are the 
polymer of a block copolymer wherein the part of the dispersion 
stabilizing resin component having an affinity with the nonaqueous solvent 
is almost quantitatively chemically bonded to the part of the insoluble 
resin component having a non-affinity with the nonaqueous solvent and show 
a high dispersion stability which has never been attained in conventional 
techniques. In particular, it has been found that when the dispersed resin 
particles are used as a liquid developer for electrostatic photography for 
reproducing precise images and being used under a severe condition, the 
liquid developer shows a very good performance. 
As the carrier liquid (nonaqueous solvent) having an electric resistance of 
at least 10.sup.9 .OMEGA..multidot.cm and a dielectric constant of not 
higher than 3.5, straight chain or branched aliphatic hydrocarbons, 
alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted 
products of them are preferably used. 
Specific examples thereof are octane, isooctane, decane, isodecane, 
decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, 
cyclodecane, ligroine, kerosine, benzene, toluene, xylene, mesitylene, 
Isopar E, Isopar G, Isopar H, Isopar L (Isopar: trade name of Exxon 
Research and Engineering Company), Shellsol 70, Shellsol 71 (Shellsol: 
trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco: trade 
name of American Mineral Spirits Co.), etc. 
These solvents can be used singly or as a mixture thereof. 
Also, the foregoing solvent can be used together with other polar organic 
solvent. Examples of such a polar organic solvent are alcohols (e.g., 
methanol, ethanol, isopropanol, butanol, and fluorinated alcohols), ethers 
(e.g., dipropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 
ethylene glycol dimethyl ether, and propylene glycol dimethyl ether), 
ketones (e.g., acetone, methyl ethyl ketone, methyl butyl ketone, methyl 
propyl ketone, diethyl ketone, and cyclohexanone), carboxylic acid esters 
(e.g., methyl acetate, ethyl acetate, ethyl formate, propyl acetate, butyl 
acetate, methyl propionate, ethyl propionate, and methyl benzoate), and 
halogenated hydrocarbons (e.g., methylene dichloride, chloroform, 
methylchloroform, carbon tetrachloride, and dichloroethane), although the 
solvent being used in the present invention is not limited thereby. 
The polar organic solvent may be added in an amount of 80% by weight or 
less, preferably 50% by weight or less, more preferably 30% by weight or 
less, based on the total weight of the carrier liquid, provided that the 
electric resistance of the resulting carrier liquid should not be less 
than 10.sup.9 .OMEGA.cm. 
In the present invention, a desired organic solvent system can be obtained 
from the dispersion medium containing the foregoing polar organic solvent 
being used as a mixture of the nonaqueous solvent, by distilling off the 
polar organic solvent by heating or under a reduced pressure after the 
polymerization granulation, or by carrying out a solvent exchange. 
In particular, when the dispersed resin particles produced by the process 
of the present invention are used as the dispersed resin particles of a 
liquid developer for electrostatic photography of the present invention, 
even when the foregoing polar organic solvent is contained in the liquid 
developer as the nonaqueous resin particle dispersion, there is no problem 
if the resistance of the carrier liquid is in the range of at least 
1.times.10.sup.9 .OMEGA..multidot.cm. 
Usually, in the step of producing the resin dispersion, it is preferred to 
use the solvent same as the carrier liquid for the liquid developer and as 
such a solvent, there are straight chain or branched aliphatic 
hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon, and 
halogenated hydrocarbons described above. 
As the monomer (A) having one polymerizable double bond group (hereinafter, 
referred to as the monofunctional monomer (A)) being used in the present 
invention, any monofunctional monomer which is soluble in the nonaqueous 
solvent but is insolubilized by being polymerized can be used. 
Practically, there are, for example, monomers represented by formula (IV) 
##STR6## 
wherein T.sup.1 represents --COO--, --OCO--, --CH.sub.2 OCO--, --CH.sub.2 
COO--, --O--, --CONHCOO--, --CONHOCO--, --SO.sub.2 --, --CON(W.sup.1)--, 
--SO.sub.2 N(W.sup.1)--, or a phenylene group (hereinafter, a phenylene 
group is referred to as --Ph--) (wherein W.sup.1 represents a hydrogen 
atom or an aliphatic group having from 1 to 8 carbon atoms, which may be 
substituted, e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 
2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, benzyl, chlorobenzyl, 
methylbenzyl, methoxybenzyl, phenethyl, 3-phenylpropyl, dimethylbenzyl, 
fluorobenzyl, 2-methoxyethyl, and 3-methoxypropyl); D.sup.1 represents a 
hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, which may 
be substituted, (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 
2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2-bromoethyl, 2-glycidylethyl, 
2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 
2-hydroxy-3-chloropropyl, 2-cyanoethyl, 3-cyanopropyl, 2-nitroethyl, 
2-methoxyethyl, 2-methanesulfonylethyl, 2-ethoxyethyl, 
N,N-dimethylaminoethyl, N,N-diethylaminoethyl, trimethoxysilylpropyl, 
3-bromopropyl, 4-hydroxybutyl, 2-furfurylethyl, 2-thienylethyl, 
2-pyridylethyl, 2-morpholinoethyl, 2-carboxyethyl, 3 -carboxypropyl, 
4-carboxybutyl, 2-phosphoethyl, 3-sulfopropyl, 4-sulfobutyl, 
2-carboxyamidoethyl, 3-sulfoamidopropyl, 2-N-methylcarboxyamidoethyl, 
cyclopentyl, chlorocyclohexyl, and dichlorohexyl) or an aralkyl group 
having from 6 to 14 carbon atoms, which may be substituted, (e.g., benzyl, 
phenethyl, 3-phenylpropyl, methylbenzyl, dimethylbenzyl, 
.alpha.-methylbenzyl, methoxybenzyl, 2-naphthylethyl, and chlorobenzyl); 
d.sup.1 and d.sup.2, which may be the same or different, each has the same 
meanings as a.sup.1 and a.sup.2 in formula (I) described above. 
Specific examples of the monofunctional monomer (A) are vinyl esters or 
allyl esters of an aliphatic carboxylic acid having from 1 to 6 carbon 
atoms (e.g., acetic acid, propionic acid, butyric acid, monochloroacetic 
acid, and trifluoropropionic acid); alkyl esters or alkyl amides having 
from 1 to 4 carbon atoms, which may be substituted, of an unsaturated 
carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, 
itaconic acid, maleic acid, etc., (examples of the alkyl group are methyl, 
ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 
trifluoroethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-nitroethyl, 
2-methoxyethyl, 2-methanesulfonylethyl, 2-benzenesulfonylethyl, 
2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl, 2-carboxyethyl, 
2-phosphoethyl, 4-carboxybutyl, 3-sulfopropyl, 4-sulfobutyl, 
3-chloropropyl, 2-hydroxy-3-chloropropyl, 2-furfurylethyl, 
2-pyridinylethyl, 2-thienylethyl, trimethoxysilylpropyl, and 
2-carboxyamidoethyl]; styrene derivatives (e.g., styrene, vinyltoluene, 
.alpha.-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, 
bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, 
chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, 
N,N-dimethylaminomethylstyrene, vinylbenzenecarboxyamide, and 
vinylbenzenesulfonamide); unsaturated carboxylic acids such as acrylic 
acid, methacrylic acid, crotonic acid, maleic acid, iraconic acid, etc.; 
cyclic acid anhydrides such as maleic acid, itaconic acid, etc.; 
acrylonitrile; methacrylonitrile; and heterocyclic compounds having a 
polymerizable double bond group (practically, the compounds described, 
e.g., in Koobunshi (High Molecular) Date Handbook, pages 175 to 184, 
edited by Koobunshi Gakkai, published by Baifuu Kan, 1986, such as, for 
example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, 
vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, and 
N-vinylmorpholine). 
The monomers (A) may be used singly or as a mixture of them. 
Furthermore, at least one kind of monomers (C) represented by formula (V), 
having a specific substituent, and copolymerizable with the monofunctional 
monomer (A) may be used together with the monomer (A) in an amount of from 
0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, per 100 
parts by weight of the monomer (A). By using the monomer (C) together with 
the monomer (A), the redispersion stability of the dispersed resin 
particles of the present invention is more improved: 
##STR7## 
wherein e.sup.1, e.sup.2, and T.sup.2 have the same meaning as d.sup.1, 
d.sup.2, and T.sup.1 in formula (IV) described above and R.sup.01 
represents an aliphatic group having 8 or more carbon atoms or a 
substituent selected from the substituents represented by formula (VI) 
EQU --A.sup.1 --B.sup.1).sub.m (A.sup.2 --B.sup.2).sub.n R.sup.21(VI) 
wherein R.sup.21 represents a hydrogen atom or an aliphatic group having 
from 1 to 18 carbon atoms (e.g., a straight-chain or branched alkyl or 
alkenyl group); B.sup.1 and B.sup.2, which may be the same or different, 
each represents --O--, --S--, --CO--, --CO.sub.2 --, --OCO--, --SO.sub.2 
--, --N(R.sup.22)--, --CON(R.sup.22)--, --N(R.sup.22)CO--, 
--N(R.sup.22)SO.sub.2 --, --SO.sub.2 N(R.sup.22)--, --NHCO.sub.2 --, or 
--NHCONH-- (wherein R.sup.22 has the same meaning as R.sup.21 described 
above); A.sup.1 and A.sup.2, which may be the same or different, each 
represents a hydrocarbon group having from 1 to 18 carbon atoms, which may 
be substituted or may have the moiety represented by formula (a) in the 
main chain bond: 
##STR8## 
wherein B.sup.3 and B.sup.4 which may be the same or different, have the 
same meanings as B.sup.1 and B.sup.2 described above; A.sup.4 represents a 
hydrocarbon group having from 1 to 18 carbon atoms (e.g., an alkyl group, 
an alkenyl group, an aralkyl group, an alicyclic group, an aromatic group, 
and a hetrocyclic group), which may be substituted; and R.sup.23 has the 
same meaning as R.sup.21 described above; and m, n, and p, which may be 
the same or different, each represents an integer of from 0 to 4, with a 
proviso that m, n, and p are not simultaneously 0. 
In the monomer (C) shown by formula (V) described above, T.sup.2 is 
preferably--COO--, --CONH--, --CON(W.sup.1)-- (wherein W.sup.1 represents 
preferably an aliphatic group (e.g., an alkyl group, an alkenyl group, and 
an aralkyl group) having from 1 to 8 carbon atoms, --OCO--, --CH.sub.2 
OCO-- or --O--. 
Also, e.sup.1 and e.sup.2, which may be the same or different, each 
represents preferably a hydrogen atom, methyl, --COO--D.sup.12, or 
--CH.sub.2 COO--D.sup.12 (wherein D.sup.12 represents preferably an alkyl 
group having from 1 to 32 carbon atoms, an alkenyl group, an aralkyl 
group, or a cycloalkyl group). 
Furthermore, it is more preferred that T.sup.2 in formula (V) represents 
--COO--, --CONH--, or --CON(W.sup.1); e.sup.1 and e.sup.2, which may be 
the same or different, each represents a hydrogen atom or methyl; and 
R.sup.01 has the same meaning as described above. 
One of R.sup.01 in formula (V) represents an aliphatic group having at 
least 8 carbon atoms, which is practically the same as the aliphatic group 
shown by R.sup.0 in formula (I) described above. 
Then, the other of R.sup.01 in formuler (V), i.e., the substituent shown by 
formula (VI) described above, is described below in detail. 
In formula (VI), A.sup.1 and A.sup.2 each is more specifically constituted 
by an optional combination of the atomic groups such as 
--C(R.sup.24)(R.sup.25)-- (wherein R.sup.24 and R.sup.25 each represents a 
hydrogen atom, an alkyl group, a halogen atom, etc.), --(CH.dbd.CH)--, a 
cyclohexylene group (hereinafter, the cyclohexylene group is shown by 
(--C.sub.6 H.sub.10 --) including 1,2-cyclohexylene, 1,3-cyclohexylene, 
and 1,4-cyclohexylene), and the group of formula (a) described above. 
Also, in the linkage group --T.sup.2 --(A.sup.1 --B.sup.1).sub.m --(A.sup.2 
--B.sup.2).sub.n --R.sup.21 in formula (V) described above, it is 
preferred that the linked main chain constituted from T.sup.2 to R.sup.21 
(i.e., T.sup.2, A.sup.1, B.sup.1, A.sup.2, B.sup.2, and R.sup.21) is 
constituted the sum total of the atoms of at least 8. In the case that 
T.sup.2 represents --CON(W.sup.1) and W.sup.1 represents the substituent 
shown by formula (VI) described above (i.e., --(A.sup.1 --B.sup.1).sub.m 
--(A.sup.2 --B.sup.2).sub.n --R.sup.21) the chain constituted by W.sup.1 
is included in the linked main chain described above. Furthermore, in the 
case that A.sup.l and A.sup.2 each is a hydrocarbon group having the 
linkage group shown by formula (a) described above in the linkage of the 
main chain --B.sup.3 --(A.sup.4 --B.sup.4).sub.p --R.sup.23 is also 
included in the linked main chain described above. As the number of atoms 
of the linked main chain, when, for example, T.sup.2 represents --COO-- or 
--CONH--, the oxo group (.dbd.O group) or the hydrogen atom are not 
included in the number of atoms, and the carbon atom, the ether-type 
oxygen atom, and the nitrogen atom are included in the number of atoms. 
Accordingly, the number of atoms of --COO-- and --CONH-- is 2. Similarly, 
when R.sup.21 represents --C.sub.9 H.sub.19, the hydrogen atoms are not 
included in the number of atoms and the carbon atoms are included in the 
number of atoms. Accordingly, in this case, the number of atoms is 9. 
Preferred examples of the monomer (C) shown by formula (V) wherein R.sup.01 
represents the substituent shown by formula (VI) described above, that is, 
the monomer having the specific polar group, are illustrated below. 
However, the present invention is not limited to the following compounds 
with respect to the monomer (C). 
In the following formulae, 
a represents --H or --CH.sub.3 ; 
R.sub.1 ' represents --C.sub.n H.sub.2n+1 (wherein n is an integer of from 
1 to 18); 
i represents an integer of from 2 to 12; 
k represents an integer of from 2 to 5; 
R.sub.2 ' represents --C.sub.m H.sub.2m+1 (wherein m is an integer of from 
6 to 18); 
R.sub.3 ' represents --H or --C.sub.m H.sub.2m+1 (wherein m is an integer 
of from 6 to 18); and 
r represents an integer of from 1 to 5. 
##STR9## 
Each of the foregoing monomers (C) having a long-chain aliphatic group or a 
substituent having the total atom number of at least 9 is copolymerized 
with the monomer (A) to form insoluble resin particles dispersed in the 
nonaqueous solvent. It is considered that since the polymer component 
corresponding to the monomer (C) has the substituent as described above 
and hence has an affinity for the nonaqueous solvent, the resulting 
insolubilized resin particles, contain the polymer component more oriented 
to the surface of the particle or adjacent to the surface than oriented in 
the inside of the resin particle which is a polar resin particle, so that 
the affinity of the surface of the resin particles for the nonaqueous 
solvent is improved to restrain the occurrence of the aggregation of the 
particles, whereby the dispersion stability is greatly improved. 
Then, the dispersion stabilizing resin (P) being used in the present 
invention is described in detail. 
The weight average molecular weight (Mw) of the resin (P) is from 
1.times.10.sup.4 to 1.times.10.sup.6, and preferably from 3.times.10.sup.4 
to 5.times.10.sup.5. 
If the molecular weight is less than the foregoing range, the dispersion 
stability of the resin particles is lowered and if the molecular weight is 
over the foregoing range, the particle size distribution of the resin 
particles is increased to reduce the effect of the present invention. 
The resin (P) contains the repeating unit shown by formula (I) in an amount 
of at least 50% by weight based on the weight of the polymer: 
##STR10## 
wherein V.sup.0 represents --COO--, --OCO--, --(CH.sub.2).sub.r COO--, 
--(CH.sub.2).sub.r OCO--, --O--, --CONHCOO--, --CONHCONH--, --COND.sup.11 
--, --SO.sub.2 ND.sup.11 -- or a phenylene group (--Ph--) (wherein 
D.sup.11 represents a hydrogen atom or a hydrocarbon group having from 1 
to 22 carbon atoms and r represents an integer of from 1 to 4); a.sup.1 
and a.sup.2, which may be the same or different, each represents a 
hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group which 
may be substituted, --COO--D.sup.12, or --COO--D.sup.12 through a 
hydrocarbon group (wherein D.sup.12 represents a hydrocarbon group which 
may be substituted); and R.sup.0 represents an aliphatic group having from 
8 to 32 carbon atoms (e.g., a straight-chain or branched alkyl or alkenyl 
group). 
In formula (I), D.sup.11 in the substituents shown by V.sup.0 represents a 
hydrogen atom or a hydrocarbon group having from 1 to 22 carbon atoms as 
described above and preferred examples of the hydrocarbon group are an 
alkyl group having from 1 to 22 carbon atoms, which may be substituted 
(e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, 
dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosabyl, docosanyl, 
2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 
2-methoxyethyl, and 3-bromopropyl), an alkenyl group having from 4 to 18 
carbon atoms, which may be substuted (e.g., 2-methyl-1-propenyl, 
2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 
2-hexenyl, 4-methyl-2-hexenyl, decenyl, dodecenyl, tridecenyl, 
hexadecenyl, octadecenyl, and linolel), an aralkyl group having from 7 to 
12 carbon atoms, which may be substituted (e.g., benzyl, phenethyl, 
3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, 
bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl, and 
dimethoxybenzyl), an alicyclic group having from 5 to 8 carbon atoms, 
which may be substituted (e.g., cyclohexyl, 2-cyclohexylethyl, and 
2-cyclopentylethyl), and an aromatic group having from 6 to 12 carbon 
atoms, which may be substituted (e.g., phenyl, naphthyl, tollyl, xylyl, 
propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, 
ethoxyphenyl, butoxyohenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, 
bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, 
ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, 
propioamidophenyl, and dodecyloylamidophenyl). 
When V.sup.0 represents a phenylene group (--Ph--), the benzene ring may 
have a substituent such as a halogen atom (e.g., chlorine and bromine), an 
alkyl group (e.g., methyl, ethyl, propyl, butyl, chloromethyl, and 
methoxymethyl), etc. 
V.sup.0 is more preferably --COO--, --OCO--, --COND.sup.11 --, --O--, or a 
phenylene group. 
In formula (I), a.sup.1 and a.sup.2, which may be the same or different, 
each preferably represents a hydrogen atom, a halogen atom (e.g., chlorine 
and bromine), a cyano group, an alkyl group having from 1 to 6 carbon 
atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and 
hexyl),--COO--D.sup.12, or --CH.sub.2 COO--D.sup.12 (wherein D.sup.12 
preferably represents an alkyl group having from 1 to 22 carbon atoms, an 
alkenyl group, an aralkyl group, an alicyclic group, or an aryl group and 
these groups may be substituted as described practically in the case of 
D.sup.11. 
Then, the functional group shown by formula (II) contained in the resin (P) 
is described in detail. 
The functional group of formula (II) shown below is bonded to the copolymer 
component as a substituent and/or one terminal of the main chain of the 
polymer of the resin (P): 
##STR11## 
wherein Z.sup.0 represents --O--R.sup.1 or --NR.sup.2 (R.sup.3) (wherein 
R.sup.1 represents a monovalent organic residue wherein the atom adjacent 
to the oxygen atom is a carbon atom and R.sup.2 and R.sup.3, which may be 
the same or different, each represents a hydrogen atom or the monovalent 
organic residue same as that shown by R.sup.1 with a proviso that both 
R.sup.2 and R.sup.3 are not simultaneously a hydrogen atom. 
When the functional group is contained as the copolymer component, the 
content thereof is preferably from 0.5 to 10 parts by weight per 100 parts 
by weight of the polymer of the resin (p). If the content thereof is over 
the range, the particle distribution of the dispersed resin particles 
obtained by the polymerization reaction is broadened. 
In a more preferred embodiment, the functional group is bonded to one 
terminal of the main chain of the resin (P). 
As a preferred embodiment of R.sup.1 in formula (II), there is a 
hydrocarbon group having from 1 to 22 carbon atoms, which may be 
substituted. 
Examples of the hydrocarbon group for R.sup.1 are an aliphatic group having 
from 1 to 22 carbon atoms (e.g., an alkyl group such as methyl, ethyl, 
propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 
dodecyl, tridecyl, tetradecyl, pentadecyl, hexaecyl, octadecyl, nanodecyl, 
eicosanyl, docosanyl, etc.; an alkenyl group such as ethenyl, propenyl, 
butenyl, pentenyl, pentadienyl, hexenyl, hexadienyl, octenyl, decenyl, 
dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, 
etc.; an alicyclic group such as cyclopentyl, cyclohexyl, cycloheptyl, 
cyclooctyl, cyclohexcenyl, cyclooctenyl, adamantyl, etc.; and an aralkyl 
group such as benzyl, phenethyl, 3-phenylpropyl, .alpha.-benthylbenzyl, 
.beta.-methylphenethyl, naphthylmethyl, naphthylethyl, naphthylpropyl, 
etc.) and an aromatic group (e.g., phenyl and naphthyl). 
These hydrocarbon groups may have a substituent such as a halogen atom 
(e.g., fluorine, chlorine, bromine, and iodine), a hydroxy group, a cyano 
group, a carboxy group, a sulfo group, an amino group, a formyl group, a 
phosphono group, a cyclic acid anhydride group, etc., although the present 
invention is not limited thereto. 
Other preferred embodiment of R.sup.1 may be a monovalent organic residue 
bonded to the oxygen atom with a carbon atom and constituted through 
various linkage groups. 
As the linkage group, any bonding group may be used but specific examples 
of the linkage group are --C(d.sup.1)(d.sup.2)-- (wherein, d.sup.1 and 
d.sup.2, which may be the same or different, each represents a hydrogen 
atom, a halogen atom (e.g., chlorine and bromine), a hydroxy group, a 
cyano group, an alkyl group (e.g., methyl, ethyl, 2-chloroethyl, 
2-hydroxyethyl, propyl, butyl, and hexyl), an aralkyl (e.g., benzyl and 
phenethyl), a phenyl group, etc.], --CH(d.sup.3)--CH(d.sup.4)-- (wherein 
d.sup.3 and d.sup.4 have the same meaning as d.sup.1 and d.sup.2 ]. 
--C.sub.6 H.sub.10 --, --C.sub.6 H.sub.4 --, --O--, --S--, --N(d.sup.5)-- 
(wherein D.sup.5 represents a hydrogen atom or a hydrocarbon group such 
as, practically, a hydrocarbon group having from 1 to 12 carbon atoms 
(e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, 
2-methoxyethyl, 2-chloroethyl, 2-cyanoethyl, benzyl, methylbenzyl, 
phenethyl, phenyl, tollyl, chlorophenyl, methoxyphenyl, and butylphenyl)), 
--CO--, --COO--, --OCO--, --NHCOO--, --NHCONH--, --CON(d.sup.5)--, 
--SO.sub.2 N(d.sup.5)--, --SO.sub.2 --, --NHCONH--, --NHCOO--, 
--NHSO.sub.2 --, --CONHCOO--, --CONH--CONH--, a heterocyclic ring (5- or 
6-membered ring having at least one kind of a hetero atom such as O, S, N, 
etc., or the condensed ring of them; examples thereof are thiophene, 
pyridine, furan, imidazole, piperidine, and morpholine), and 
--Si(d.sup.6)(d.sup.7 )-- (d.sup.6 and d.sup. 7, which may be the same or 
different, each represents a hydrocarbon group or --OD.sup.8 (wherein 
d.sup.8 represents a hydrocarbon group) and these hydrocarbons are same as 
those described as d.sup.5 above). These linkage groups may be used singly 
or may be preferably used as an organic residue constituted by a 
combination of these linkage groups. 
There is no particular restriction on the monovalent organic residue but it 
is preferred that the total atom number of the substituents constituting 
the organic residue does not exceed 22. 
When Z.sup.0 in formula (II) is --NR.sup.2 (R.sup.3), the substituents 
shown by R.sup.2 and R.sup.3 are the same as those defined for R.sup.1. 
In the present invention, what is important in formula (II) is the partial 
structure shown by the following formula 
##STR12## 
and R.sup.1, R.sup.2, and R.sup.3 are not limited to those exemplified 
above. In the case that the functional group shown by formula (II) is 
contained in the chain of a copolymerization component, any vinylic 
compounds containing the functional group copolymerizable with a monomer 
corresponding to, for example, the repeating unit shown by formula (II) 
can be used as a coplymerization component, and they can be represented by 
formula (VII) 
##STR13## 
wherein f.sup.1, f.sup.2, and V.sup.2 have the same meaning as a.sup.1, 
a.sup.2, and V.sup.0 in formula (I) described above; 
--S--C(.dbd.S)--Z.sup.0 represents the same functional group as in formula 
(II); and X.sup.0 represents a divalent organic residue bonding --V.sup.2 
-- and --S--C(.dbd.S)--Z.sup.0, such as those defined for R.sup.1 in 
formula (II) or a combination, and preferably those having the total atom 
number constituting the portion --(V.sup.2 --X.sup.0 ]-- of from 6 to 20. 
The functional group shown by formula (II) is preferably bonded to one 
terminal of the main chain of the polymer chain of the resin (P). 
In the preferred embodiment, the functional group is bonded to the terminal 
of the main chain directly or through a linkage group. The linkage group 
is exemplified with those defined for R.sup.1 in formula. (II) or a 
combination thereof. 
A preferred dispersion stabilizing resin (P) is a comb-type block copolymer 
of a mono-functional macromonomer (M) with a comonomer. 
The macromonomer (M) is an addition polymerizable macromonomer having a 
weight average molecular weight of from 1.times.10.sup.3 to 
2.times.10.sup.4 (preferably from 2.times.10.sup.3 to 1.5.times.10.sup.4) 
and copolymerizable with the monomer corresponding to the repeating unit 
shown by formula (I) described above, and the macromononer being obtained 
by bonding the polymerizable double bond group shown by formula (III) to 
one terminal only of the main chain of a polymer containing the repeating 
unit shown by formula (I) described above: 
##STR14## 
wherein b.sup.1, b.sup.2, and V.sup.1 have the same meanings as a.sup.1, 
a.sup.2, and V.sup.0 in formula (I) described above, respectively. 
In the macromonomer (M), the content of the repeating unit shown in formula 
(I) is preferably from 50 to 100% by weight, more preferably from 70 to 
100% by weight, based on the weight of the macromonomer. 
As a comonomer to copolymerize with the macromonomer, any monomer 
corresponding to the repeating unit shown by formula (I) may be used and 
practically there are the same monomers as the compounds illustrated for 
the monofunctional monomer (A) described above. 
The content of the monofunctional macromonomer (M) in the resin (P) is from 
1 to 60% by weight, preferably from 5 to 40% by weight, based on the 
weight of the polymer of the resin (P). 
If the content of the monofunctional macromonomer (M) is less than 1% by 
weight, the effect of introducing the graft structure in the resin (P) is 
lessen, so that the effect of improving the dispersion stability of the 
resin particles is reduced. Also, if the content thereof is more than 60% 
by weight, the copolymerizability with the comonomer is undesirably 
lowered. 
The polymerizable double bond group shown by formula (III) is bonded to one 
terminal of the main chain of the macromonomer containing the repeating 
unit shown by formula (I) directly or through a linkage group which is 
exemplified with those defined for R.sup.1 of formula (II) or a 
combination thereof. 
Specific examples of the polymerizable double bond group shown by formula 
(III) are illustrated below but the invention is not limited thereto. (In 
addition, in the case of bonding the polymerizable double bond group of 
formula (III) to the polymer main chain of the macromonomer (M) through a 
linkage group, the double bond group is shown together with the linkage 
group.) 
In the following formulae showing the polymerizable double bond groups; 
b represents --H or --CH.sup.3 ; 
X represents --S-- or a direct bond; 
m.sub.1 represents an integer of from 1 to 12; and 
n.sub.1 represents an integer of from 2 to 12. 
##STR15## 
The macromonomer (M) being used in the present invention can be produced by 
a conventionally known synthesis method. 
For example, there are (1) a method by an ionic polymerization method of 
reacting various reagents to the terminal of a living polymer obtained by 
an anionic polymerization or a cationic polymerization to form a macromer; 
(2) a method by a radical polymerization method of reacting various 
reagents and an oligomer having a reactive group bonded to the terminal 
thereof obtained by a radical polymerization, using a polymerization 
initiator and/or a chain-transfer agent each containing a reactive group 
such as a carboxy group, a hydroxy group, an amino group, etc., in the 
molecule to form a macromer; (3) a method by a polyadditional condensation 
method of introducing a polymerizable double bond to an oligomer obtained 
by a polyadditional or polycondensation reaction as in the foregoing 
radical polymerization method, etc. 
Specifically, the monofunctional macromer (M) can be synthsized by the 
methods described in P. Drefuss & R. P. Quirk, Polym. Sci. Eng., 7, 551 
(1987); P. F. Rempp & E Franta, Adv. Polym. Sci., 58, 1 (1984); V. Percec, 
Appl. Polym. Sci., 285, 95 (1984), R. Asami & M. Takari, Makvamol. Chem. 
Suppl., 12, 163 (1985); P. Rempp et al, Makavamol. Chem. Suppl., 8, 3 
(1984), Yusuke Kawakami, Kagaku Kogyo (Chemical Industry), 38, 56 (1987); 
Yuuya Yamashita, Koobunshi (High Molecule), 31, 988 (1982); Shiro 
Kobayashi, Koobunshi (High Molecule), 50, 625 (1981); Toshinobu 
Higashinura, Nippon Setchaku Kyokai Shi (Journal of Adhesive Sci. of 
Japan, 18, 536 (1982); Kooichi Ito, Koobunshi Kako (High Molecular 
Working), 35, 262 (1986), Koshiro Higashi & Takashi Tuda, Kinoo Zairyou 
(Functional Material), 1987, No. 10, 5, etc., and the literatures and the 
patents cited therein. 
Examples of the foregoing polymerization initiator having a reactive group 
in the molecule are azobis series compounds such as 
4,4'-azobis(4-canovaleric acid), 4,4'-azobis(4-cyanovaleric acid 
chloride), 2,2'-azobis(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 
2,2'-azobis(2-(5-hydroxy-3,4,5,6-tetrahydropurimidine-2-yl)propane), 
2,2'-azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propioamide) 
, 2,2,-azobis(2-methyl-N-(1,1-bis(hydroxymethyl)ethyl)propioamide), 
2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propioamide), 
2,2'-azobis(2-amidinopropane), 
2,2'-azobis(2-methyl-N-(2-hydroxyethyl)-propioamide), 
2,2'-azobis(2-(5-methyl-2-imidazoline-2-yl)propane), 
2,2'-azobis(2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane), 
2,2'-azobis(2-(3,4,5,6-tetrahydropyrimidine-2-yl)propane), 
2,2'-azobis(2-(1-(2-hydroxyethyl)-2-imidazoline-2-yl)propane), 
2,2'-azobis(N-(2-hydroxyethyl)-2-methyl-propionamidine), 
2,2'-azobis(N-(4-aminophenyl)-2-methylpropionamidine), etc. 
As the chain-transfer agent containing a reactive group in the molecule, 
there are a mercapto compound containing the reactive group or a 
substituent capable being induced to the reactive group (e.g., 
thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic 
acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 
N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 
3-(N-(2-mercaptoethyl)carbamoyl)propionic acid, 
3-(N-(2-mercaptoethyl)amino)propionic acid, 
N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 
3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 
2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 
3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 
2-mercaptoimidazole, and 2-mercapto-3-pyridinol) and an iodized alkyl 
compound containing the reactive group or a substituent capable of being 
induced to the reactive group (e.g., iodoacetic acid, iodopropionic acid, 
2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid). 
In these compounds, the mercapto compounds are preferably used. 
The amount of the chain-transfer agent or the polymerization initiator is 
from 0.1 to 10 parts by weight, preferably from 0.5 to 5 parts by weight, 
per 100 parts by weight of the total monomers. 
The dispersion stabilizing resin (P) being used in the present invention 
can be synthesized by a conventionally known method. 
That is, in the case that the functional group shown by formula (II) is 
contained only in the polymer side chain of the resin (P), the polymer can 
be synthesized by (1) a method of polymerizing the monomer shown by 
formula (VII) described above together with an other monomer; and (2) a 
method of polymerizing a monomer containing a group capable of introducing 
the functional group shown by formula (II) together with an other monomer 
and then introducing the functional group shown by formula (II) by a high 
molecular reaction, etc. 
Also, in the case that the functional group shown by formula (II) is 
contained in one terminal of the polymer main chain of the resin (P), 
which is the preferred embodiment of the present invention, there are (1) 
a method of polymerizing a mixture of a monomer corresponding to the 
repeating unit shown by formula (I), the foregoing macromonomer (M), and 
the chain-transfer agent containing the functional group shown by formula 
(II) with a polymerization initiator (e.g., an azobis compound and a 
peroxide); (2) a method of polymerizing a mixture of the monomer 
corresponding to the repeating unit shown by formula (I) and the 
macromonomer (M) using a polymerization initiator containing the 
functional group; (3) a method of using a chain-transfer agent containing 
the functional group and a polymerization initiator containing the 
functional group in the foregoing polymerization; and (4) a method of 
carrying out the polymerization reaction using a compound containing an 
amino group, a halogen atom, an epoxy group, an acid halide group, etc., 
as a substituent for the chain-transfer agent or the polymerization 
initiator in each of the foregoing three methods, and thereafter 
introducing the functional group into the polymer by a high molecular 
reaction, etc. 
Practically, the dispersion stabilizing resin (P) can be produced by the 
methods described in P. Dreyfuss & R. P. Quirk, Encycl. Polym. Sci. Eng., 
7, 551 (1987); Yoshiki Nakajo & Yuuya Yamashita, Senryo to Yakuhin (Dyes 
and Chemicals), 30, 232 (1985); Akira Ueda & Susumu Nagai, Kagaku to Kogyo 
(Science and Industry), 60, 57 (1986), etc. and the literatures, etc., 
cited therein. 
As specific examples of the foregoing chain-transfer agent containing the 
specific functional group or a substituent capable of being induced to the 
functional group, the mercapto compounds and ionized alkyl compounds 
described above as the chain-transfer agents containing a reactive group 
used in the synthesis method of the macromonomer (M) can be used. In these 
compounds, the mercapto compounds are preferred. 
Also, as the foregoing polymerization initiator containing the specific 
functional group or a substituent capable of being induced into the 
functional group, azobis compounds described above as the polymerization 
initiator containing the reactive group used in the macromonomer (M) can 
also be used. 
The using amount of the chain-transfer agent or the polymerization 
initiator is from 0.1 to 10 parts by weight, preferably from 0.5 to 10 
parts by weight, per 100 parts by weight of the sum of the total monomers 
and the total macromonomers (M). 
Furthermore, the dispersion stabilizing resin (P) can be also easily 
synthesized by (1) a method of reacting a reagent containing the 
functional group shown by formula (II) at the terminal of a living polymer 
obtained by a conventionally known anionic polymerization or cationic 
polymerization, or (2) a method (a method by an ionic polymerization 
method) of reacting a reagent containing a specific reactive group (e.g., 
--OH, --COOH, --SO.sub.3 H, --SH, --NH.sub.2, --PO.sub.3 H.sub.2, --NCO, 
--NCS, an epoxy group, --COCl, and --SO.sub.2 Cl) with the terminal of the 
foregoing living polymer, followed by a high molecular reaction to 
introduce the functional group. 
Practically, the dispersion stabilizing resin (P) can be synthesized 
according to the methods similar to the methods described in the 
literatures, the patents, etc., illustrated for the synthesis methods of 
the macromonomer (M) described above. 
As a more preferred embodiment of the synthetic method, the functional 
group can be easily introduced into one terminal of the polymer main chain 
by carrying out a photopolymerization reaction using an organic compound 
containing the functional group shown by formula (II) as the 
polymerization initiator. Practically, the dispersion stabilizing resin 
(P) can be synthesized by the methods described in Takayuki Ootu, Kobunshi 
(High Molecule), 37, 248 (1988); Shunichi Hinokimori & Ryuuichi Ootu, 
Polym. Rep. Jap., 37, 3508 (1988); JP-A-64-111, JP-A-64-26619, etc. 
The dispersion stabilizing resin (P) is soluble or semi-soluble in the 
nonaqueous solvent which is used for the polymerization granulation 
reaction. The semi-soluble resin means that when the resin (P) is mixed 
with the nonaqueous solvent at a temperature of 25.degree. C., the state 
of the mixture is in a dispersion of a microgel-form resin having a mean 
particle size of not larger than 0.1 .mu.m. The resin (P) is preferably 
soluble in an organic solvent and it is sufficient for the resin (P) to 
dissolve in an amount of 5 parts by weight or more in 100 parts by weight 
of toluene at 25.degree. C. 
The production process of the nonaqueous resin dispersion of the present 
invention is as follows. 
In general, the dispersion stabilizing resin (P) as described above and the 
monofunctional monomer (A) may be polymerized by heating in a nonaqueous 
solvent under the irradiation of light (ultraviolet rays) having 
wavelengths of not longer than 400 n.m. in a degassed atmosphere. 
Practically, there are (1) a method of irradiating a mixture of the 
dispersion stabilizing resin (P), the monomer (A), and the nonaqueous 
solvent with ultraviolet rays; (2) a method of adding dropwise the monomer 
(A) into a mixture of the dispersion stabilizing resin (P) and the 
nonaqueous solvent under the irradiation of ultraviolet rays; (3) a method 
of adding a part of the monomer (A) to a nonaqueous solvent containing the 
whole amount of the dispersion stabilizing resin (P) and the residual 
amount of the monomer (A) under the irradiation of ultraviolet rays; and 
(4) a method of adding a mixture of the dispersion stabilizing resin (P) 
and the monomer (A) to the nonaqueous solvent under the irradiation of 
ultraviolet rays, etc. 
As the light source for the ultraviolet rays being used in the present 
invention, an ordinary light source can be used and practically, there are 
a mercury lamp (high pressure or low pressure), a xenon lamp, a deep UV 
lamp, a metal halide lamp, etc., and the light of the light source is used 
by cutting wavelengths of longer than 400 n.m. with a filter. 
The total amount of the dispersion stabilizing resin (P) and the monomer 
(A) is from about 5 to 80 parts by weight, preferably from 10 to 60 parts 
by weight, per 100 parts by weight of the nonaqueous solvent. The amount 
of the dispersion stabilizing resin (P) is from 1 to 50 parts by weight, 
preferably from 3 to 30 parts by weight, per 100 parts by weight of the 
total monomers (A). 
The polymerization temperature is from about 30.degree. to 180.degree. C., 
and preferably from 40.degree. to 100.degree. C. The reaction time is 
preferably from 1 to 15 hours. 
When a polar solvent such as alcohols, ketones, ethers, esters, etc., is 
used together with the nonaqueous solvent used for the reaction or when 
unreacted materials of the monomers (A) remain, it is preferred to remove 
them by distilling off by heating to a temperature of higher than the 
boiling point of the solvent or the monomer (A), or distilling off under a 
reduced pressure. 
Furthermore, the nonaqueous solvent used at the polymerization granulation 
may be changed with a desired nonaqueous solvent. In this case, as a 
matter of course, it is preferred that the boiling point of the nonaqueous 
solvent being used for the exchange is higher than the boiling point used 
for the reaction. 
The resin particles of the nonaqueous resin dispersion thus produced are 
fine particles having a uniform particle size distribution and, at the 
same time, show a very stable dispersibility. Also, when the resin 
particles are fixed by heating, etc., a strong coated layer is formed and 
thus show an excellent fixing property. 
The nonaqueous resin dispersion thus obtained is suitable as dispersed 
resin particles of a liquid developer for electrostatic photography. 
The liquid developer of the present invention comprises a nonaqueous 
solvent having an electric resistance of at least 1.times.109 .OMEGA.cm 
and a dielectric constant of not higher than 3.5 containing the dispersed 
resin particles described above. 
As the nonaqueous solvent, straight chain or branched aliphatic 
hydrocarbon, alicyclic hydrocarbons, aromatic hydrocarbons, and the 
halogen substituted products of them can be preferably used. Examples 
thereof are octane, isooctane, decane, isodecane, decaline, nonane, 
dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, 
toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L 
(Isopar: trade name of Exxon Research and Engineering Company), Shellsol 
70, Shellsol 71 (Shellsol: trade name of Shell Oil Co.), Amsco OMS, Amsco 
460 solvent (Amsco: trade name of American Mineral Spirits Co.), etc. They 
can be used singly or as a mixture thereof. 
As the solvent which can be used together with the foregoing nonaqueous 
solvent, there are alcohols (e.g., methanol, ethanol, propanol, butanol, 
and fluorinated alcohols), ketones (e.g., acetone, methyl ethyl ketone, 
and cyclohexanone), carboxylic acid esters (e.g., methyl acetate, ethyl 
acetate, propyl acetate, butyl acetate, methyl propionate, and ethyl 
propionate), ethers (e.g., diethyl ether, dipropyl ether, tetrahydrofuran, 
and dioxane), halogenated hydrocarbons (e.g., methylene dichloride, 
chloroform, carbon tetrachloride, dichloroethane, and methylchloroform). 
It is preferred that the foregoing solvent used together with the 
nonaqueous solvent being used in the present invention is distilled off by 
heating or under a reduced pressure after the polymerization granulation 
but even when the solvent is carried in the liquid developer as the latex 
particle dispersion, there is no problem if the electric resistance of the 
liquid of the liquid developer meets the condition of at least 
1.times.10.sup.9 .OMEGA.cm. 
Usually, it is preferred to use the same nonaqueous solvent as the carrier 
liquid used in the step of producing the resin dispersion and as described 
above, straight chain or branched aliphatic hydrocarbons, alicyclic 
hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc., are 
used. 
The liquid developer of the present invention preferably contains a charge 
controlling agent for precisely controlling the electroscopic property of 
the resin particles dispersed in the organic solvent. 
As the charge controlling agent for the liquid developer of the present 
invention, conventionally known agents can be used. For example, the metal 
salts of a fatty acid such as naphthenic acid, octenic acid, oleic acid, 
stearic acid, etc.; the metal salts of sulfosuccinic acid esters; the 
oil-soluble metal sulfonates described in JP-B-45-556 (the term "JP-B" as 
used herein means an "examined published Japanese patent application"), 
JP-A-52-37435, JP-A-52-37049, etc.; the metal salts of phosphoric acid 
ester described in JP-B-45-9594; the metal salts of abietic acid or 
hydrogenated abietic acid described in JP-B-48-25666; the calcium 
alkylbenzenesulfonates described in JP-B-55-2620; the metal salts of 
aromatic carboxylic acid or sulfonic acid described in JP-A-52-107837, 
JP-A-52-38937, JP-A-57-90643, and JP-A-57-139753; nonionic surface active 
agents such as polyoxyethylated alkylamine, etc.; fats and oils such as 
lecithin, linseed oil, etc.; polyvinylpyrrolidone; organic acid esters of 
polyhydric alcohols; phosphoric acid ester type surface active agents 
described in JP-A-57-210345; and the sulfonic acid resin described in 
JP-B-56-24944 can be used. Also, the amino acid derivatives described in 
JP-A-60-21056 and JP-A-61-50951 can be used. 
Furthermore, the reaction products of a maleic anhydride copolymer or 
itaconic anhydride copolymer and a primary or secondary amine described in 
JP-A-59-30917, JP-A-59-29938, and JP-A-59-38264; the copolymer containing 
maleic acid half acylamide and N-substituted maleinimide described in 
JP-A-59-36787; and further the quaternarized amine polymers described in 
JP-A-54-31739, JP-B-56-24944, etc., can be also used. 
For the liquid developer of the present invention, if desired, a coloring 
agent may be used. There is no particular restriction on the coloring 
agent and various pigments and dyes conventionally known can be used. For 
example, there are metal powders such as an aluminum powder, etc.; metal 
oxides such as magnetic iron oxide, zinc oxide, titanium oxide, silicon 
dioxide, etc.; metal salts such as powdered lead cadmium-seleniumchromate, 
etc.; Hansa Yellow (C.I. 11680), Benzidine Yellow G (C.I. 21090), 
Benzidine Orange (C.I. 21110), Fast Red (C.I. 37085) Brilliant Carmine 3B 
(C.I. 16015-Lake), Phthalocyanine Blue (C.I. 74160), Phthalocyanine Green 
(C.I. 74260), Victoria Blue (C.I. 42595-Lake), Spirit Black (C.I. 50415), 
Oil Blue (C.I. 74350), Alkali Blue (C.I. 42770A), Fast Scarlet (C.I. 
12315), Rhodamine 6B (C.I. 45160), Fast Sky Blue (C.I. 74200-Lake), 
Nigrosine (C.I. 50415), carbon black, etc. Also, surface-treated pigments 
such as, for example, carbon black dyed with Nigrosine and graft carbon 
graft-polymerized with a polymer can be used. 
In the case of coloring the dispersed resin itself, as one of the coloring 
methods, there is a method of physically dispersing a pigment or a dye in 
the dispersed resin and a method of dyeing the dispersed resin with a 
preferred dye as described in JP-A-57-48738. 
A method of chemically bonding the dispersed resin with a dye as disclosed 
in JP-A-53-54029 and a method of using a monomer previously containing a 
dye in the case of producing the dispersed resin by a polymerization 
granulation method to form a copolymer containing the dye as described in 
JP-B-44-22955 can also be employed. 
The liquid developer of the present invention may contain, if desired, 
various additives for improving the charging characteristics and the 
imaging characteristics, and examples thereof are described, e.g., in 
Yuuji Harasaki, Denshi Shashin (Electrophotography), Vol. 16, No. 2, page 
44 are used, such as higher alcohols, fluorized alcohols, polyethers, 
olefin waxes, silicone oils, and hetrocyclic compounds. But the additives 
are not limited thereto. 
The amount of each main component of the liquid developer of the present 
invention is as follows. 
The amount of the toner particles composed of the resin (and a coloring 
agent being used if desired) as the main component(s) are preferably from 
0.5 to 50 parts by weight per 1,000 parts by weight of the carrier liquid. 
If the amount thereof is less than 0.5 parts by weight, the image density 
obtained is insufficient, while of the amount is over 50 parts by weight, 
a fog is liable to form on non-imaged portions. 
Furthermore, the foregoing dispersion stabilizing carrier liquid-soluble 
resin is, if necessary, used and the amount is from about 0.5 to 100 parts 
by weight to 1,000 parts by weight of the carrier liquid. 
The amount of the foregoing charge controlling agent is preferably from 
0.001 to 1.0 part by weight to 1,000 parts by weight of the carrier 
liquid. 
Furthermore, if desired, various additives may be added to the liquid 
developer and the upper limit of the total amounts of these additives are 
restricted by the electric resistance of the liquid developer. That is, if 
the electric resistance of the liquid developer in a state of removing the 
toner particles is lower than 1.times.10.sup.9 .OMEGA.cm, a continuous 
gradation image having a good quality is reluctant to obtain and hence it 
is necessary to control the addition amount of each additive within the 
limit. 
As a photoconductive material to which the liquid developer of the present 
invention is applied, there are well-known organic photoconductive 
materials and inorganic photoconductive materials. Also, dielectrics 
charged by a charging conductor can be used. 
As the organic photoconductive materials, there are well-known various 
organic photoconductive materials as described in Research Disclosure, No. 
10938 (May, 1973), page 61 st seq., "Electrophotographic Elements, 
Materials, and Process" 
Specific examples which are practically used are the electrophotographic 
photoreceptor composed of poly-N-vinylcarbazole and 
2,4,7-trinitrofluoren-9-one as described in U.S. Pat. No. 3,484,237; the 
photosensitive material composed of poly-N-vinylcarbazole sensitized with 
a pyrylium salt series dye as described in JP-B-48-25658; the 
electrophotographic photoreceptor composed of an organic pigment as the 
main component described in JP-A-49-37543; the electrophotographic 
photoreceptor containing an eutetic complex composed of a dye and a resin 
as the main component described in JP-A-47-10735; and the 
electrophotographic photoreceptor composed of copper phthalcyanine 
dispersed in a resin described in JP-B-52-1667. Other electrophotographic 
photoreceptors are described in Denshishashin Gakkai Shi (Journal of 
Electrophotographic Society), Vol. 25, No. 3, 62-76(1986). 
As the inorganic photoconductive material being used in the present 
invention, there are typically various kinds of inorganic compounds 
disclosed in R. M. Schaffert, Electro Photography, 260-374(1975), 
published by Focal press (London). Specific examples thereof are zinc 
oxide, titanium oxide, zinc sulfide, cadmium sulfide, a selenium-tellurium 
alloy, a selenium-arsenic alloy, and selenium-telluriumarsenic alloy. 
Then, the effect of the present is described in more detail with reference 
to the Production Examples of the monofunctional macromonomer (M), the 
dispersion stabilizing resin (P), and the dispersed resin particles of the 
present invention and the Examples of the present invention, but the 
present invention is not limited thereto. 
Production Example of Monofunctional Macromonomer (M): (M-1) 
A mixed solution of 100 g of octadecyl methacrylate, 3 g of 
mercpatopropionic acid, and 200 g of toluene was heated to 75.degree. C. 
with stirring under a nitrogen gas stream. Then, after adding thereto 1.0 
g of 2,2'-azobisisobutyronitrile (A.I.B.N.), the reaction was carried out 
for 4 hours, further after adding thereto 0.5 g of A.I.B.N., the reaction 
was carried out for 3 hours, and further after adding thereto 0.3 g of 
A.I.B.N., the reaction was carried out for 3 hours. Then, to the reaction 
mixture were added 8 g of glycidyl methacrylate, 1.0 g of 
N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone and the 
resultant mixture was stirred for 12 hours at 100.degree. C. After 
cooling, the reaction mixture was reprecipitated in 2 liters of methanol 
to provide 82 g of a white powder of the polymer (M-1) shown below. The 
weight average molecular weight (Mw) of the polymer was 6,500. 
##STR16## 
Production Example 2 of Monofunctional Macromonomer (M): (M-2) 
A mixed solution of 100 g of dodecyl methacrylate, 3 g of thioethanol, and 
200 g of toluene was heated to 70.degree. C. with stirring under a 
nitrogen gas stream. Then, after adding to the mixture 1.0 g of A.I.B.N, 
the reaction was carried out for 4 hours, furthermore, after adding 
thereto 0.5 g of A.I.B.N., the reaction was carried out for 3 hours, and 
thereafter, after further adding thereto 0.3 g of A.I.B.N., the reaction 
was carried out for 3 hours. Then, after cooling the reaction mixture to 
room temperature, 10.9 g of 2-carboxyethyl methacrylate was added to the 
reaction mixture and then a mixed solution of 14.4 g of 
dichlorohexylcarbodiimide (D.C.C.), 1 g of 4-(N,N-dimethylamino)pyridine, 
and 150 g of methylene chloride was added dropwise thereto over a period 
of one hour. Then, 1.0 g of t-butylhydroquinone was added to the mixture 
and the resulting mixture was stirred for 4 hours as it was. 
To the mixture was added 10 g of an aqueous solution of 85% formic acid and 
the resulting mixture was stirred for 2 hours as it was. Crystals thus 
precipitated were recovered by filtration and reprecipitated in 2 liter of 
methanol. The oily product thus precipitated was collected by decantation, 
dissolved in 200 ml of tetrahydrofuran, and the solution was 
reprecipitated again in one liter of methanol. The oily product was 
collected and dried under a reduced pressure to provide 60 g of the 
polymer (M-2) shown below having a weight average molecular weight of 
6,800. 
##STR17## 
Production Example 3 of Monofunctional Macromonomer (M): (M-3) 
A mixed solution of 60 g of octadecyl methacrylate, 40 g of dodecyl 
acrylate, 150 g of tetrahydrofuran, and 50 g of isopropyl alcohol was 
heated to 75.degree. C. with stirring under a nitrogen gas stream. Then, 
after adding to the reaction mixture 6.0 g of 4,4'-azobis(4-cyanovaleric 
acid) (A.C.V.), the reaction was carried out for 5 hours and after further 
adding thereto 1.0 g of A.C.V., the reaction was carried out for 4 hours. 
After cooling, the reaction mixture was reprecipitated in 1.5 liters of 
methanol and the oily product thus precipitated was collected by 
decantation and dried under a reduced pressure. The amount of the oily 
product thus obtained was 85 g. 
To 50 g of the oily product (oligomer) thus obtained were added 15 g of 
glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 1.0 g of 
2,2'-methylenebis(6-t-butyl-p-cresol) and the resulting mixture was 
stirred for 15 hours at 100.degree. C. After cooling, the reaction mixture 
was reprecipitated in one liter of petroleum ether to provide 42 g of a 
white powder of the polymer (M-3) shown below. The weight average 
molecular weight of the polymer was 1.0.times.10.sup.4. 
##STR18## 
Production Example 3 of Monofunctional Macromonomer (M): (M-4) 
A mixed solution of 100 g hexadecyl methacrylate, 4 g of 
2-mercaptoethylamine, and 200 g of tetrahydrofuran was heated to 
70.degree. C. with stirring under a nitrogen gas stream. Then, after 
adding to the mixture 1.0 g of A.I.B.N., the reaction was carried out for 
4 hours and after further adding thereto 0.5 g of A.I.B.N., the reaction 
was carried out for hours. Then, after adjusting the temperature of the 
reaction mixture to 30.degree. C., 10 g of 2-(methacrolyloxyethyl) 
isocyanate, 0.1 g of tetra(butoxy) thitanate, and 0.5 of 
t-butylhydroquinone were added to the reaction mixture and the resulting 
mixture was stirred for 8 hours. After cooling, the operation of 
reprecipitating the reaction mixture in 2 liters of methanol was repeated 
twice to provide 63 g of a light yellow viscous product of the polymer 
(M-4) shown below. The weight average molecular weight of the polymer was 
6,600. 
##STR19## 
Production Examples 5 to 15 of Monofunctional macromonomers (M): (M-5) to 
(M-15) 
By the method of using each mercapto compound containing a reactive group 
as the chain-transfer agent as in the method of Production Example 2 of 
the monofunctional macromonomer (M), each of the macromonomers (M) 
described in Table A shown below was produced. Mws of the macromonomers 
(M) obtained were in the range of from 6.times.10.sup.3 to 
1.times.10.sup.4. 
TABLE A 
__________________________________________________________________________ 
Production Example of Mono-Functional Macromonomer (M) 
Production 
Example 
Macromonomer (M) 
Chemical Structure of Macromonomer (M) 
__________________________________________________________________________ 
5 M-5 
##STR20## 
6 M-6 
##STR21## 
7 M-7 
##STR22## 
8 M-8 
##STR23## 
9 M-9 
##STR24## 
10 M-10 
##STR25## 
11 M-11 
##STR26## 
12 M-12 
##STR27## 
13 M-13 
##STR28## 
14 M-14 
##STR29## 
15 M-15 
##STR30## 
__________________________________________________________________________ 
Production Example 1 of Dispersion Stabilizing Resin (P): (P-1) 
A mixed solution of 97 g of octadecyl methacrylate, 3 g of monomer (B-1) 
having the following structure, and 200 g of toluene was heated to 
70.degree. C. with stirring under a nitrogen gas stream. Then, after 
adding to the mixture 1.2 g of A.I.B.N, the reaction was carried out 4 
hours and after further adding thereto 0.8 g of A.I.B.N., the reaction was 
carried out 4 hours. After cooling, the reaction mixture was 
reprecipitated in one liter of methanol and the precipitates formed were 
recovered by filtration and dried to provide 78 g of the polymer (P-1) 
shown below having a weight average molecular weight (Mw) of 
3.5.times.10.sup.4. 
##STR31## 
Production Examples 2 to 12 of Dispersion Stabilizing Resins (P): (P-2) to 
(P-12) 
By the method similar to Production Examples of the resin (P-1), each of 
the resins (P) shown in Table B below was produced. Mws of the polymers 
obtained were in the range of from 3.times.10.sup.4 to 5.times.10.sup.4. 
TABLE B 
__________________________________________________________________________ 
Production Example of Dispersion Stabilizing Resin [P] 
Production 
Example 
Resin [P] 
Polymerization Components of Resin [P] (weight 
__________________________________________________________________________ 
ratio) 
2 P-2 
##STR32## 
3 P-3 
##STR33## 
4 P-4 
##STR34## 
5 P-5 
##STR35## 
6 P-6 
##STR36## 
7 P-7 
##STR37## 
8 P-8 
##STR38## 
9 P-9 
##STR39## 
10 P-10 
##STR40## 
11 P-11 
##STR41## 
12 P-12 
##STR42## 
__________________________________________________________________________ 
Production Example 13 of Dispersion Stabilizing Resin (P): (P-13) 
A mixed solution of 100 g of hexadecyl methacrylate, 1.2 g of initiator 
(I-1) shown below, and 100 g of tetrahydrofuran was heated to 60.degree. 
C. with stirring under a nitrogen gas stream. The solution was 
photopolymerized by light-irradiating it for 12 hours with a 
light-pressure mercury lamp of 400 watts from the distance of 10 cm 
through a glass filter. 
The reaction mixture was reprecipitated in 1.5 liters of methanol and the 
precipitates were collected by filtration and dried to provide 80 g of a 
polymer (resin (P-13)) having Mw of 4.5.times.10.sup.4. 
##STR43## 
Production Examples 14 to 26 of Dispersion Stabilizing Resins (P): (P-14) 
to (P-26) 
By following the same procedure as the production example of the resin 
(P-13) except that 100 g of each of the monomers shown in Table C below 
was used in place of 100 g of hexadecyl methacrylate, each of the polymers 
(P-14) to (P-26) was produced. 
Mws of the polymers obtained were in the range of from 3.5.times.10.sup.4 
to 5.times.10.sup.4. 
TABLE C 
__________________________________________________________________________ 
Production Example of Dispersion Stabilizing Resin [P] 
##STR44## 
Production 
Example 
Resin [P] 
a X Y x/y (weight ratio) 
__________________________________________________________________________ 
14 P-14 CH.sub.3 
COOC.sub.18 H.sub.37 
-- 100/0 
15 P-15 CH.sub.3 
COOC.sub.12 H.sub.25 
-- 100/0 
16 P-16 CH.sub.3 
COOC.sub.18 H.sub.37 
##STR45## 70/30 
17 P-17 H OCOC.sub.17 H.sub.35 
-- 100/0 
18 P-18 H OC.sub.18 H.sub.37 
-- 100/0 
19 P-19 CH.sub.3 
COOC.sub.20 H.sub.41 
-- 100/0 
20 P-20 CH.sub.3 
COOC.sub.18 H.sub.37 
##STR46## 80/20 
21 P-21 CH.sub.3 
COOC.sub.16 H.sub.33 
##STR47## 90/10 
22 P-22 CH.sub.3 
COOC.sub.13 H.sub.27 
##STR48## 85/15 
23 P-23 CH.sub.3 
COOC.sub.18 H.sub.37 
##STR49## 80/20 
24 P-24 CH.sub.3 
COOC.sub.12 H.sub.25 
##STR50## 60/40 
25 P-25 H COOC.sub.13 H.sub.37 
-- 100/0 
26 P-26 H COOC.sub.18 H.sub.37 
-- 100/0 
__________________________________________________________________________ 
Production Example 27 of Dispersion Stabilizing Resin (P): (P-27) 
A mixture of 90 g of octadecyl methacrylate, 10 g of macromonomer (M-2), 
0.9 g of the initiator (I-2) shown below, and 100 g of toluene was heated 
to 50.degree. C. under a nitrogen gas stream. The solution was 
photopolymerized by light-irradiating it for 12 hours with a high-pressure 
mercury lamp of 400 watts from a distance of 10 cm through a glass filter. 
The reaction mixture was reprecipitated in 1.5 liters of methanol and the 
precipitates formed were collected by filtration and dried to provide 80 g 
of the polymer (resin (P-27)) having Mw of 5.times.10.sup.4. 
##STR51## 
Production Examples 28 to 39 of Dispersion Stabilizing Resins (P): (P-28) 
to (P-39) 
By following the same procedure as the production Example of the resin 
(P-27) except that 0.03 mol of each of the initiators described in Table D 
shown below in place of 0.9 g of the initiator (I-2), each of the polymers 
(P-28) to (P-39) was produced. 
Mws of the polymers obtained were in the range of from 4.times.10.sup.4 to 
5.times.10.sup.4. 
TABLE D 
__________________________________________________________________________ 
Production Example of Dispersion Stabilizing Resin [P] 
##STR52## 
ExampleProduction 
Resin [P] 
Initiator [I] 
##STR53## 
__________________________________________________________________________ 
28 P-28 
##STR54## 
##STR55## 
29 P-29 
##STR56## 
##STR57## 
30 P-30 
##STR58## 
##STR59## 
31 P-31 
##STR60## 
##STR61## 
32 P-32 
##STR62## 
##STR63## 
33 P-33 
##STR64## 
##STR65## 
34 P-34 
##STR66## 
##STR67## 
35 P-35 
##STR68## 
##STR69## 
36 P-36 
##STR70## 
##STR71## 
37 P-37 
##STR72## 
##STR73## 
38 P-38 
##STR74## 
##STR75## 
39 P-39 
##STR76## 
##STR77## 
__________________________________________________________________________ 
Production Examples 40 to 48 of Dispersion Stabilizing Resins (P) (P-40) to 
(P-48) 
By following the same procedure as the production example of the resin 
(P-27) except that each of the monomers and each of the macromonomers 
described in Table E shown below were used in place of 90 g of octadecyl 
methacrylate and 10 g of the macromonomer (M-2), each of the polymers 
(P40) to (P-48) was produced. 
Mws of the polymers obtained were in the range of from 4.times.10.sup.4 to 
6.times.10.sup.4. 
TABLE E 
__________________________________________________________________________ 
Production Example of Dispersion Stabilizing Resin [P] 
Production 
Example 
Resin [P] 
Monomer Macromonomer (M) 
__________________________________________________________________________ 
40 P-40 Hexadecyl methacrylate 
85 
g M-3 15 
g 
41 P-41 Docosenyl methacrylate 
90 
g M-4 10 
g 
42 P-42 Dodecyl methacrylate 
90 
g M-5 10 
g 
43 P-43 Tridecyl methacrylate 
67 
g M-6 13 
g 
Dodecyl acrylate 
20 
g 
44 P-44 Dodecyl methacrylate 
80 
g M-7 20 
g 
45 P-45 4-(Dodecyloxycarbonyl)styrene 
70 
g M-8 15 
g 
Octadecyl methacrylate 
15 
g 
46 P-46 Eicosanyl methacrylate 
80 
g M-9 20 
g 
47 P-47 Octadecyl acrylate 
84 
g M-13 
16 
g 
48 P-48 Dodecyl acrylate 
60 
g M-14 
10 
g 
Octadecyl methacrylate 
30 
g 
__________________________________________________________________________ 
Production Example 49 of Dispersion Stabilizing Resin (P): (P-49) 
A mixed solution of 85 g of tetradecyl methacrylate, 15 g of the 
macromonomer (M-11), and 200 g of tetrahydrofuran was heated to 65.degree. 
C. with stirring under a nitrogen gas stream. 
Then, after adding 3 g of A.C.V. to the mixture, the reaction was carried 
out for 4 hours and after further adding thereto 1.0 g of A.C.V., the 
reaction was carried out for 4 hours. After cooling the reaction mixture, 
2 g of the compound (A) shown below was added to the reaction mixture, 
furthermore, a mixed solution of 4 g of D.C.C. , 0.5 g of 
4-(N,N-dimethylamino)pyridine, and 10 g of methylene chloride was added 
dropwise thereto at 25.degree. C. over a period of one hour, and after 
further carrying out the reaction as they were, 10 g of an aqueous 
solution of 85% formic acid was added to the reaction mixture followed by 
stirring for 2 hours. 
Precipitates thus formed were collected by filtration, reprecipitated in 
one liter of methanol twice, and the precipitates formed were collected by 
filtration and dried to provide 60 g of the polymer (resin (P-49)) having 
Mw of 6.times.10.sup.4. 
##STR78## 
Production Example 1 of Dispersed Resin Particles: D-1 and Comparison 
Examples 1 and 2 
A mixed solution of 8 g of the dispersion stabilizing resin (P-14), 50 g of 
methyl methacrylate, 50 g of methyl acrylate, and 150 g of Isopar H was 
heated to 50.degree. C. with stirring under a nitrogen gas stream. The 
solution was photopolymerized by irradiating it with a high-pressure 
mercury lamp of 400 watts for 10 hours from a distance of 10 cm through a 
glass filter. After cooling, the reaction mixture was filtered with a 
nylon cloth of 200 mesh to provide a white dispersion, which was a latex 
having a polymerization ratio of 98% and a mean particle size of 0.18 
.mu.m. The particle size was measured by CAPA-500 (trade name, made by 
HORIBA, Ltd.). 
Then, under the same synthesis conditions as Production Example 1 of the 
dispersed resin particles of the present invention, that is, by the 
concentration (40% by weight) of a monomer (A) and the concentration (8% 
by weight to the monomer) of a dispersion stabilizing resin (P), a 
comparison test was carried out using a conventional polymerization 
reaction. 
Comparison Example 1: RD-1 
A mixed solution of 8 g of a dispersion stabilizing resin (RP-1) having the 
structure shown below, 50 g of methyl methacrylate, 50 g of methyl 
acrylate, and 150 g of Isopar H was heated to 60.degree. C. with stirring 
under a nitrogen gas steam. To the mixture was added 0.8 g of 
2,2'-azobis(isovaleronitrile) (A.I.V.N.) and the polymerization reaction 
was initiated. 
With the progress of the reaction, after 10 minutes, a white turbidity 
formed, after one hour, aggregates formed, and after 2 hours, a polymer 
formed was precipitated. 
Comparison Dispersion Stabilizing Resin (RP-1): 
##STR79## 
Then, a synthesis example (comparison example) capable of polymerization 
granulation using a polymerization initiator was shown below. 
Comparison Example 2: RD-2 
A mixed solution of 25 g of the dispersion stabilizing resin (RP-1) 
described above, 50 g of methyl methacrylate, 50 g of methyl acrylate, and 
566 g of Isopar H was heated to 60.degree. C. with stirring under a 
nitrogen gas stream. Then, after adding to the reaction mixture, 0.8 g of 
A.I.V.N., the reaction was carried out for 2 hours and after further 
adding thereto 0.5 g of A.I.V.N., the reaction was carried out for 3 
hours. After cooling, the reaction mixture obtained was filtered through a 
nylon cloth of 200 mesh to provide a white dispersion, which was a latex 
having a polymerization ratio of 92% and a mean particle size of 0.25 
.mu.m. 
As described above, in the process of polymerization granulation with the 
conventionally known polymerization initiator, the granulation of a resin 
was possible by lowering the concentration of the monomer and by using a 
dispersion stabilizing resin having a polymerizable double bond group in 
an amount of more than three times as compared with the method of the 
present invention. 
This is assumed to be caused by that the bonding effect of the dispersion 
stabilizing resin (RP-1) to the polymer of the monomer (A) which is 
insolubilized by causing a polymerization reaction is lowered as compared 
with the process of the present invention. 
Then, after preparing an Isopar G dispersion of the solid component 
concentration of 10% by weight using each of the resin particles (D-I) of 
the present invention and the resin particles (RD-2) obtained in 
Comparison Example 2, each dispersion was subjected to a centrifugal 
precipitation under a forced condition of a rotation number of 
1.times.10.sup.3 r.p.m. for 10 minutes, thereafter, the precipitates 
obtained were allowed to stand in a ultrasonic wave generator for 30 
minutes, and the redispersibility of the resin particles was compared. 
As the results, in the resin particles (D-1) of the present invention, the 
existence of coarse particles was not found by a visual observation and 
also by the measurement with CAPA-500, the particle size distribution was 
almost same as that before the centrifugal precipitation and no change was 
observed. 
On the other hand, in the comparison resin particles (RD-1), the existence 
of many coarse resin particles was visually observed. Furthermore, when 
the particle size distribution was measured by CAPA-500, the mean particle 
size of 0.25 .mu.m before the centrifugal precipitation was changed to 
0.40 .mu.m, i.e., the particle size distribution was very broadened and it 
is observed that the resin particles having particle sizes of at least 1 
.mu.m were contained in an amount of 30%. 
The excellence of the redispersion stability of the resin particles of the 
present invention is considered to be caused by that a sufficient amount 
of the dispersion stabilizing resin having a solvation property is 
chemically bonded to the resin particle portion of a non-solvation 
property with a good efficiency. In other words, in the resin particles of 
the present invention, the resin composed of an AB block copolymer of a 
polymer portion of solvation and a polymer portion of non-solvation is in 
a dispersed state. 
Production Example 2 of Dispersed Resin Particles: D-2 and Comparison 
Examples 3 and 4 
A mixed solution of 5 g of the dispersion stabilizing resin (P-40), 100 g 
of vinyl acetate, and 145 g of Isopar H was heated to 60.degree. C. with 
stirring under a nitrogen gas stream. The solution was photopolymerized by 
light-irradiating with a high-pressure mercury lamp of 400 watts for 10 
hours from a distance of 10 cm through a glass filter. After cooling, the 
polymerization product was filtered through a nylon cloth of 200 mesh to 
provide a white dispersion, which was a latex having a polymerization 
ratio of 98% and a mean particle size of 0.18 .mu.m. In addition, the 
particle sizes were measured by CAPA-500. 
Then, as described in the case of Production Example 1, the comparison 
examples of carrying out the polymerization granulation by conventional 
polymerization reactions are shown below. 
Comparison Example 3: RD-3 
A mixed solution of 5 g of the dispersion stabilizing resin (RP-2) having 
the structure shown below, 100 g of vinyl acetate, and 145 g of Isopar H 
was heated to 60.degree. C. with stirring under a nitrogen gas stream. 
Then, 0.8 g of A.I.V.N was added to the solution as a polymerization 
initiator and the polymerization reaction was initiated. With the progress 
of the reaction, after 10 minutes, a white turbidity occurred and further 
after 1.5 hours, a large amount of precipitates formed, whereby a 
dispersion was not obtained. 
Comparison Dispersion Stabilizing Resin (RP-2) 
##STR80## 
Comparison Example 4: RD-4 
A mixed solution of 10 g of the dispersion stabilizing resin (RP-2) 
described above, 100 g of vinyl acetate, and 400 g of Isopar G was heated 
to 70.degree. C. with stirring under a nitrogen gas stream. After adding 
to the solution 1.2 g of A.I.V.N., the reaction was carried out for 2 
hours, then after adding thereto 0.5 of A.I.V.N, the reaction was carried 
out for 2 hours, and after further adding thereto 0.5 g of A.I.V.N., the 
reaction was carried out for 2 hours. Then, the temperature of the 
reaction mixture was raised to 100.degree. C. to distill off unreacted 
vinyl acetate. After cooling, the reaction mixture was filtered through a 
nylon cloth of 200 mesh to provide a white dispersion, which was a latex 
having a polymerization ratio of 88% and a mean particle size of 0.19 
.mu.m. 
Then, on the dispersed resin particles (D-2) of the present invention and 
the comparison dispersed resin particles (RD-4) obtained as above, the 
redispersibility was evaluated by the same manner as the case of 
Production Example 1. 
In the dispersed resin particles (D-2) of the present invention, the change 
of the particle size distribution after the redispersion was not observed. 
On the other hand, in the comparison sample (RD-4), after the redispersion, 
many coarse particles formed by aggregation were observed and also as the 
result of measuring the particle size distribution by CAPA-500, it was 
found that the mean grain size was changed to 0.45 .mu.m and resin 
particles having particle sizes of 1 .mu.m or more were contained in an 
amount of 25%. 
From the above results, it could be seen that the dispersed resin particles 
obtained by the production process of the present invention showed very 
good dispersion stability and redispersion stability. 
Production Example 3 of Dispersed Resin Particles: D-3 and Comparison 
Examples 5 and 6 
A mixed solution of 10 g of the dispersion stabilizing resin (P-3), 70 g of 
benzyl methacrylate, 30 g of benzyl acrylate, and 290 g of Isopar H was 
heated to 40.degree. C. with stirring under a nitrogen gas stream. 
The solution was light-irradiated for 8 hours under the same 
light-irradiation condition as in Production Example 1. After cooling, the 
product was filtered through a nylon cloth of 200 mesh to provide a white 
dispersion, which was a latex having a polymerization ratio of 98% and a 
mean particle size of 0.25 .mu.m. 
Comparison Example 5: RD-5 
A mixed solution of the dispersion stabilizing resin (RP-3) having the 
structure shown below, 70 g of benzyl methacrylate, 30 g of benzyl 
acrylate, and 542 g of Isopar H was heated to 50.degree. C. with stirring 
under a nitrogen gas stream. Then, after adding to the solution 0.8 g of 
2,2'-azobis(2 -cyclopropionitrile) (A.C.P.P.), the reaction was carried 
out for 3 hours and after further adding thereto 0.5 g of A.C.P.P., the 
reaction was carried out for 2 hours. Also, the temperature of the system 
was raised to 75.degree. C. and after further adding thereto 0.5 g of 
A.I.V.N., the reaction was carried out for 3 hours. 
After cooling, the reaction mixture was filtered through a nylon cloth of 
200 mesh to provide a white dispersion having a mean grain size of 1.2 
.mu.m and a very broad particle size distribution. 
Comparison Dispersion Stabilizing Resin (RP-3) 
##STR81## 
Comparison Example 6: RD-6 
A mixed solution of 25 g of the dispersion stabilizing resin (RP-3) and 547 
g of Isopar H was heated to 50.degree. C. with stirring under a nitrogen 
gas stream. Then, to the solution was added dropwise a mixed solution of 
70 g of benzyl methacrylate, 30 g of benzyl acrylate, and 0.8 g of 
A.C.P.P. over a period of one hour. After 2 hours since the end of the 
addition of the mixed solution, 0.5 g of A.C.P.P. was added to the mixture 
and the reaction was carried out for 2 hours. Also, after further adding 
thereto 0.5 g of A.I.V.N., the reaction was carried out for 3 hours at 
75.degree. C. 
The white dispersion thus obtained was a dispersion of resin particles 
having a polymerization ratio of 95% and a mean particle size of 0.26 
.mu.m. 
On each of the dispersed resin particles (D-3) of the present invention and 
the comparison dispersed resin particles (RD-6) thus obtained, the 
redispersibility was evaluated by the same manner as the case of 
Production Example 1. 
In the dispersed resin particles (D-3) of the present invention, the change 
of the particle size distribution after the redispersion was not observed. 
On the other hand, in the comparison dispersed resin particles (RD-6), many 
coarse particles formed by aggregation after the redispersion were 
observed and about a half of the particles were precipitated without 
dispersing. 
From the above results, it could be seen that the dispersed resin particles 
obtained by the production process of the present invention showed very 
good dispersion stability and redispersion stability. 
Production Examples 4 to 17 of Dispersed Resin Particles: D-4 to D-7 
By following the same procedure as Production Example 1 of dispersed resin 
particles except for using each of the dispersion stabilizing resins 
described in Table F shown below in place of 8 g of the dispersion 
stabilizing resin (P-14), the dispersed resin particles (D-4) to (D-17) 
were produced. 
The mean particle sizes of the resin particles in the dispersions obtained 
were in the range of from 0.15 .mu.m and the particle size distributions 
were sharp. 
TABLE F 
______________________________________ 
Production Example of Dispersed Resin Particles 
Production Dispersion Dispersion Stabilizing 
Example Resin Particles 
Resin [P] and Amount 
______________________________________ 
4 D-4 P-1 10 g 
5 D-5 P-5 9 g 
6 D-6 P-10 10 g 
7 D-7 P-17 8 g 
8 D-8 P-18 9 g 
9 D-9 P-22 10 g 
10 D-10 P-26 10 g 
11 D-11 P-27 7 g 
12 D-12 P-30 7 g 
13 D-13 P-38 7 g 
14 D-14 P-41 8 g 
15 D-15 P-49 8 g 
16 D-16 P-39 8 g 
17 D-17 P-31 8 g 
______________________________________ 
Production Examples 18 to 38 of Dispersed Resin Particles: D-18 to D-38 
Each solution obtained by dissolving each definite amount of each compound 
described in Table G shown below with respect to the dispersion 
stabilizing resin (P) and the monomer (A) in 125 g of Isopor H was heated 
to 50.degree. C. with stirring under a nitrogen gas stream. The solution 
was light-irradiated for 12 hours under the same condition as Production 
Example D-1. 
Then, the reaction mixture was heated to 100.degree. C. at a reduced 
pressure of from 10 to 15 mmHg to distill off the unreacted monomer. After 
cooling, the product was filtered through a nylon cloth of 200 mesh to 
provide each white dispersion of resin particles. 
All the dispersed resin particles thus obtained showed a good 
mono-dispersibility and the mean particle sizes were in the range of from 
0.15 to 0.25 .mu.m. 
TABLE G 
__________________________________________________________________________ 
Production Example of Dispersion Resin Particles 
Dispersion 
Polymerization Ratio 
Production 
Dispersed Resin Stabilizing 
(weight % from 
Example 
Particles [D] 
Monomer (A) Resin [P] 
solid component) 
__________________________________________________________________________ 
18 D-18 Vinyl acetate 100 
g P-4 
18 
g 90% 
19 D-19 Vinyl acetate 80 g P-9 
12 
g 88% 
Vinyl propionate 20 g 
20 D-20 Methyl methacrylate 75 g P-11 
16 
g 98% 
Ethyl methacrylate 25 g 
21 D-21 Ethyl methacrylate 100 
g P-13 
10 
g 98% 
22 D-22 Benzyl methacrylate 100 
g P-31 
12 
g 96% 
23 D-23 Methyl methacrylate 60 g P-16 
10 
g 98% 
Ethyl methacrylate 30 g 
Acrylic acid 10 g 
24 D-24 Styrene 55 g P-26 
20 
g 85% 
Vinyltoluene 45 g 
25 D-25 Vinyl acetate 95 g P-34 
10 
g 86% 
Crotonic acid 5 g 
26 D-26 Vinyl methyl ether 20 g P-38 
8 g 88% 
Vinyl acetate 80 g 
27 D-27 Ethyl methacrylate 95 g P-41 
12 
g 98% 
N,N-Dimethylaminoethyl 
5 g 
methacrylate 
28 D-28 Methyl methacrylate 95 g P-22 
11 
g 97% 
Hexadecyl acrylate 5 g 
29 D-29 Styrene 50 g P-33 
10 
g 88% 
Vinyl acetate 50 g 
30 D-30 Vinyl acetate 98.5 
g P-45 
10 
g 89% 
Octadecyl methacrylate 
1.5 
g 
31 D-31 Vinyl acetate 98 g P-30 
10 
g 92% 
Dodecyl methacrylate 2 g 
32 D-32 Vinyl acetate 97 g P-17 
14 
g 89% 
##STR82## 3 g 
33 D-33 Methyl methacrylate 66 g P-35 
12 
g 96% 
Methyl acrylate 30 g 
##STR83## 4 g 
34 D-34 Methyl methacrylate 78 g P-47 
12 
g 99% 
Butyl acrylate 20 g 
Octadecyl acrylate 2 g 
35 D-35 Vinyl acetate 95 g P-49 
10 
g 92% 
##STR84## 5 g 
36 D-36 Benzyl methacrylate 92 g P-33 
15 
g 98% 
##STR85## 8 g 
37 D-37 Methyl vinyl ether 97 g P-18 
16 
g 86% 
Octadecyl vinyl ether 
3 g 
38 D-38 Methyl methacrylate 75 g P-22 
13 
g 98% 
Ethyl acrylate 15 g 
Dodecyl acrylate 10 g 
__________________________________________________________________________ 
Comparison Production Example 7 of Dispersed Resin Particles: RD-7 
By following the same procedure as Comparison Production Example 2 (RD-2) 
described above except that 20 g of the dispersion stabilizing resin 
(RP-2) described above was used in place of 25 g of the dispersion 
stabilizing resin (RP-1), a white dispersion of latex particles having a 
polymerization ratio of 93% and a mean particle size of 0.22 .mu.m was 
obtained. 
Comparison Production Example 8 of Dispersed Resin Particles: RD-8 
By following the same procedure as Comparison Production Example 4 (RD-4) 
described above except that 14 g of the dispersion stabilizing resin 
(RP-1) described above was used in place of 10 g of the dispersion 
stabilizing resin (RP-2), a white dispersion of latex particles having a 
polymerization ratio of 88% and a mean particle size of 0.18 .mu.m was 
obtained. 
Example 1 of Liquid Developer 
After placing 10 g of a dodecyl methacrylate/acrylic acid copolymer 
(copolymerization ratio: 95/5 by weight ratio), 10 g of Nigrosine, and 30 
g of Isopar G together with glass beads in a paint shaker (manufactured by 
Tokyo Seiki K.K.), they were dispersed for 4 hours to provide a dispersion 
of Nigrosine. 
Then, by diluting 6.5 (as solid components) of the resin dispersion (D-2) 
obtained in Production Example 2 of dispersed resin particles, 2.5 g of 
the Nigrosine dispersion described above, 15 g of branched octadecyl 
alcohol FOC-180 (made by Nissan Chemical Industries, Ltd.), and 0.07 g of 
an octadecene-half maleic acid octadecylamide copolymer with one liter of 
Isopar G, a liquid developer for electrostatic photography was prepared. 
Preparation of Comparison Liquid Developers A and B 
By following the production of the liquid developer described above except 
that each of the resin dispersions shown below was used in place of the 
resin dispersion (D-2), two kinds of comparison liquid developers A and B 
were prepared. 
Comparison Liquid Developer A: 
Resin dispersion (RD-4) prepared in Comparison Example 4 of dispersed resin 
particles was used. 
Comparison Liquid Developer B: 
Resin dispersion (RD-7) prepared in Comparison Example 7 of dispersed resin 
particles was used. 
By using each of these liquid developers thus prepared as the liquid 
developer for an all automatic plate-making machine ELP404V (trade name, 
manufactured by Fuji Photo Film Co.), ELP Master 11 Type (trade name, 
manufactured by Fuji Photo Film Co.) which was an electrophotographic 
photoreceptor was exposed and developed. The plate making speed was 7 
plates/minutes. Furthermore, the presence of stains by the attachment to 
toners to the development apparatus after processing 3,000 plates of ELP 
Master 11 Type was observed. The blackened ratio (imaged area) of the 
duplicated image was evaluated using an original of 30%. 
The results obtained are shown in Table H. 
TABLE H 
______________________________________ 
Staining of 
Developing 
Image of the 
No. Test Developer Apparatus 3,000th Plate 
______________________________________ 
1 Inven- Example 1 .smallcircle. 
.smallcircle. 
tion No toner Clear 
residue formed 
2 Com- Developer x x 
par- A Toner residue 
Lacking of 
ative formed character, blurring 
Exam- of solid black 
ple A portion, occurrence 
of background fog 
3 Com- Developer .smallcircle. 
.DELTA. 
para- B Toner residue 
Blurring of fine 
tive formed line, etc., 
Exam- slightly observed. 
ple B Lowering of Dmax 
______________________________________ 
When printing plates were prepared using each of the liquid developers 
under the foregoing plate-making condition, the developer which did not 
cause stains on the developing apparatus and gave clear images on the 
3,000th printing plate was only the liquid developer of the present 
invention. 
On the other hand, printing was conducted by an ordinary manner using each 
offset printing master plate (ELP plate) obtained by using each liquid 
developer, the number of prints until lacking of characters, blurs on the 
solid black portion, etc., formed on the images of a print was compared. 
Each printing master plate obtained by using each liquid developer directly 
after plate-making gave more than 10,000 prints having good printed 
images. 
However, when each liquid developer was used under severe plate-making 
conditions (conventionally, the plate-making speed was 2 or 3 
plates/minute and the blackened ratio of the duplicated image was about 8 
to 10%), the 3,000th master plate had clear images in the case of using 
only the liquid develope of the present invention, and in the comparison 
liquid developer A and the comparison liquid developer B, bad influences 
(lowering of D.sub.max, blurring of fine lines, black pepper-form stains 
on the non-imaged portions, etc.) were observed on the image quality of 
the images of the 3,000th master plate. 
This is because in the comparison liquid develope A and the comparison 
liquid developer B, when the liquid developer is used repeatedly for a 
long period of time, stains form on the developing apparatus (in 
particular, on the back surface of the electrode) by the developer since 
the resin particles of the liquid developer is insufficient in the 
redispersion stability, whereby the developing electrode does not 
sufficiently function to reduce the image quality, and further the resin 
particles attached on the developing apparatus are aggregated to form 
coarse particles which attach at random to the master plate to cause 
stains at the non-imaged portions. 
Accordingly, when printing was conducted by using the 3,000th master plate 
obtained using the comparison liquid developer A and the comparison liquid 
developer B, stains at the non-imaged portions and lacking of images 
occurred even on the 1st print. 
These results show that the resin particles of the present invention are 
clearly excellent. 
Example 2 of Liquid Developer 
By diluting 6 g (as solid components) of the resin dispersion (D-1) 
obtained in Production Example 1 of dispersed resin particles, 15 g of 
branched hexadecyl alcohol FOC-1600 (trade name, made by Nissan Chemical 
Industries, Ltd.), and 0.08 g of an octadecyl vinyl ether/half maleic acid 
dodecylamide copolymer with one liter of Isopar G, a liquid developer for 
electrostatic photography was prepared. 
Preparation of Comparison Liquid Developers C and D 
By following the same procedure as the production of the liquid developer 
described above except that each of the resin dispersions shown below was 
used in place of the resin dispersion (D-I), the comparison liquid 
developers C and D were prepared. 
Comparison Liquid Developer C: 
Resin dispersion (RD-2) prepared in Comparison Production Example 2 of 
dispersed resin particles was used. 
Comparison Liquid Developer D: 
Resin dispersion (RD-8) prepared in Comparison Production Example 8 of 
dispersed resin particles was used. 
These liquid developers were used for an electrophotographic plate-making 
system and various characteristics were evaluated. The results obtained 
are shown in Table I. 
TABLE I 
______________________________________ 
Staining of 
Developing 
Image of the 
No. Test Developer Apparatus 3,000th Plate 
______________________________________ 
1 Inven- Example 2 .smallcircle. 
.smallcircle. 
tion No toner Clear 
residue formed 
2 Com- Developer x .DELTA. 
par- C Toner residue 
Blurring of fine 
ative formed line, etc., 
Exam- slightly observed. 
ple C Lowering of Dmax 
3 Com- Developer x.about..DELTA. 
x 
para- D Toner residue 
Lacking of 
tive formed a character, blurring 
Exam- little of solid black 
ple D portion, occurrence 
of background fog 
______________________________________ 
In Table I, the measurement of stains of the developing apparatus and the 
evaluations of the image of the 3,000th master plate were conducted as in 
Example 1. Also, other terms were evaluated as follows. 
(Note): Preparation of Plate Image 
Preparation of Electrophotographic Photoreceptor P-1 
In a 500 milli-liter glass-made container were placed 1.9 parts by weight 
of an X-type nonmetal phthalocyanine (made by Dainippon Ink and Chemicals, 
Inc.) as an organic photoconductive compound, 0.15 parts by weight of the 
thiobarbituric acid compound having the structure shown below, 17 parts by 
weight of the binder resin B-1 having the structure shown below, and 100 
parts by weight of a mixed solution of tetrahydrofuran and cyclohexan at 
8/2 by weight ratio together with glass beads and after dispersing with a 
paint shaker for 60 minutes, the glass beads were filtered away to provide 
a dispersion for a photoconductive layer. 
Then, the dispersion for photoconductive layer was coated on a grained 
aluminum plate of 0.25 mm in thickness and dried to provide a printing 
master plate for electrophotographic plate making having a photoconductive 
layer of 6.0 .mu.m in dry thickness. 
##STR86## 
After electrostatically charging the surface of an electrophotographic 
photoreceptor P-1 prepared as shown above to a potential of +450 volts in 
the dark, the surface of the photoreceptor was exposed by a 
gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 
nm) of 2.8 mW output as a light source under an exposure of 60 
ergs/cm.sup.2 at a pitch of 25 .mu.m, and a scanning speed of 300 
meters/sec. and then developed using each of the liquid developers 
described above by applying a bias voltage of 30 volts to the counter 
electrode to obtain a toner image. Furthermore, the toner image was fixed 
by heating to 100.degree. C. for one minute. 
Each master plate thus obtained was immersed in a processing liquid E-1 
having the following composition for 30 seconds to remove the 
photoconductive layer at the non-imaged portions and after washing with 
water for 30 seconds, air-dried with a dryer. 
Composition of Processing Liquid E-1: 
______________________________________ 
Potassium Silicate 40 g 
Potassium Hydroxide 10 g 
Ethanol 100 g 
Water 800 g 
______________________________________ 
The existence of lacking of fine lines and fine characters of the imaged 
portions of the printing master plate was visually evaluated with a 
magnifying lens (made by PEAK K.K.) of 60 magnifications. 
Then, when printing plates were made using each of the liquid developers 
under the plate-making conditions described above, only the liquid 
developer of the present invention did not stain the developing apparatus 
and gave clear images on the 3,000th printing plates. 
After gumming each offset printing plate prepared by treating each master 
plate under the same condition as described above in (Note), the printing 
plate was mounted on an offset printing machine, (Oliver Model 52, 
manufactured by Sakurai Seisakusho K.K.) and the number of prints obtained 
without causing background stains on the non-imaged portions of the print 
and problems on the quality of the imaged portions thereof was determined 
(the larger number of the prints shows the better printing resistance). 
The master plates obtained using the liquid developers directly after the 
initiation of plate-making gave a print having good printed images even 
after printing more than 100,000 prints. 
However, the 3,000th master plate only obtained using the liquid developer 
of the present invention had clear images, and in the case of using the 
comparison liquid developer C and the comparison liquid developer D, bad 
influences (lower of D.sub.max, blurring of fine lines, black pepper-form 
stains on the non-imaged portions, etc.) were observed on the image 
quality of the images formed on the 3,000th master plate. 
This is because in the comparison liquid developer C and the comparison 
liquid developer D, when the liquid developer is used repeatedly for a 
long period of time, stains form on the developing apparatus (in 
particular, on the back surface of the electrode) since the resin 
particles in the liquid developer are insufficient in the redispersion 
stability, whereby the developing electrode does not sufficiently function 
and reduces the image quality, and further resin particles attached onto 
the developing apparatus aggregate to form coarse particles which attach 
at random on the plate to cause background stains on the non-imaged 
portions. 
Accordingly, when printing was conducted using the 3,000th printing plate 
obtained using the comparison liquid developer C and the comparison liquid 
developer D, background stains on the non-imaged portions and lacking on 
the imaged portions formed on the 1st print. 
These results show that the resin particles of the present invention are 
clearly excellent. 
Examples 3 to 18 of Liquid Developer 
By following the same procedure as Example 1 of liquid developer except 
that 6.5 g (solid components) of each of the dispersed resin particles 
described in Table J shown below was used in place of 6.5 g of the 
dispersed resin particles (D-2), each of liquid developers was prepared. 
TABLE J 
______________________________________ 
Dispersed Resin 
Example Particles (D) 
______________________________________ 
3 D-18 
4 D-19 
5 D-20 
6 D-1 
7 D-11 
8 D-14 
9 D-15 
10 D-24 
11 D-30 
12 D-31 
13 D-32 
14 D-35 
15 D-37 
16 D-34 
17 D-33 
18 D-38 
______________________________________ 
Each liquid developer was operated by the same manner as in Example 1 and 
the properties were determined. Each of the liquid developers of Examples 
3 to 10 showed a good result even after making 3,000 printing plates as in 
Example 2. 
Furthermore, each of the liquid developers 11 to 18 each using the 
dispersion obtained by polymerization granulation of the monomer (A) of 
the present invention in the presence of a small amount of a 
monofunctional monomer having a long chain alkyl group copolymerizable 
with the foregoing monomer or a monofunctional monomer having at least two 
polar groups, had better properties and after making 3,500 printing 
plates, stains did not form on the developing apparatus and the images on 
the 3,500th printing plate had no stains and was clear. 
As described above, each of the liquid developers of the present invention 
showed the good result. 
Examples 19 to 36 
By following the same procedure as Example 2 except that 6.0 g (as solid 
components) of each of the dispersed resin particles described in Table K 
shown below was used in place of the dispersed resin particles D-1, each 
of liquid developers was prepared. 
TABLE K 
______________________________________ 
Dispersed Resin 
Example Particles (D) 
______________________________________ 
19 D-4 
20 D-6 
21 D-8 
22 D-9 
23 D-10 
24 D-12 
25 D-16 
26 D-17 
27 D-20 
28 D-3 
29 D-22 
30 D-24 
31 D-27 
32 D-39 
33 D-33 
34 D-36 
35 D-38 
36 D-28 
______________________________________ 
Each of the liquid developers thus prepared was operated by the same manner 
as in Example 2 and the properties were determined. 
Each of the liquid developers of Examples 19 to 32 showed a good result 
even after making 3,000 printing plates as in Example 2. 
Furthermore, each of the liquid developers of Examples 33 to 36 using the 
dispersion obtained by the polymerization granulation of the monomer (A) 
of the present invention in the presence of a small amount of a 
monofunctional monomer having a long chain alkyl group copolymerizable 
with the foregoing monomer or a monofunctional monomer having at least two 
polar groups, had better properties and after making 3,500 printing 
plates, stains did not form on the developing apparatus and the images on 
the 3,500th printing plate had no stain and was clear. 
As described above, each of the liquid developers of the present invention 
showed the good result. 
Example 37 
A mixture of 100 g of the white resin dispersion (D-23) described above and 
3 g of Victoria Blue B was heated to a temperature of from 70.degree. C. 
to 80.degree. C. followed by stirring for 6 hours. After cooling to room 
temperature, the mixture was filtrated through a nylon cloth of 200 mesh 
to remove the remaining dye and to provide a blue resin dispersion having 
a mean particle size of 0.20 .mu.m. 
By diluting 5.5 g (as solid components) of the foregoing blue resin 
dispersion, 0.06 f of the polymer having the structure shown below, and 10 
g of branched tetradecyl alcohol FOC-1400 (trade name, made by Nissan 
Chemical Industries, Ltd.) with one liter of Isopar G, a liquid developer 
for electrostatic photography was prepared. 
##STR87## 
When the liquid developer was operated by the same manner as in Example 1 
and the formation of stains on the developing apparatus was evaluated, the 
developer showed the good result as in Example 1. Herein, an 
electrophotographic photoreceptor 8-2 was used. 
Preparation of Electrophotographic Photoreceptor P-2 
A mixture of 34 g of the binder resin (B-2) having the structure shown 
below, 6 g of the binder resin (B-3) having the structure shown below, 200 
g of photoconductive zinc oxide, 0.2 g of phthalic anhydride, 0.01 g of 
phenol, 0.018 g of the cyanine dye (A) having the structure shown below, 
and 300 g of toluene was dispersed for 10 minutes using a homogenizer at a 
rotation number of 1.times.10.sup.4 rpm to provide a dispersion for 
forming a photoconductive layer. 
The dispersion was coated on a paper subjected to an electrically 
conductive treatment with a wire bar at dry coated amount of 25 g/m.sup.2, 
dried at 100.degree. C. for 20 seconds, and further heated to 120.degree. 
C. for one hour. Then, the coated paper was allowed to stand for 24 hours 
in the dark at 20.degree. C. and 65% RH to provide an electrophotographic 
photoreceptor P-2. 
##STR88## 
Then, after electrostatically charging an electrophotoreceptor P-2 prepared 
as shown above to -6 kV in the dark and exposing the surface of the 
photoreceptor using a gallium-aluminum-arsenic semiconductor laser of 2.0 
mW (oscillation wavelength 780 nm) output as a light source under the 
exposure of 45 ergs/cm.sup.2 at a pitch of 25 .mu.m and a scanning speed 
of 300 meters/sec., the photoreceptor was developed using the liquid 
developer of the present invention prepared by the above procedure, 
thereafter, was rinsed through a rinse bath of an Isopar G liquid, and 
heated to 60.degree. C. for 30 seconds to provide a toner image. 
When the image of the printing plate after making 3,000 printing plates by 
repeating the plate-making process as described above was evaluated, 
copying paper having clear blue image without having background stains at 
the non-imaged portions could be obtained. 
The nonaqueous resin dispersion of the present invention obtained by the 
photopolymerization process by the irradiation of ultraviolet rays having 
a wavelength of not longer than 400 nm is excellent in the dispersion 
stability and the redispersion stability as compared with a conventional 
nonaqueous resin dispersion by a polymerization granulation process using 
a polymerization initiator. 
Also, when 3,000 printing plates were made using the nonaqueous resin 
dispersion of the present invention as the liquid developer, stains were 
not formed on the developing apparatus and the image on the 3,000th 
printing plate was clear. Furthermore, when printing was conducted using 
the 3,000th printing plate, excellent prints without having background 
stains on the non-imaged portions and lacking on the imaged portions were 
obtained. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modification can be made therein without 
departing from the spirit and scope thereof.