Liquid developer for electrostatic photography

A liquid developer for electrostatic photography comprising resin grains dispersed in a non-aqueous solvent having an electric resistance of at least 10.sup.9 cm and a dielectric constant of not higher than 3.5 is disclosed. The dispersed resin grains contained therein are grains of a copolymer obtained by polymerizing a solution containing at least one monofunctional monomer (A) which is soluble in the aforesaid non-aqueous solvent but becomes insoluble after being polymerized and at least one monfunctional macromonomer (M) having a number average molecular weight of not more than 1.times.10.sup.4 and having a polymerizable double bond group represented by formula (M-II) bonded to only one terminal of a polymer main chain composed of a recurring unit represented by formula (M-I) in the presence of a dispersion stabilizing resin which is a polymer having at least a recurring unit represented by formula (I), a part of which has been crosslinked, and has a polymerizable double bond group copolymerizable with the monofunctional monomer (A) bonded to only one terminal of at least one polymer main chain thereof, the dispersion stabilizing resin being soluble in the non-aqueous solvent. The liquid developer is excellent in redispersibility, storability, stability, image-reproducibility and fixability.

FIELD OF THE INVENTION 
This invention relates to a liquid developer for electrophotography, which 
comprises a resin dispersed in a liquid carrier having an electric 
resistance of at least 10.sup.9 .OMEGA. cm and a dielectric constant of 
not higher than 3.5, and more particularly to a liquid developer excellent 
in re-dispersibility, storability, stability, image-reproducibility, and 
fixability. 
BACKGROUND OF THE INVENTION 
In general, a liquid developer for electrophotography is prepared by 
dispersing an inorganic or organic pigment or dye such as carbon black, 
nitrosine, phthalocyanine blue, etc., a natural or synthetic resin such as 
an alkyd resin, an acrylic resin, rosine, synthetic rubber, etc., in a 
liquid having a high electric insulating property and a low dielectric 
constant, such as a petroleum aliphatic hydrocarbon, and further adding a 
polarity-controlling agent such as a metal soap, lecithin, linseed oil, a 
higher fatty acid, a vinyl pyrrolidone-containing polymer, etc. to the 
resulting dispersion. 
In such a developer, the resin is dispersed in the form of insoluble latex 
grains having a grain size of from several .mu.m to several hundred nm. In 
a conventional liquid developer, however, the soluble 
dispersion-stabilizing resin and the polarity-controlling agent are 
insufficiently bonded to the insoluble latex grains, so that the soluble 
dispersion-stabilizing resin and the polarity-controlling agent become 
freely dispersed in the liquid developer with ease. Accordingly, the 
soluble dispersion-stabilizing resin would be split off from the insoluble 
latex grains after storage of the liquid developer for a long period of 
time or after repeated use thereof, so that the grains would thereafter 
defectively precipitate, coagulate or accumulate, or the polarity would 
thereby become indistinct. Since the grains once coagulated and 
accumulated are reluctant to redisperse, the grains would be adhered to 
everywhere in the developing machine, and, as a result, cause stain of 
images formed and malfunction of the developing machine such as clogging 
of the liquid-feeding pump. 
In order to overcome such defects, a means of chemically bonding the 
soluble dispersion-stabilizing resin and the insoluble latex grains is 
disclosed in U.S. Pat. No. 3,990,980. However, the liquid developer 
disclosed was still insufficient, although the dispersion stability to 
spontaneous precipitation of the grains was improved in some degree. When 
the liquid developer was actually used in a developing apparatus, the 
toner adhered to parts of the apparatus and solidified to form a film 
thereon, and the thus solidified toner grains could hardly be 
re-dispersed. In addition, the solidified toner grains caused stain of the 
images duplicated and troubles in the apparatus. Accordingly, the liquid 
dispersion as disclosed in U.S. Pat. No. 3,990,980 was found to have a 
defect that the redispersion stability was still insufficient for 
practical use. 
In accordance with the method of preparing the resin grains as disclosed in 
U.S. Pat. No. 3,990,980, there is an extreme limitation on the combination 
of the dispersing stabilizer to be used and the monomers to be 
insolubilized, in order to prepare monodispersed grains having a narrow 
grain size distribution. Mostly, the resin grains prepared by the method 
would contain a large amount of coarse grains having a broad grain size 
distribution, or would be polydispersed grains having two or more 
different mean grain sizes. In accordance with such a method, it is 
difficult to obtain monodispersed grains having a narrow grain size 
distribution and having a desired mean grain size, and the method often 
results in large grains having a grain size of 1 .mu.m or more, or 
extremely fine grains having a grain size of 0.1 .mu.m or less. In 
addition, the dispersion stabilizer to be used in the method has another 
problem in that it must be prepared by an extremely complicated process 
requiring a long reaction time. 
In order to overcome the aforesaid defects, a method of improving the 
dispersibility, the redispersibility, and the storage stability of 
insoluble dispersion resin grains by forming the grains of a copolymer 
from a monomer to be insolubilized and a monomer containing a long chain 
alkyl moiety is disclosed in JP-A-60-179751 (corresponding to EP-A-155788) 
and JP-A 62-151868 (the term "JP-A" as used herein means an "unexamined 
published Japanese patent application"). 
Also, a method of improving the dispersibility, the re-dispersibility, and 
the storage stability of insoluble dispersion resin grains by forming the 
grains by polymerizing a monomer being stabilized in the presence of a 
polymer utilizing a di-functional monomer or a polymer utilizing a high 
polymer reaction is disclosed in JP-A-60-185962 and JP-A-61-43757. 
On the other hand, a method of printing a large number of prints of 5000 or 
more prints has recently been developed, using an offset printing master 
plate by electrophotography. In particular, because of further improvement 
of the master plate, it has become possible to print 10,000 or more prints 
of large size by electrophotography. In addition, noticeable progress has 
been made in shortening the operation time in an electrophotomechanical 
system, and the step of development-fixation in the system has been 
conveniently accelerated. 
The grains prepared by the methods disclosed in aforesaid JP-A-60-179751 
and JP-A-61-151868 might be good in the mono-dispersibility, 
re-dispersibility, and storage stability of the grains, but showed 
unsatisfactory performance with respect to the printability for master 
plates of a large size and quickening of the fixation time. 
Also, the dispersion resin grains prepared by the methods disclosed in 
aforesaid JP-A-60-185962 and 61-43757 were not always satisfactory in the 
points of the dispersibility and re-dispersibility of the grains and in 
the point of printability in the case of a shortened fixation time or in 
the case of master plates of a large size (e.g., A-3 size (297.times.420 
mm.sup.2)) or larger. 
SUMMARY OF THE INVENTION 
This invention has been made for solving the aforesaid problems inherent in 
conventional liquid developers. 
An object of this invention is to provide a liquid developer excellent in 
dispersion stability, redispersibility, and fixability, and in particular 
to provide a liquid developer excellent in dispersion stability, 
re-dispersibility, and fixability even in an electrophotomechanical system 
wherein the development-fixation step is quickened and master plates of a 
large size are used. 
Another object of the present invention is to provide a liquid developer 
capable of forming an offset printing plate precursor having excellent 
ink-receptivity to printing ink and excellent printing durability by 
electrophotography. 
Still another object of the present invention is to provide a liquid 
developer which is suitable for various electrostatic photographic uses 
and various transferring uses, in addition to the above-mentioned uses. 
A further object of the present invention is to provide a liquid developer 
which can be used in any and every liquid developer-using system, for 
example, for ink-jet recording, cathode ray tube recording, or recording 
by pressure variation or electrostatic variation. 
The above described objects can be attained by the present invention as set 
forth hereinbefore. 
According to this invention, there is provided a liquid developer for 
electrostatic photography comprising resin grains dispersed in a 
non-aqueous solvent having an electric resistance of at least 10.sup.9 
.OMEGA. cm and a dielectric constant of not higher than 3.5, wherein the 
dispersed resin grains are grains of a copolymer obtained by polymerizing 
a solution containing at least one monofunctional monomer (A) which is 
soluble in the aforesaid non-aqueous solvent, but becomes insoluble after 
being polymerized and at least one monofunctional macromonomer (M) having 
a number average molecular weight of not more than 1.times.10.sup.4 and 
having a polymerizable double bond group represented by following formula 
(M-II) bonded to only one terminal of a polymer main chain composed of a 
recurring unit represented by following formula (M-I), in the presence of 
a dispersion-stabilizing resin which is a polymer having at least a 
recurring unit represented by the following formula (I), a part of which 
has been crosslinked, and has a polymerizable double bond group 
copolymerizable with the monofunctional monomer (A) bonded to only one 
terminal of at least one polymer main chain thereof, said 
dispersion-stabilizing resin being soluble in the non-aqueous solvent; 
##STR1## 
wherein T.sup.1 represents --COO--, --OCO--, --CH.sub.2 OCO--, --CH.sub.2 
COO--, --O-- or --SO.sub.2 --; A.sup.1 represents an aliphatic group 
having from 6 to 32 carbon atoms; and 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 having from 1 to 8 carbon atoms, 
--COO--Z.sup.1 or --COO--Z.sup.1 bonded via a hydrocarbon group having 
from 1 to 8 carbon atoms (wherein Z.sup.1 represents a hydrogen atom or a 
hydrocarbon group having from 1 to 18 carbon atoms); 
##STR2## 
wherein V.sup.0 represents --COO--, --OCO--, --CH.sub.2).sub.l COO--, 
--CH.sub.2).sub.l OCO--, --O--, --SO.sub.2 --, --CONHCOO--, --CONHCONH--, 
--CON--, 
##STR3## 
(wherein D.sup.1 represents a hydrogen atom or a hydrocarbon group having 
from 1 to 22 carbon atoms and l represents an integer of from 1 to 3); 
R.sup.0 represents a hydrocarbon group having from 1 to 22 carbon atoms, 
which may contain --O--, --CO--, --CO.sub.2 --, --OCO--, --SO.sub.2 --, 
##STR4## 
(wherein D.sup.2 has the same meaning as D.sup.1) in the carbon chain 
thereof, and b.sup.1 and b.sup.2, which may be the same or different, each 
represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon 
group having from 1 to 8 carbon atoms, --COO--D.sup.3, or --COO--D.sup.3 
bonded via a hydrocarbon group having from 1 to 8 carbon atoms (wherein 
D.sup.3 represents a hydrogen atom or a hydrocarbon group having from 1 to 
8 carbon atoms which may be substituted); 
##STR5## 
wherein V.sup.1 has the same meaning as V.sup.0 of formula (M-I) and 
c.sup.1 and c.sup.2, which may be the same or different, have the same 
meaning as b.sup.1 and b.sup.2 of formula (M-I).

DETAILED DESCRIPTION OF THE INVENTION 
Then, the liquid developer of this invention is described in detail. 
As the liquid carrier for the liquid developer of this invention having an 
electric resistance of at least 10.sup.9 .OMEGA. cm and a dielectric 
constant of not higher than 3.5, straight chain or branched aliphatic 
hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and 
halogen-substituted derivatives thereof can be preferably used. Examples 
thereof are octane, isooctane, decane, isodecane, decalin, nonane, 
dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, 
toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L 
(Isopar: trade name of Exxon Co.), Shellsol 70, Shellsol 71 (Shellsol: 
trade name of Shell Oil Co.), Amsco OMS and Amsco 460 Solvent (Amsco: 
trade name of Americal Mineral Spirits Co.). They may be used singly or as 
a combination thereof. 
The non-aqueous dispersion resin grains (hereinafter are often referred to 
as "latex grains") which are the most important constituting element in 
this invention are a copolymer resin obtained by polymerizing (a so-called 
polymerization granulation method) the aforesaid monomer (A) and the 
macromonomer (M) in the presence of the dispersion-stabilizing resin which 
is the polymer having at least a recurring unit represented by the 
aforesaid formula (I), a part of which has been crosslinked, has a 
polymerizable double bond group copolymerizable with the monofunctional 
monomer (A) bonded to only one terminal of at least one polymer chain 
thereof, and is soluble in the non-aqueous solvent. 
As the non-aqueous solvent for use in this invention, any solvents miscible 
with the aforesaid liquid carrier for the liquid developer for 
electrostatic photography can be basically used in this invention. 
That is, the non-aqueous solvent being used in the production of the 
dispersion resin grains may be any solvent miscible with the aforesaid 
liquid carrier and preferably includes straight chain or branched 
aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and 
halogen-substituted derivatives thereof. Specific examples thereof are 
hexane, octane, isooctane, decane, isodecane, decalin, nonane, 
isododecane, and isoparaffinic petroleum solvents such as Isopar E, Isopar 
G, Isopar H, Isopar L, Shellsol 70, Shellsol 71, Amsco OMS, and Amsco 460. 
They may be used singly or as a combination thereof. 
Other solvents which can be used together with the aforesaid organic 
solvent in this invention include alcohols (e.g., methanol, ethanol, 
propyl alcohol, butyl alcohol, 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), and halogenated 
hydrocarbons (e.g., methylene dichlorine, chloroform, carbon 
tetrachloride, dichloroethane, and methyl chloroform). 
It is preferred that the non-aqueous solvents which are used as a mixture 
thereof are distilled off by heating or under a reduced pressure after the 
polymerization granulation. However, even when the solvent is carried in 
the liquid developer as a dispersion of the latex grains, it gives no 
problem if the liquid electric resistance of the developer is in the range 
of satisfying the condition of at least 10.sup.9 .OMEGA. cm. 
In general, it is preferred that the same solvent as the liquid carrier is 
used in the step of forming the resin dispersion and as such a solvent, 
there are straight chain or branched aliphatic hydrocarbons, alicyclic 
hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc., as 
described above. 
The dispersion-stabilizing resin (dispersion stabilizer) which is used for 
forming a stable resin dispersion of the copolymer insoluble in the 
aforesaid non-aqueous solvent formed by copolymerizing the monofunctional 
monomer (A) and the macromonomer (M) in a non-aqueous solvent is a resin 
soluble in the non-aqueous solvent, which is a polymer having at least a 
recurring unit shown by the aforesaid formula (I), a part of which has 
been crosslinked, and has a polymerizable double bond group 
copolymerizable with the aforesaid monomer (A) bonded to only one terminal 
of at least one polymer main chain thereof, which is one of the features 
of this invention. 
Then, the dispersion stabilizer (dispersion stabilizing resin) in this 
invention is described in detail. 
In formula (I) showing the recurring unit of the copolymer component, the 
hydrocarbon groups may be substituted. 
In formula (I), T.sup.1 preferably represents --COO--, --OCO--, --CH.sub.2 
OCO--, or --CH.sub.2 COO--. 
A.sup.1 preferably represents a hydrocarbon group having from 8 to 22 
carbon atoms and includes practically aliphatic groups such as octyl, 
decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, 
eicosanyl, octenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, 
hexadecenyl, octadecenyl, dococenyl, etc. 
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., 
fluorine, chlorine, and bromine), a cyano group, a hydrocarbon group 
having from 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and 
phenyl), --COO--Z.sup.1 or --COO--Z.sup.1 bonded via a hydrocarbon group 
having from 1 to 6 carbon atoms (wherein Z.sup.1 represents a hydrogen 
atom or a hydrocarbon atom having from 1 to 18 carbon atoms (e.g., methyl, 
ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 
hexadecyl, octadecyl, butenyl, hexenyl, octenyl, decenyl, benzyl, 
phenethyl, phenyl, chlorobenzyl, bromobenzyl, methylbenzyl, chlorophenyl, 
bromophenyl, and tolyl)). More preferably, either a.sup.1 or a.sup.2 
represents a hydrogen atom. 
The dispersion-stabilizing resin in this invention may further have a 
recurring unit other than the recurring unit shown by the formula (I) in 
addition to the recurring unit of the formula (I). 
Such recurring units other than that shown by the formula (I) which can be 
used in this invention include any monofunctional monomers copolymerizable 
with the monomer corresponding to the recurring unit shown by the formula 
(I). 
As such other recurring unit, there are practically recurring units shown 
by the following formula (IV); 
##STR6## 
wherein T.sup.2 represents --COO--, --OCO--, --CH.sub.2 OCO--, --CH.sub.2 
COO--, --SO.sub.2 --, --O--, --S--, 
##STR7## 
--NHCO--, --CH.sub.2 NHCO--, --NHSO.sub.2 --, --CH.sub.2 NHSO.sub.2 --, 
--CONHCOO--, --CONHSO.sub.2 --, --NHCONH-- or 
##STR8## 
In the above formulae, W.sup.1 represents a hydrogen atom or a substituted 
or unsubstituted hydrocarbon group having from 1 to 18 carbon atoms (e.g., 
methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, 
octadecyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-chloroethyl, 2-cyanoethyl, 
2-methoxycarbonylethyl, 2-carboxyethyl, butenyl, hexenyl, octenyl, 
cyclohexyl, benzyl, phenethyl, phenyl, tolyl, naphthyl, chlorophenyl, 
bromophenyl, methoxyphenyl, bromobenzyl, methylbenzyl, and methoxybenzyl) 
and W.sup.2 represents a hydrogen atom, a halogen atom (e.g., fluorine, 
chlorine, and bromine), an alkyl group (e.g., methyl, ethyl, propyl, 
chloromethyl, hydroxymethyl, N,N-dimethylaminomethyl, and 
N,N-diethylaminomethyl), a hydroxy group, a carboxy group or a sulfo 
group. In the above formula, s represents an integer of from 1 to 4. 
In the above formula, Z.sup.3 represents a linkage group or a bond linking 
between Z.sup.2 and the benzene ring, and is, for example, --COO--, 
##STR9## 
a bond directly bonding between Z.sup.2 and the benzene ring, etc., 
(W.sup.3 has the same meaning as W.sup.1). 
In formula (IV), Z.sup.2 represents a hydrogen atom, an unsubstituted 
hydrocarbon group having from 1 to 6 carbon atoms (e.g., methyl, ethyl, 
propyl, butyl, heptyl, hexyl, cycloheptyl, cyclohexyl, hexenyl, and 
phenyl), a substituted aliphatic group having from 1 to 22 carbon atoms 
[in which examples of the substituent include a halogen atom (e.g., 
fluorine, chlorine, bromine, and iodine), --OH, --SH, --COOH, --SO.sub.3 
H, --SO.sub.2 H, --PO.sub.3 H.sub.2, --CN, --CONH.sub.2, --SO.sub.2 
NH.sub.2, 
##STR10## 
(W.sup.4 and W.sup.5 each has the same meaning as W.sup.1), --OCOW.sup.6, 
--O--W.sup.6, --S--W.sup.6, 
##STR11## 
--COOW.sup.6, --SO.sub.2 W.sup.6 (W.sup.6, W.sup.7, and W.sup.8 each 
represents a hydrocarbon group having from 1 to 18 carbon atoms, which may 
be substituted, and has practically the same meaning as W.sup.1)], a 
heterocyclic group (e.g., thiophene, pyran, furan, pyridine, morpholine, 
piperidine, imidazole, benzimidazole, and thiazole), or an aromatic group 
which may be substituted (e.g., phenyl, naphthyl, tolyl, xylyl, mesityl, 
fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl, dibromophenyl, 
trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, carboxyphenyl, 
sulfophenyl, carboxyamidophenyl, sulfoamidophenyl, methoxycarbonylphenyl, 
acetamidophenyl, cyanophenyl, nitrophenyl, and methanesulfonylphenyl). 
In formula (IV), e.sup.3 and e.sup.4, which may be the same or different, 
each has the same meaning as a.sup.1 and a.sup.2 in the formula (I) 
described above. 
Furthermore, the polymer in this invention may contain monomers other than 
the monomer corresponding to the recurring unit shown by the above formula 
(IV), and examples thereof are maleic acid, maleic anhydride, itaconic 
anhydride, vinylnaphthalenes, and vinyl heterocyclic compounds having a 
vinyl group directly substituted to the ring (e.g., vinylpyridine, 
vinylimidazole, vinylthiophene, vinylpyrrolidone, vinylbenzoimidazole, and 
vinyltriazole). 
The dispersion stabilizing resin of this invention is a polymer containing 
a polymer component selected from the recurring units shown by formula (I) 
as the homopolymer component or as a copolymer component. This polymer is 
obtained by copolymerizing the monomer corresponding to the recurring unit 
shown by (I) with another monomer copolymerizable with the monomer 
corresponding to the recurring unit (I) (e.g., a monomer corresponding to 
the recurring unit shown by aforesaid formula (IV) as a copolymerizable 
copolymer component, a pat of the polymer being crosslinked, and the 
polymer has a polymerizable double bond group bonded to only one terminal 
of at least one polymer main chain. 
When the dispersion stabilizing resin of this invention contains a 
copolymer obtained by copolymerizing a monomer corresponding to the 
recurring unit shown by formula (I) and other monomer (e.g., a monomer 
corresponding to the recurring unit shown by the formula (IV)) 
copolymerizable with said monomer as a copolymer component, the proportion 
of the monomer corresponding to the recurring unit shown by formula (I) is 
at least 30 parts by weight, preferably at least 50 parts by weight, and 
more preferably at least 70 parts by weight to 100 parts by weight of the 
whole monomers. 
As a method of introducing the crosslinked structure into the polymer, a 
conventionally known method can be utilized. 
That is, there is a method of polymerizing the monomer(s) in the presence 
of a polyfunctional monomer or a method of incorporating a functional 
group progressing a crosslinking reaction and performing the crosslinking 
by polymer reaction. A method of crosslinking the polymer and chain by 
polymerizing a monomer having at least two functional groups and a monomer 
corresponding to the recurring unit shown by formula (I) is preferred. 
Practical examples of the polymerizable functional groups include CH.sub.2 
.dbd.CH--, CH.sub.2 .dbd.CH--CH.sub.2 --, 
##STR12## 
CH.sub.2 .dbd.CH--NHCO--, CH.sub.2 .dbd.CH--CH.sub.2 --NHCO--, CH.sub.2 
.dbd.CH--SO.sub.2 --, CH.sub.2 .dbd.CH--CO--, CH.sub.2 .dbd.CH--O--, and 
CH.sub.2 .dbd.CH--S--. The monomer may have two or more the aforesaid 
polymerizable functional groups and in this case they may be the same or 
different. 
Specific examples of the monomer having two or more polymerizable monomers 
are as follows. 
Examples of the monomer having same polymerizable functional groups are 
styrene derivatives such as divinylbenzene, trivinylbenzene, etc.; 
methacrylic acid, acrylic acid, or crotonic acid esters of a polyhydric 
alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, 
polyethylene glycols #200, #400, and #600, 1,3-butylene glycol, neopentyl 
glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, 
trimethylolethane, and pentaerythritol) or a polyhydroxyphenol (e.g., 
hydroquinone, resorcinol, catechol, and the derivative thereof), vinyl 
ethers, and allyl ethers; vinyl esters of a dibasic acid (e.g., malonic 
acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic 
acid, phthalic acid, and itaconic acid), allyl esters, vinylamides, and 
allyl amides; and condensates of polyamides (e.g., ethylenediamine, 
1,3-propylenediamine, and 1,4-butylenediamine) and a carboxylic acid 
having a vinyl group (e.g., methacrylic acid, acrylic acid, crotonic acid, 
and allylacetic acid). 
Also, examples of the monomer having different polymerizable functional 
groups are vinyl group-having ester derivatives or amide derivatives 
(e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl 
itaconate, allyl acrylate, allyl itaconate, vinyl methacryloylacetate, 
vinyl methacryloylpropionate, allyl methacryloylpropionate, methacrylic 
acid vinyloxycarbonyl methyl ester, acrylic acid 
vinyloxycarbonylmethyloxycarbonylethylene ester, N-allylacrylamide, 
N-allylmethacrylamide, N-allylitaconic acid amide, and 
methacryloylpropionic acid allyl amide) of vinyl group-having carboxylic 
acids (e.g., methacrylic acid, acrylic acid, methacryloylacetic acid, 
acryloylacetic acid, methacryloylpropionic acid, acryloylpropionic acid, 
itaconiloylacetic acid, itaconoloylpropionic acid, and reaction products 
of carboxylic acids and alcohols or amines (e.g., 
allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 
2-allyloxycarbonylbenzoic acid, and allylaminocarbonylpropionic acid)); 
and condensates of aminoalcohols (e.g., aminoethanol, 1-aminopropanol, 
1-aminobutanol, 1-aminohexanol, and 2-aminobutanol) and vinyl group having 
carboxylic acids. 
In this invention, by performing the polymerization using the monomer 
having two or more polymerizable functional groups in an amount of not 
more than 15% by weight, and preferably not more than 10% by weight of 
whole monomers, the partially crosslinked resin can be formed. 
Also, the polymerizable double bond group bonding to one terminal only of 
the polymer chain has a chemical structure of directly bonding to one 
terminal of the polymer main chain or bonding thereto through an optional 
linkage group. 
Practically, the polymerizable double bond group has the chemical structure 
shown by formula (V): 
##STR13## 
wherein T.sup.3 has the same meaning as T.sup.2 in the aforesaid formula 
(IV); f.sup.1 and f.sup.2, which may be the same or different, each has 
the same meaning as e.sup.1 and e.sup.2 in the aforesaid formula (IV); and 
U.sup.1 represents a linkage group capable of bonding 
##STR14## 
to one terminal of the polymer main chain directly or through an optional 
linkage group. 
The linkage group is composed of an optional combination of the atomic 
groups of a carbon-carbon bond (single bond or double bond), a 
carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, 
nitrogen, and silicon), or a hetero atom-hetero atom bond. 
Examples of the linkage group are 
##STR15## 
(wherein Z.sup.4 and Z.sup.5 each represents a halogen atom (e.g., 
fluorine, chlorine, and bromine), a cyano group, a hydroxy group, an alkyl 
group (e.g., methyl, ethyl, and propyl)), 
##STR16## 
(wherein Z.sup.6 and Z.sup.7 each represents a hydrogen, a hydrocarbon 
group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 
pentyl, hexyl, benzyl, phenethyl, phenyl, and tolyl), or --OZ.sup.8 
(wherein Z.sup.8 has the same meaning as the hydrocarbon group shown by 
Z.sup.6)). 
Then, the polymerizable double bond shown by the aforesaid formula (V), 
which is bonded to only one terminal of the polymer main chain, is 
practically shown below. In the practical examples shown below, A 
represents --H, --CH.sub.3, or --CH.sub.2 COOCH.sub.3 ; B represents --H 
or --CH.sub.3 ; n represents an integer of from 2 to 10, m represents 2 or 
3; l represents 1, 2 or 3; p represents an integer of from 1 to 4; and q 
represents 1 or 2. 
##STR17## 
The dispersion-dispersing resin in this invention having the polymerizable 
double bond group bonded to only one terminal of the polymer main chain 
can be easily prepared by (1) a method of reacting various reagents to the 
terminal of a living polymer obtained by an anion polymerization or cation 
polymerization or (2) a method of reacting having a "specific reactive 
group" (e.g., --OH, --COOH, --SO.sub.3 H, --NH.sub.2, --SH, --PO.sub.3 
H.sub.2, --NCO, --NCS, 
##STR18## 
--COCl, and --SO.sub.2 Cl) to the terminal of the aforesaid living polymer 
and then introducing a polymerizable double bond group by a macromolecular 
reaction (a method by an ion polymerization), or (3) a method of 
performing a radical polymerization using a polymerization initiator 
and/or a chain transfer agent containing the aforesaid "specific reactive 
group" in the molecule and then introducing a polymerizable double bond 
group therein by performing a macromolecular reaction utilizing the 
"specific reactive group" bonded to only one terminal of the polymer main 
chain. 
Practically, the polymerizable double bond group can be introduced into the 
polymer according to the methods described in P. Dreyfuss & R. P. Quirk, 
Encycl. Polymer Sci. Eng., 7, 551(1987), Yoshiki Nakajo and Yuya 
Yamashita, Senryo to Yakuhin (Dyes and Chemicals), 30, 232(1985), Akira 
Ueda and Susumu Nagai, Kagaku to Kogyo (Science and Industry), 60 (1986), 
Koichi Ito, Kobunshi Kako (Polymer Processing), 35, 262(1986), V. Percec, 
Applied Polymer Science, 35, 97(1985) and the literature references cited 
therein. 
Furthermore, more practically, a polymer having the "specific reactive 
group" bonded to only one terminal of the polymer main chain and the 
aforesaid crosslinked structure is produced by (1) a method of 
polymerizing a mixture of at least one monomer corresponding to the 
recurring unit shown by the aforesaid formula (I), a polyfunctional 
monomer for introducing the aforesaid crosslinked structure, and a chain 
transfer agent having the aforesaid "specific reactive group" in the 
molecule using a polymerization initiator (e.g., an azobis compound and a 
peroxide), (2) a method of polymerizing the aforesaid mixture without 
containing the chain transfer agent using a polymerization initiator 
having the aforesaid "specific reactive agent" in the molecule, or (3) a 
method of polymerizing the aforesaid mixture using the chain transfer 
agent and the polymerization initiator, each having the aforesaid 
"specific reactive group", and then a polymerizable double bond is 
introduced into the polymer by performing a macromolecular reaction 
utilizing the "specific reactive group". 
Examples of the chain transfer agent include mercapto compounds each having 
the "specific reactive group" or a substituent capable of being induced 
into the "specific 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, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 
mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, and 2-mercapto 
3-mercapto-3-pyridinol) and iodized alkyl compounds each containing the 
"specific reactive group" or a substituent capable of being induced into 
the "specific reactive group" (e.g., indoacetic acid, iodopropionic acid, 
2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid. 
In these compounds, the mercapto compounds are preferred. 
Also, examples of the polymerization initiator containing the "specific 
reactive group" or a substituent capable of being induced into the 
"specific reactive group" include 4,4'-azobis(4-cyanovaleric 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-tetrahydropyrimidin-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], and 
2,2'-azobis-(2-amidinopropane). 
The amount of the chain transfer agent or the polymerization initiator is 
from about 0.5 to about 15 parts by weight, and preferably from 1 to 10 
parts by weight to 100 parts by weight of the whole monomers. 
The dispersion stabilizing resin for use in this invention may be soluble 
in an organic solvent, and practically the dispersion stabilizing resin of 
at least 5 parts by weight of which is soluble in 100 parts by weight of 
toluene at 25.degree. C. may be used in this invention. 
The weight average molecular weight of the dispersion stabilizing resin for 
use in this invention 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. 
The monomers which are used for the production of the aforesaid non-aqueous 
dispersion resin grains (dispersed resin grains) are classified into the 
monofunctional monomer (A) which is soluble in the non-aqueous solvent, 
but becomes insoluble after being polymerized and the monofunctional 
macromonomer (M) forming a copolymer with the monomer (A). 
As the monomer (A) for use in this invention, any monofunctional monomers 
which are insoluble in the non-aqueous solvent, but become insoluble 
thereon by being polymerized can be used. Practically, monomers shown by 
following formula (A-I) can be used: 
##STR19## 
wherein V.sup.5 represents --COO--, --OCO--, --CH.sub.2 OCO--, --CH.sub.2 
COO--, --O--, --CONHCOO--, --CONHOCO--, --SO.sub.2 --, 
##STR20## 
(wherein D.sup.6 represents a hydrogen or an aliphatic group having from 1 
to 18 carbon atoms, which may be substituted (e.g., methyl, ethyl, propyl, 
butyl, 2-chloroethyl, 2-bromoethyl, benzyl, chlorobenzyl, methylbenzyl, 
methoxybenzyl, phenethyl, 3-phenylpropyl, dimethylbenzyl, fluorobenzyl, 
2-methoxyethyl, and 3-methoxypropyl)); R.sup.3 represents a hydrogen atom 
or an aliphatic 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-chlororopyl, 2-cyanoethyl, 3-cyanopropyl, 2-nitroethyl, 
2-methoxyethyl, 2-methanesulfonylethyl, 2-ethoxyethyl, 
N,N-dimethylaminoethyl, N,N-diethylaminoethyl, trimethoxysilylpropyl, 
3-bromopropyl, 4-hydroxybutyl, 2-flufurylethyl, 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); and b.sup.5 and 
b.sup.6, which may be the same or different, each has the same meaning as 
b.sup.1 or b.sup.2 in the aforesaid formula (M-1). 
Specific examples of monofunctional monomer (A) include vinyl esters or 
allyl esters of aliphatic carboxylic acids having from 1 to 6 carbon atoms 
(e.g., acetic acid, propionic acid, butyric acid, monochloroacetic acid, 
and trifluoropropionic acid); alkyl esters or alkylamides (the alkyl 
moiety having from 1 to 4 carbon atoms) of an unsaturated carboxylic acid 
such as acrylic acid, crotonic acid, itaconic acid, maleic acid, etc., 
(the alkyl group includes, for example, 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, 
chlorome,thylstyrene, hydroxymethylstyrene, methoxymethylstyrene, 
N,N-dimethylaminomethylstyrene, vinylbenzenecarboxyamide, and 
vinylbenzenesulfoamide); unsaturated carboxylic acids such as acrylic 
acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.; 
cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile; 
methacrylonitrile; and heterocyclic compounds having a polymerizable 
double bond group (practical examples are the compounds described in 
Polymer Date Handbook, Foundation, pages 175 to 184, edited by Polymer 
Society of Japan, 1986, such as N-vinylpyridine, N-vinylimidazole, 
N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, 
vinylthiazole, N-vinylmorpholine, etc. 
The monofunctional monomers (A) may be used singly or as a mixture thereof. 
The monofunctional macromonomer (M) is a macromonomer having a number 
average molecular weight of not more than 1.times.10.sup.4 having a 
polymerizable double bond group copolymerizable with the monomer (A) shown 
by the aforesaid formula (M-II) bonded to one terminal of the main chain 
of the polymer composed of the recurring unit shown by the aforesaid 
formula (M-I). 
In the formulae (M-I) and (M-II), the hydrocarbon groups included in 
b.sup.1, b.sup.2, V.sup.0, R.sup.0, c.sup.1, c.sup.2, and V.sup.1 each has 
the carbon atom number (as the unsubstituted hydrocarbon group) defined 
above and may be substituted. 
In the formula (M-I), D.sup.1 in the substituents shown by V.sup.0 
represents a hydrogen atom or a hydrocarbon group having from 1 to 22 
carbon atoms 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, eicosanyl, 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 substituted (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, octadecenyl, and linolenyl), 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-cyclopenthylethyl), and an aromatic group having 
from 6 to 12 carbon atoms, which may be substituted (e.g., phenyl, 
naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, 
dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, 
chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, 
methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, 
acetamidophenyl, propioamidophenyl, and dodecyloylamidophenyl). 
When V.sup.0 shows 
##STR21## 
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). 
##STR22## 
R.sup.0 preferably represents a hydrocarbon group having from 1 to 22 
carbon atoms and practically shows the same meaning as described above for 
D.sup.1. R.sup.0 may have --O--, --CO--, --CO.sub.2 --, --OCO--, 
--SO.sub.2 --, t,0410 (wherein D.sup.2 has the same meaning as D.sup.1). 
In the formula (M-I), b.sup.1 and b.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 3 carbon atoms (e.g., methyl, ethyl, and propyl), --COOD.sup.3, or 
--CH.sub.2 COOD.sub.3 (wherein D.sup.3 represents a hydrogen atom, an 
alkyl group having from 1 to 18 carbon atoms, an alkenyl group, an aralkyl 
group, an aliphatic group, or an aryl group and each of these groups may 
be substituted and has the same meaning as those described above for 
D.sup.1). 
Furthermore, in the macromonomer (M) for use in this invention, R.sup.0 in 
the formula (M-I) showing the recurring unit constituting the macromonomer 
preferably contains a component shown by following formula (M-Ia) having 
the features of containing at least one specific polar group shown by 
B.sup.1 and at least one specific polar group shown by B.sup.2 and thus 
having at least 2 specific polar groups as recurring unit moieties in the 
molecule 
##STR23## 
wherein b.sup.1, b.sup.2, and V.sup.0 are same as described above; B.sup.1 
and B.sup.2, which may be the same or different, each represents --O--, 
--CO--, --CO.sub.2 --, --OCO--, --SO.sub.2 --, 
##STR24## 
(wherein D.sup.5 has the same meaning as D.sup.1 in the aforesaid formula 
(M-I)); A.sup.1 and A.sup.2, which may be same or different, each 
represents a hydrocarbon group having from 1 to 18 carbon atoms, which may 
be substituted or may have 
##STR25## 
in the main chain bond (wherein the hydrocarbon group is an alkyl group, 
an alkenyl group, an aralkyl group, or an alicyclic group). 
Preferred examples of the aforesaid aliphatic groups are the same as the 
preferred examples of the aliphatic group shown by R.sup.0 in the formula 
(M-I) described above. 
In the above formula, B.sup.3 and B.sup.4, which may be the same or 
different, have the same meaning as B.sup.1 and B.sup.2 described above 
and A.sup.3 represents a hydrocarbon group having from 1 to 18 carbon 
atoms, which may be substituted, as shown by A.sup.1 or A.sup.2 described 
above. 
Furthermore, practically, A.sup.1 and A.sup.2 in the formula (M-Ia) each is 
composed of an optional combination of the atomic group such as 
##STR26## 
(wherein D.sup.7 and D.sup.8 each represents a hydrogen atom, an alkyl 
group, or a halogen atom), 
##STR27## 
(wherein B.sup.3, B.sup.4, A.sup.3, R.sup.1, and p are same as described 
above), etc. 
Furthermore, m, n, and p, which may be the same or different, each 
represents 0, 1, 2, or 3, with the proviso that m, n, and p cannot be 0 at 
the same time. 
In the formula (M-Ia), R.sup.1 represents a hydrogen atom or a hydrocarbon 
group having from 1 to 22 carbon atoms and preferably represents an 
aliphatic group having from 1 to 22 carbon atoms, which may be 
substituted. Practical examples thereof are the same as the preferred 
examples of R.sup.0 in the aforesaid formula (M-I). 
Furthermore, it is preferred that in the formula (M-Ia), the total atomic 
number of each atomic group of V.sup.0, A.sup.1, B.sup.1, A.sup.2, 
B.sup.2, and R.sup.1 is at least 8. 
The recurring unit shown by the formula (M-Ia) is further described 
practically although the scope of this invention is not limited thereto. 
In the following chemical formulae, a represents --H or --CH.sub.3, R 
represents an alkyl group having from 1 to 18 carbon atoms, R' represents 
a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms, 
k.sub.1 and k.sub.2 each represents an integer of from 1 to 12, and 
l.sub.1 represents an integer of from 1 to 100. 
##STR28## 
The macromonomer (M) for use in this invention has the aforesaid chemical 
structure that the polymerizable double bond group shown by the formula 
(M-II) bonded to only one terminal of the polymer main chain composed of 
the recurring unit shown by the formula (M-I) directly or via an optional 
linkage group. 
In the formula (M-II), V.sup.1 has the same meaning as V.sup.0 in the 
formula (M-I); c.sup.1 and c.sup.2, which may be the same or different, 
each has the same meaning as b.sup.1 or b.sup.2 in the aforesaid formula 
(M-I). 
Also, V.sup.1, c.sup.1, and c.sup.2 are preferably the same as those 
described above for V.sup.0, b.sup.1, and b.sup.2 in the formula (M-I). It 
is more preferred that one of c.sup.1 and c.sup.2 in the formula (M-II) is 
a hydrogen atom. 
The linkage group which links the moiety shown by the formula (M-I) and the 
moiety shown by the formula (M-II) is composed of an optional combination 
of the atomic group of a carbon-carbon bond (single bond or double bond), 
a carbon-hetero atom bond (examples of the hetero atom are oxygen atom, 
sulfur atom, nitrogen atom, and silica atom), and a hetero atom-hetero 
atom bond. 
Preferred examples of the macromonomer (M) used in this invention are those 
shown by the following formulae (M-VI) and (M-VIa): 
##STR29## 
In the formulae (M-VI) and (M-VIa), symbols other than Z are the same as 
the symbols in the aforesaid formula (M-I), (M-Ia) and (M-II) and Z 
represents a simple bond, or a linkage group selected from the atomic 
groups of 
##STR30## 
(wherein D.sup.9 and D.sup.10 each represents a hydrogen atom, a halogen 
atom (e.g., fluorine, chlorine, and bromine), a cyano group, a hydroxy 
group, or an alkyl group (e.g., methyl, ethyl, and propyl), 
##STR31## 
(wherein D.sup.11 and D.sup.12 each represents a hydrogen atom or the 
hydrocarbon group as described above on D.sup.1) or a linkage group 
constituted by an optional combination of these atomic groups. 
Particularly preferred examples of b.sup.1, b.sup.2, c.sup.1, c.sup.2, 
V.sup.0, and V.sup.1 in the formulae (M-VI) and (M-VIa) are shown below. 
That is, V.sup.0 is --COO--, --OCO--, --O--, --CH.sub.2 COO--, or 
--CH.sub.2 OCO--; V.sup.1 is the aforesaid ones (wherein D.sup.1 is a 
hydrogen atom; and b.sup.1, b.sup.2, c.sup.1, and c.sup.2 are a hydrogen 
atom or a methyl group. 
Then, specific examples of 
##STR32## 
shown in the formulae (M VI) and (M-VIa) are shown below, though the 
present invention is not limited thereto. 
In the following chemical formulae, b represents --H or --CH.sub.3, m.sub.1 
represents an integer of from 1 to 12, and n.sub.1 represents an integer 
of 2 to 12. 
##STR33## 
Also, the macromonomer (M) for use in this invention may contain other 
recurring unit together with the recurring unit shown by the formula (M-I) 
or (M-Ia) as a copolymer component. As such other copolymer components, a 
monomer capable of copolymerizing with the monomer corresponding to the 
recurring unit shown by the formula (M-I) can be used in this invention. 
Examples thereof are unsaturated carboxylic acids such as acrylic acid, 
methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinylacetic 
acid, 4-pentenoic acid, etc.; esters or amides of these unsaturated 
carboxylic acids; vinyl esters, or allyl esters of fatty acids having from 
1 to 22 carbon atoms; vinyl ethers; styrene and styrene derivatives; and 
heterocyclic compounds having an unsaturated bonding group. Practically, 
there are the compounds illustrated above for the monomer (A). 
It is preferred, the content of the recurring unit shown by the formula 
(M-I) or (M-Ia) is at least 40% by weight and more preferably from 60 to 
100% by weight of the whole recurring units in the macromonomer (M). 
If the content of the component shown by the formula (M-I) or (M-Ia) is 
less than 40% by weight, the mechanical strength of the imaged portions 
formed by the dispersion resin grains is not sufficiently retained, 
whereby the effect of improving the printing resistance is not obtained in 
the case of use for offset master plates. 
The number average molecular weight of the macromonomer (M) in this 
invention is preferably from 1.times.10.sup.3 to 1.times.10.sup.4, and 
more preferably from 2.times.10.sup.3 to 9.times.10.sup.3. 
If the upper limit of the number average molecular weight of the 
macromonomer (M) exceeds 1.times.10.sup.4, the printing resistance is 
lowered. On the other hand, if the molecular weight is below the lower 
limit, there is a tendency of causing stains. Thus, it is preferred that 
the molecular weight is not less than 1.times.10.sup.3. 
The macromonomer (M) in this invention can be prepared by conventionally 
known synthesis methods. 
For example, there are (1) a method by an ion polymerization method of 
forming the macromer by reacting various reagents to the terminal of a 
living polymer obtained by an anion polymerization or a cation 
polymerization, (2) a method by a radical polymerization method of forming 
the macromer by reacting an oligomer having a reactive group at the 
terminal obtained by a radical polymerization using a polymerization 
initiator and/or a chain transfer agent having a reactive group such as a 
carboxy group, a hydroxy group, an amino group, etc., in the molecule, and 
(3) a method by a polycondensation method of introducing a polymerizable 
double bond group into an oligomer obtained by a poly-addition or 
poly-condensation reaction in the same manner as the aforesaid radical 
polymerization method. 
Practically, the macromonomer (M) can be prepared by the methods described 
in P. Dreyfuss & R. P. Quirk, Encycl. 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, Makamol. Chem. Suppl., 
12, 163(1985), P. Rempp. et al, Makamol Chem. Suppl., 8, 3(1984), Yushi 
Kawakami, Kagaku Kogyo (Chemical Industry), 38, 56(1987), Yuya Yamashita, 
Kobunshi (High Polymer), 31, 988(1982), Shiro Kobayashi, ibid., 30, 
625(1981), Toshinobu Higashimura, Journal of Adhesive Society of Japan, 
18, 536(1982), Koichi Ito, Kobunshi Kako (Polymer Processing), 35, 
262(1986), and Kishiro Higashi and Takashi Tsuda, Kino Zairyo (Functional 
Materials), 1987, No. 10, page 5 and the literature references, patents, 
etc., cited therein. 
Examples of the polymerization initiator having the specific reactive group 
in the molecule are azobis compounds such as 4,4'-azobis(4-cyanovaleric 
acid), 4,4'-azobis(4-cyanovaleric acid chloride), 
2,2'-azobis-(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 2,2'-azobis[2 
methyl-N-(2-hydroxyethyl)propioamide], 
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propioamide}, 
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propioamide} 
, 2,2'-azobis[2-(5-methyl-2-imiszolin-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-tetrahydropyrimidin-2-yl)propane], 
2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrapyrimidin-2-yl)propane], 
2,2'-azobis{2-[1-(2-hydroxyethyl -2-imidazolin-2-yl]propane}, 
2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamidine], and 
2,2'-azobis[N-(4-aminophenyl)-2-methylpropionamidine]. 
Also, examples of the chain transfer agent having the specific reactive 
group in the molecule are mercapto compounds having the reactive group or 
a substituent capable of being converted into 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 iodized alkyl 
compounds having the reactive group or a substituent capable of being 
induced into 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 preferred. 
The chain transfer agent or the polymerization initiator is used in an 
amount of preferably from 0.5 to 20 parts by weight, and more preferably 
from 1 to 10 parts by weight per 100 parts by weight of the monomer 
corresponding to the recurring unit shown by the formula (I) or (Ia). 
The dispersion resin grains for use in this invention may be prepared by 
polymerizing the aforesaid dispersion-stabilizing resin, the monomer (A), 
and the macromonomer (M) described above in a non-aqueous solvent by 
heating in the presence of a polymerization initiator such as benzoyl 
peroxide, azobis-isobutyronitrile, butyllithium, etc. 
Practically, the dispersion resin can be produced by (1) a method of adding 
the polymerization initiating agent to a solution composed of the 
dispersion stabilizing agent, the monomer (A), and the macromonomer (M), 
(2) a method of adding dropwise the monomer (A) and the macromonomer (M) 
together with a polymerization initiator to a solution of the dispersion 
stabilizing resin, (3) a method of optionally adding a part of a mixture 
of the monomer (A) and the macromonomer (M) together with a polymerization 
initiator to a solution containing a whole amount of the dispersion 
stabilizing resin and the remaining mixture of the monomer (A) and the 
macromonomer (M), or (4) a method of optionally adding a solution of the 
dispersion stabilizing resin, the monomer (A), and the macromonomer (M) 
together with a polymerization initiator to the non-aqueous solvent. 
The total amount of the monomer (A) and the macromonomer (M) is from about 
5 to 80 parts by weight, and preferably from 10 to 50 parts by weight to 
100 parts by weight of the non-aqueous solvent. 
The amount of the soluble resin which is the dispersion stabilizing resin 
for the liquid developer of this invention is from 1 to 100 parts by 
weight, and preferably from 5 to 50 parts by weight per 100 parts of the 
total amount of the monomers. 
The amount of the polymerization initiator being used is typically from 0.1 
to 5% by weight of the total amount of the monomers. 
Also, the polymerization temperature is from about 50.degree. to 
180.degree. C., and preferably 60.degree. to 120.degree. C. The reaction 
time is preferably from 1 to 15 hours. 
When the above-described polar solvent such as alcohols, ketones, ethers, 
esters, etc., is used together with the non-aqueous solvent in the 
reaction or when the unreacted monomer (A) remains without being 
polymerization-granulated, it is preferred that the polar solvent or the 
unreacted monomer is distilled off by heating the reaction mixture to a 
temperature of higher than the boiling point of the polar solvent or the 
monomer, or is distilled off under reduced pressure. 
The molecular weight of the dispersion resin in this invention is from 
1.times.10.sup.3 to 1.times.10.sup.6, and preferably from 1.times.10.sup.4 
to 5.times.10.sup.5. 
The non-aqueous dispersion resin prepared as described above exists as fine 
grains having a uniform grain size distribution and, at the same time, 
shows a very stable dispersibility. In particular, even when the liquid 
developer containing the non-aqueous dispersion resin grains (or 
non-aqueous latex grains) is repeatedly used for a long period of time in 
a developing apparatus, the dispersibility of the resin grains in the 
developer is well maintained. Also, even when the developing speed is 
increased, the resin is easily re-dispersed in the liquid developer and no 
occurrence of stains by sticking of the resin grains to parts of the 
developing apparatus is observed under such high load conditions. 
Also, when the resin grains are fixed by heating, a strong film is formed, 
which shows an excellent fixability of the dispersion resin grains. 
In particular, the non-aqueous dispersion resin described in JP-A-62-151868 
is resin grains obtained by copolymerizing a monomer being insolubilized 
by polymerization and a copolymerizable monomer having at least two ester 
bonds, etc., in the molecule and the resin grains have greatly improved 
dispersibility and printing resistance as compared to conventional resin 
grains. However, when these resin grains are used for printing plate 
making machines using an offset printing master plate of a large size 
(e.g., EPL-560 and EPL 820, made by Fuji Photo Film Co., Ltd.) or the 
processing speed of the printing plate making machine is increased, there 
remains a problem with respect to the dispersibility of the resin grains. 
On the other hand, with the resin grains in this invention, no such problem 
occurs even under such a severe condition. 
As described above, the liquid developer of this invention is excellent in 
the dispersion stability, redispersibility, and fixability even in the 
case of quickening the development-fix steps and using master plates of a 
large size. 
For the liquid developer of this invention may be used, if desired, 
coloring agents. There is no particular restriction on the coloring agents 
and conventional various pigments or dyes can be used. 
When the dispersion resin itself is to be colored, a pigment or a dye is 
physically dispersed in the dispersion resin as one method, and various 
kinds of pigments and dyes are known, which can be used in the method. 
Examples of the coloring agent are a magnetic iron powder, a lead iodine 
powder, carbon black, nigrosine, alkali blue, hansa yellow, quinacridone 
red, and phthalocyanine blue. 
As another method of coloring the liquid developer, the dispersion resin 
may be dyed with a desired dye, for example, as disclosed in 
JP-A-57-48738. As still other methods, the dispersion resin may be 
chemically bonded to a dye, for example, as disclosed in JP-A-53-54029; or 
a previously dye containing monomer is used in polymerizing granulation to 
obtain a dye-containing polymer, for example, as disclosed in 
JP-B-44-22955. (The term "JP-B" as used herein means an "examined Japanese 
patent publication".) 
Various additives may be added to the liquid developer of the present 
invention so as to enhance the charging characteristic or to improve the 
image-forming characteristic. For example, the substances described in Y. 
Harasaki, Electrophotography, Vol. 16, No. 2, page 44 can be used for such 
purpose. 
Specifically, useful additives include metal salts of 
di-2-ethylhexylsulfosuccinic acid, metal salts of naphthenic acid, metal 
salts of higher fatty acids, lecithin, poly(vinylpyrrolidone) and 
copolymers containing half-maleic acid amide component. 
The amounts of the main constituting components of the liquid developer of 
the present invention are further explained below. 
The amount of the toner grains consisting essentially of a resin and a 
colorant is preferably from about 0.5 to about 50 parts by weight per 1000 
parts by weight of the liquid carrier. If it is less than about 0.5 part 
by weight, the image density would be insufficient. However, if it is more 
than about 50 pats by weight, the non-image area would thereby be fogged. 
In addition, the above-mentioned liquid carrier-soluble resin for 
enhancing the dispersion stability ma also be used, if desired, and it may 
be added in an amount of from about 0.5 part by weight to about 100 parts 
by weight, to 1000 parts by weight of the liquid carrier. The 
above-mentioned charge-adjusting agent is preferably used in an amount of 
from about 0.001 to about 1.0 part by weight per 1000 parts by weight of 
the liquid carrier. In addition, various additives may also be added to 
the liquid developer of the present invention, if desired, and the upper 
limit of the total amount of the additives is to be defined in accordance 
with the electric resistance of the liquid developer. Specifically, if the 
electric resistance of the liquid developer, from which toner grains are 
removed, is lower than 10.sup.9 .OMEGA. cm, images with good continuous 
gradation could hardly be obtained. Accordingly, the amounts of the 
respective additives are required to be properly controlled within the 
said limitation. 
The following examples are intended to illustrate the embodiments of this 
invention in greater detail, but not to limit the present invention in any 
way. 
PRODUCTION EXAMPLE 1 OF DISPERSION STABILIZING RESIN: P-1 
A mixture of 100 g of octadecyl methacrylate, 2.0 g of divinylbenzene, 150 
g of toluene, and 50 g of isopropanol was heated to 80.degree. C. with 
stirring in a nitrogen gas stream and, after adding thereto 5.0 g of 
2,2'-azobis(cyanovaleric acid) (A.C.V), the reaction was carried out for 8 
hours. After cooling, the reaction mixture was re-precipitated in 2 liters 
of methanol to form a white powder, which was collected by filtration and 
dried. 
A mixture of 50 g of the white powder thus obtained, 8.0 g of allyl 
glycidyl ether, 0.5 g of t-butylhydroquinone, 0.5 g of 
N,N-dimethyldodecylamine, and 100 g of toluene was heated to 100.degree. 
C. and stirred for 20 hours. The reaction mixture was re-precipitated in 1 
liter of methanol to provide a light yellow powder, which was collected by 
filtration and dried. The amount of the product was 43 g and the weight 
average molecular weight thereof was 9.5.times.10.sup.4. 
PRODUCTION EXAMPLES 2 TO 10 OF DISPERSION STABILIZING RESIN: P-2 TO P-10 
By following the same procedure as Production Example 1 described above 
except that each of the monomers shown in Table 1 below was used in place 
of octadecyl methacrylate, each of dispersion stabilizing resins P-2 to 
P-10 was produced. The weight average molecular weights of the resins thus 
obtained were from 9.0.times.10.sup.4 to 10.5.times.10.sup.4. 
TABLE 1 
______________________________________ 
Dispersion 
Production 
Stabilizing 
Example Resin Monomer 
______________________________________ 
2 P-2 Dodecyl Methacrylate 
100 g 
3 P-3 Tridecyl Methacrylate 
100 g 
4 P-4 Octyl Methacrylate 
50 g 
Dodecyl Methacrylate 
50 g 
5 P-5 Octadecyl Methacrylate 
80 g 
Butyl Methacrylate 
20 g 
6 P-6 Dodecyl Methacrylate 
92 g 
N,N-dimethylaminoethyl 
8 g 
Methacrylate 
7 P-7 Octadecyl Methacrylate 
95 g 
2-(Trimethoxysilyloxy)- 
5 g 
ethyl Methacrylate 
8 P-8 Hexadecyl Methacrylate 
100 g 
9 P-9 Tetradecyl Methacrylate 
100 g 
10 P-10 Docosanyl Methacrylate 
100 g 
______________________________________ 
PRODUCTION EXAMPLES 11 TO 23 OF DISPERSION STABILIZING RESIN: P-11 TO P-23 
By following the same procedure as Production Example 1 except that each of 
the polyfunctional monomers and the oligomers shown in Table 2 below was 
used in place of 2.0 g of divinyl benzene as a crosslinking polyfunctional 
monomer, each of dispersion stabilizing resins P-11 to P-23 shown in Table 
2 was produced. The compound ISP-22GA used in Preparation Example 17 has 
the following formula: 
##STR34## 
TABLE 2 
__________________________________________________________________________ 
Dispersion 
Production 
Stabilizing Amount 
Weight Average 
Example 
Resin Crosslinking Monomer or Oligomer 
(g) Molecular Weight 
__________________________________________________________________________ 
11 P-11 Ethylene Glycol Dimethacrylate 
2.5 10.5 .times. 10.sup. 4 
12 P-12 Diethylene Glycol Dimethacrylate 
2.5 10 .times. 10.sup.4 
13 P-13 Vinyl Methacrylate 
5 9.8 .times. 10.sup.4 
14 P-14 Isopropenyl Methacrylate 
8 8.6 .times. 10.sup.4 
15 P-15 Divinyl Adipate 10 8.8 .times. 10.sup.4 
16 P-16 Diallyl Glutaconate 
10 9.5 .times. 10.sup.4 
17 P-17 ISP-22GA (trade name, made by 
3.0 10 .times. 10.sup.4 
Okamura Seiyu K.K.) 
18 P-18 Triethylene Glycol Diacrylate 
1.0 9.3 .times. 10.sup.4 
19 P-19 Trivinylbenzene 0.8 11.2 .times. 10.sup.4 
20 P-20 Polyethylene Glycol #400 
3.0 9.6 .times. 10.sup.4 
Diacrylate 
21 P-21 Polyethylene Glycol Dimethacrylate 
3.5 10.5 .times. 10.sup.4 
22 P-22 Trimethylolpropane Triacrylate 
2.0 12 .times. 10.sup.4 
23 P-23 Polyethylene Glycol #600 Diacrylate 
3.0 9.5 .times. 10.sup.4 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 24 OF DISPERSION STABILIZING RESIN: P-24 
A mixture of 100 g of octadecyl methacrylate, 3 g of thiomalic acid, 4.5 g 
of divinylbenzene, 150 g of toluene, and 50 g of ethanol was heated to 
60.degree. C. under a nitrogen gas stream and, after adding thereto 0.5 g 
of 2,2'-azobis(isobutyronitrile) (A.I.B.N), the reaction was carried out 
for 5 hours. Then, 0.3 g of A.I.B.N. was added to the reaction mixture and 
the reaction was further carried out for 3 hours. Further, 0.2 g of 
A.I.B.N. was added thereto and the reaction was carried out for 3 hours. 
After cooling, the reaction mixture was re-precipitated in 2 liters of 
methanol to form a white powder, which was collected by filtration and 
dried. The amount of the product was 85 g. 
Then, a mixture of 50 g of the powder thus obtained and 100 g of toluene 
was heated to 40.degree. C. and stirred to dissolve the powder. Then, 
after adding thereto 0.2 g of t-butylhydroquinone, 8 g of vinyl acetate, 
and 0.03 g of mercury acetate, the reaction was carried out for 2 hours. 
Then, the temperature of the reaction mixture was raised to 70.degree. C. 
and, after adding thereto 1.2.times.10.sup.-3 ml of 100% sulfuric acid, 
the reaction was carried out for 18 hours. After the reaction was over, 
3.6 of sodium acetate trihydrate was added to the reaction mixture 
followed by stirring for 30 minutes and after cooling, the reaction 
mixture was re-precipitated in 1.5 liters of methanol to provide 41 g of a 
slightly brownish powder. The weight average molecular weight of the 
powder was 10.5.times.10.sup.4. 
PRODUCTION EXAMPLES 25 TO 30 OF DISPERSION STABILIZING RESINS: P-25 TO P-30 
By following the same procedure as Production Example 24 described above 
except that each of the mercapto compounds shown in Table 3 below was used 
in place of 3 g of thiomalic acid, each of dispersion stabilizing resins 
P-25 to P-30 was produced. The weight average molecular weight of each of 
the resins obtained was also shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Dispersion 
Production 
Stabilizing Weight Average 
Example 
Resin Mercapto Compound Molecular Weight 
__________________________________________________________________________ 
25 P-25 HSCH.sub.2 COOH 2.5 g 
8.8 .times. 10.sup.4 
26 P-26 
##STR35## 3.0 g 
9.5 .times. 10.sup.4 
27 P-27 HSCH.sub.2 CH.sub.2 NH(CH.sub.2).sub.2 COOH 
3.5 g 
8.5 .times. 10.sup.4 
28 P-28 HSCH.sub.2 CH.sub.2 NHCO(CH.sub.2).sub.2 COOH 
4.0 g 
9.0 .times. 10.sup.4 
29 P-29 HSCH.sub.2 CH.sub.2 OOC(CH.sub.2).sub.2 COOH 
4.0 g 
9.5 .times. 10.sup.4 
30 P-30 HSCH.sub.2 CH.sub.2 OOCCHCHCOOH 
4.0 g 
10 .times. 10.sup.4 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 31 OF DISPERSION STABILIZING RESIN: P-31 
By following the same procedure as Production Example 24 except that a 
mixture of 100 g of dodecyl methacrylate, 4 g of ethylene glycol 
methacrylate, 4 g of thioglycolic acid 2,3-epoxypropyl ester, and 200 g of 
toluene was used in place of the mixture used in the example, the 
polymerization reaction was carried out. 
Then, 6 g of crotonic acid, 1.0 g of 
2,2'-methylenebis-(6-t-butyl-p-cresol), and 0.8 g of 
N,N-dimethyldodecylamine were added to the reaction mixture, and the 
reaction was further carried out for 20 hours with stirring at 100.degree. 
C. The reaction mixture obtained was re-precipitated in 2 liters of 
methanol and a light yellow viscous product obtained was collected by a 
decantation method and dried. The amount of the product was 75 g and the 
weight average molecular weight thereof was 6.5.times.10.sup.4. 
PRODUCTION EXAMPLES 32 TO 40 OF DISPERSION STABILIZING RESINS: P-32 TO P-40 
By following the same procedure as the Production Example 31 described 
above, except that each of the methacrylates and each of the carboxylic 
acid compounds having a polymerizable double bond group shown in Table 4 
below were used in place of 100 g of dodecyl methacrylate and 6 g of 
crotonic acid, respectively, each of dispersion stabilizing resins P-32 to 
P-40 was produced. 
The weight average molecular weights of the resins thus obtained were from 
6.0.times.10.sup.4 to 7.5.times.10.sup.4. 
TABLE 4 
__________________________________________________________________________ 
Dispersion 
Production 
Stabilizing 
Example 
Resin Methacrylate Carboxylic Acid 
__________________________________________________________________________ 
32 P-32 Octadecyl Methacrylate 
100 
g Crotonic Acid 6 g 
33 P-33 Dodecyl Methacrylate 
100 
g Methacrylic Acid 
6 g 
34 P-34 Hexadecyl Methacrylate 
100 
g Acrylic Acid 5 g 
35 P-35 Octadecyl Methacrylate 
100 
g 4-Vinylbenzoic Acid 
7 g 
36 P-36 Dodecyl Methacrylate 
95 g 4-Pentenoic Acid 
6 g 
2-Hydroxyethyl Methacrylate 
5 g 
37 P-37 Tridecyl Methacrylate 
95 g 3-Butenoic Acid 
5.5 
g 
3-Chloropropyl Methacrylate 
5 g 
38 P-38 Dodecyl Methacrylate 2,4,6-Trifluorophenyl Methacrylate 
90 10 
g g 
##STR36## 7 g 
39 P-39 Docosanyl Methacrylate 
100 
g 
##STR37## 7.5 
g 
40 P-40 Tetradecyl Methacrylate 
100 
g 3-Butenoic Acid 
5.8 
g 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 41 OF DISPERSION STABILIZING RESIN: P-41 
A mixture of 100 g of tridecyl methacrylate, 1.2 g of divinylbenzene, and 
200 g of tetrahydrofuran was heated to 70.degree. C. with stirring under 
nitrogen gas stream and, after adding thereto 6 g of 
4,4'-azobis(4-cyanopentanol), the reaction was carried out for 8 hours. 
Then, after cooling the reaction mixture, 6.2 g of methacrylic anhydride, 
0.8 g of t-butylhydroquinone, and one drop of concentrated sulfuric acid 
were added thereto, and the mixture was stirred for one hour at 30.degree. 
C. and further stirred for 3 hours at 50.degree. C. After cooling, the 
reaction mixture thus obtained was re-precipitated in 2 liters of methanol 
and, after removing the solution by decantation, a brownish viscous 
product thus formed was collected by filtration and dried. The amount of 
the product was 88 g and the weight average molecular weight thereof was 
11.3.times.10.sup.4. 
PRODUCTION EXAMPLE 42 OF DISPERSION STABILIZING RESIN: P-42 
A mixture of 100 g of octadecyl methacrylate, 1.1 g of ethylene glycol 
diacrylate, and 200 g of tetrahydrofuran was heated to 70.degree. C. with 
stirring under a nitrogen gas stream and, after adding thereto 5 g of 
4,4'-azobis(4-cyanopentanol), the reaction was carried out for 5 hours. 
Furthermore, 1.0 g of the aforesaid azobis compound was added to the 
reaction mixture, and the reaction was further carried out for 5 hours. 
The resulting reaction mixture was cooled to 20.degree. C. in a water bath 
and, after adding thereto 3.2 g of pyridine and 1.0 g of 
2,2'-methylenebis-(6-t-butyl-p-cresol), the resulting mixture was stirred. 
Then, to the mixture was added dropwise 4.2 g of methacrylic acid chloride 
over a period of 30 minutes in such a manner that the reaction temperature 
was not over 25.degree. C., and the mixture obtained was stirred for 4 
hours at temperature of from 20.degree. to 25.degree. C. Then, the 
reaction mixture was re-precipitated in a mixture of 1.5 liter of methanol 
and 0.5 liter of water to obtain a white powder, which was collected by 
filtration and dried. The amount of the product was 82 g and the weight 
average molecular weight thereof was 11.2.times.10.sup.4. 
PRODUCTION EXAMPLES 43 TO 51 OF DISPERSION STABILIZING RESINS: P-43 TO P-51 
By following the same procedure as Production Example 42 except that each 
of the acid chlorides shown in Table 5 below was used in place of 
methacrylic acid chloride, each of dispersion stabilizing resins P-32 to 
P-51 was produced. The weight average molecular weights of the resins 
obtained were from 10.times.10.sup.4 to 20.times.10.sup.4. 
TABLE 5 
______________________________________ 
Pro- Dispersion 
duction 
Stabilizing 
Example 
Resis Acid Chloride 
______________________________________ 
43 P-43 CH.sub.2CHCOCl 
44 P-44 
##STR38## 
45 P-45 
##STR39## 
46 P-46 CH.sub.2CHCOOCH.sub.2 CH.sub.2 COCl 
47 P-47 
##STR40## 
48 P-48 
##STR41## 
49 P-49 
##STR42## 
50 P-50 
##STR43## 
51 P-51 
##STR44## 
______________________________________ 
PRODUCTION EXAMPLE 52 OF DISPERSION STABILIZING RESIN: P-52 
A mixture of 100 g of dodecyl methacrylate, 0.8 g of ethylene glycol 
methacrylate, and 200 g of tetrahydrofuran was heated to 65.degree. C. 
under nitrogen gas stream and, after adding thereto 4 g of 
2,2'-azobis(4-cyanovaleric acid chloride), the mixture was stirred for 10 
hours. The reaction mixture obtained was cooled below 25.degree. C. in a 
water bath, and 2.4 g of allyl alcohol was added thereto. Then, 2.5 g of 
pyridine was added dropwise to the mixture in such a manner that the 
reaction temperature was not over 25.degree. C. and the resulting mixture 
was stirred for one hour as it was. Furthermore, after stirring the 
mixture for 2 hours at 40.degree. C., the reaction mixture was 
re-precipitated in 2 liters of methanol, and a light yellow viscous 
product was obtained by decantation and dried. The amount of the product 
was 80 g and the weight average molecular weight thereof was 
10.5.times.10.sup.4. 
PRODUCTION EXAMPLES 53 TO 61 OF DISPERSION STABILIZING RESINS: P-53 TO P-61 
By following the same procedure as Production Example 24 described above 
except that each of the methacrylates and each of the polyfunctional 
monomers shown in Table 6 below were used in place of octedecyl 
methacrylate and divinylbenzene used in the example, respectively, each of 
dispersion stabilizing resins P-53 to P-61 was produced. The weight 
average molecular weights of the resins thus obtained were from 
9.0.times.10.sup.4 to 12.times.10.sup.4. 
TABLE 6 
__________________________________________________________________________ 
Dispersion 
Production 
Stabilizing 
Example 
Resin Methacrylate Polyfunctional Monomer 
__________________________________________________________________________ 
55 P-53 Dodecyl Methacrylate 
100 g 
Divinylbenzene 
4 g 
54 P-54 Tridecyl Methacrylate 
100 g 
Divinylbenzene 
4 g 
55 P-55 Dodecyl Methacrylate 
100 g 
Trivinylbenzene 
1.3 g 
56 P-56 Octadecyl Methacrylate 
100 g 
Ethylene Glycol 
5 g 
Dimethacrylate 
57 P-57 Hexadecyl Methacrylate 
100 g 
Propylene Glycol 
5 g 
Dimethacrylate 
58 P-58 Dodecyl Methacrylate 
70 g 
Divinylbenzene 
4 g 
Octadecyl Acrylate 
30 g 
59 P-59 Octadecyl Methacrylate 
90 g 
Ethylene Glycol 
4 g 
Diacrylate 
Dodecyl Acrylate 
10 g 
60 P-60 Tridecyl Methacrylate 
94 g 
Trimethylopropane 
1.5 g 
Trimethyacrylate 
2-Chloroethyl Methacrylate 
6 g 
61 P-61 Tetradecyl Methacrylate 
90 g 
Divinylbenzene 
4 g 
Styrene 10 g 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 62 OF DISPERSION STABILIZING RESIN: P-62 
A mixture of 97 g of octadecyl methacrylate, 3 g of thioglycolic acid, 6 g 
of divinylbenzene, and 200 g of toluene was heated to 85.degree. C. with 
stirring under nitrogen gas stream and after adding thereto 1.0 g of 
2,2'-azobis(cyclohexylcyanamide) (A.B.C.C.), the reaction was carried out 
for 5 hours. Furthermore, 0.6 g of A.B.C.C. was added thereto and the 
reaction was further carried out for 4 hours. After cooling the reaction 
mixture to 25.degree. C., 6 g of allyl alcohol was added to the reaction 
mixture, and, after adding thereto dropwise a mixture of 8 g of 
dicyclohexylcarbodiimide (D.C.C.), 0.4 g of 4-(N,N-dimethylamino)pyridine 
(D.M.A.P.), and 10 g of methylene chloride over a period of 30 minutes, 
the reaction was carried out for 4 hours. Insoluble materials were removed 
by filtration, and the filtrate was re-precipitated from 3 liters of 
methanol to form white precipitates, which were then collected by 
filtration and dried. The amount of the product was 66 g and the weight 
average molecular weight was 3.6.times.10.sup.4. 
PRODUCTION EXAMPLE 63 OF DISPERSION STABILIZING RESIN: P-63 
A mixture of 96 g of hexadecyl methacrylate, 4 g of 2-mercaptoethanol, 7 g 
of divinylbenzene, 160 g of toluene, and 40 g of ethanol was heated to 
80.degree. C. with stirring under nitrogen gas stream and, after adding 
thereto 2 g of A.I.B.N., the reaction was carried out for 4 hours. 
Furthermore, 1.0 g of A.I.B.N. was added to the reaction mixture and the 
reaction was further carried out for 4 hours. The reaction mixture was 
re-precipitated in 3 liters of methanol to form precipitates, which were 
then collected by filtration and dried. The yield of the product was 78 g. 
A mixture of 50 g of the aforesaid reaction product, 5 g of 4-pentenoic 
acid, and 150 g of tetrahydrofuran was stirred at 25.degree. C. to 
dissolve the product. Then, a mixture of 6 g of D.C.C., 0.3 g of D.M.A.P., 
and 10 g of methylene chloride was added dropwise to the reaction mixture 
over a period of 30 minutes, and the mixture was stirred for 5 hours. 
After adding thereto 10 g of water followed by stirring for one hour, the 
precipitates thus formed were removed by filtration, and the filtrate 
obtained was re-precipitated to form precipitates, which were collected by 
filtration and dried. The yield of the product was 38 g and the weight 
average molecular weight of the product was 4.0.times.10.sup.4. 
PRODUCTION EXAMPLE 1 OF MACROMONOMER: M-1 
A mixture of 92 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 
g of toluene was heated to 75.degree. C. with stirring under nitrogen gas 
stream and, after adding thereto 31 g of 2,2'-azobis(cyanovaleric acid) 
(A.C.V.), the reaction was carried out for 8 hours. Then, after adding 
thereto 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, 
and 0.5 g of t-butylhydroquinone, the resulting mixture was stirred for 12 
hours at 100.degree. C. After cooling, the reaction mixture was 
re-precipitated from 2 liters of methanol to form a white powder, which 
was then collected by filtration to obtain 82 g of a white powder. The 
number average molecular weight of the polymer was 6,500. 
PRODUCTION EXAMPLE 2 OF MACROMONOMER: M-2 
A mixture of 95 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 
g of toluene was heated to 70.degree. C. with stirring under nitrogen gas 
stream and, after adding thereto 1.5 g of 2,2'-azobis(isobutyronitrile) 
(A.I.B.N.), the reaction was carried out for 8 hours. Then, to the 
reaction mixture were added 7.5 g of glycidyl methacrylate, 1.0 g of 
N,N-dimethyldodecylamine, and 0.8 g of t-butylhydroquinone, and the 
resulting mixture was stirred for 12 hours at 100.degree. C. After 
cooling, the reaction mixture was re-precipitated from 2 liters of 
methanol to obtain 85 g of a colorless transparent viscous product. The 
number average molecular weight of the polymer obtained was 2,400. 
PRODUCTION EXAMPLE 3 OF MACROMONOMER: M-3 
A mixture of 94 g of methyl methacrylate, 6 g of 2-mercaptoethanol, and 200 
g of toluene was heated to 70.degree. C. under a nitrogen gas stream and, 
after adding thereto 1.2 g of A.I.B.N., the reaction was carried out for 8 
hours. 
The reaction mixture was cooled to 20.degree. C. in a water bath and, after 
adding thereto 10.2 g of triethylamine, 14.5 g of methacrylic acid 
chloride was added dropwise to the mixture with stirring at 25.degree. C. 
Thereafter, the mixture was further stirred for one hour as it was. Then, 
0.5 g of t-butylhydroquinone was added thereto, and the resulting mixture 
was stirred for 4 hours at 60.degree. C. After cooling, the reaction 
mixture was re-precipitated from 2 liters of methanol to obtain 79 g of a 
colorless transparent viscous product. The number average molecular weight 
of the product was 4,500. 
PRODUCTION EXAMPLE 4 OF MACROMONOMER: M-4 
A mixture of 95 g of hexyl methacrylate and 200 g of toluene was heated to 
70.degree. C. under a nitrogen gas stream and, after adding thereto 5 g of 
2,2'-azobis-(cyanoheptanol), the reaction was carried out for 8 hours. 
After allowing the reaction mixture to cool, it was cooled to 20.degree. C. 
in a water bath and, after adding thereto 1.0 g of triethylamine and 21 g 
of methacrylic acid anhydride, the resulting mixture was stirred for one 
hour and then stirred for 6 hours at 60.degree. C. 
After cooling, the reaction mixture obtained was re-precipitated from 2 
liters of methanol to obtain 75 g of a colorless transparent viscous 
product. The number average molecular weight of the product was 6,200. 
PRODUCTION EXAMPLE 5 OF MACROMONOMER: M-5 
A mixture of 93 g of dodecyl methacrylate, 7 g of 3-mercaptopropionic acid, 
170 g of toluene, and 30 g of isopropanol was heated to 70.degree. C. 
under a nitrogen gas stream to provide a homogeneous solution. After 
adding thereto 2.0 g of A.I.B.N., the reaction was carried out for 8 
hours. After cooling, the reaction mixture was re-precipitated from 2 
liters of methanol, and the mixture was heated to 50.degree. C. under 
reduced pressure to distill off the solvent. The viscous product obtained 
was dissolved in 200 g of toluene and 16 g of glycidyl methacrylate, 1.0 g 
of N,N-dimethyldodecyl methacrylate, and 1.0 g of t-butylhydroquinone were 
added to the solution, followed by stirring for 10 hours at 110.degree. C. 
The reaction mixture was re-precipitated again from 2 liters of methanol 
to obtain a pale yellow viscous product. The number average molecular 
weight of the product was 3,400. 
PRODUCTION EXAMPLE 6 OF MACROMONOMER: M-6 
A mixture of 95 g of octadecyl methacrylate, 5 g of thioglycolic acid, and 
200 g of toluene was heated to 75.degree. C. with stirring under nitrogen 
gas stream and, after adding thereto 1.5 g of A.I.B.N., the reaction was 
carried out for 8 hours. Then, to the reaction mixture were added 13 g of 
glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 1.0 g of 
t-butylhydroquinone, and the resulting mixture was stirred for 10 hours at 
110.degree. C. After cooling, the reaction mixture was re-precipitated 
from 2 liters of methanol to obtain 86 g of a white powder. The number 
average molecular weight of the product was 2,300. 
PRODUCTION EXAMPLE 7 OF MACROMONOMER: M-7 
A mixture of 40 g of methyl methacrylate, 54 g of ethyl methacrylate, 6 g 
of 2-mercaptoethylamine, 150 g of toluene, and 50 g of tetrahydrofuran was 
heated to 75.degree. C. with stirring under nitrogen gas stream and, after 
adding thereto 2.0 g of A.I.B.N., the reaction was carried out for 8 
hours. 
Then, the reaction mixture was cooled to 20.degree. C. in a water bath and, 
after adding dropwise thereto 23 g of methacrylic acid anhydride in such a 
manner that the temperature was not over 25.degree. C., the mixture was 
stirred for one hour as it was. Then, 0.5 g of 
2,2'-methylenebis(6-t-butyl-p-cresol) was added thereto, and the mixture 
was stirred for 3 hours at 40.degree. C. After cooling, the reaction 
mixture was re-precipitated from 2 liters of methanol to obtain 83 g of 
viscous product. The number average molecular weight of the product was 
2,200. 
PRODUCTION EXAMPLE 8 OF MACROMONOMER: M-8 
A mixture of 95 g of methyl methacrylate and 200 g of toluene was heated to 
75.degree. C. under a nitrogen gas stream and, after adding thereto 5 g of 
A.C.V., the reaction was carried out for 8 hours. Then, 15 g of glycidyl 
acrylate, 1.0 g of N,N-dimethyldodecylamine, and 1.0 g of 
2,2'-methylenebis(6-t-butyl-p-cresol) were added to the mixture, and the 
resulting mixture was stirred for 15 hours at 100.degree. C. After 
cooling, the reaction mixture was re-precipitated from 2 liters of 
methanol to obtain 83 g of a transparent viscous product. The number 
average molecular weight of the product was 3,600. 
PRODUCTION EXAMPLE 9 OF MACROMONOMER: M-9 
A mixture of 96 g of 2-(n-hexylcarbonyloxy)ethyl methacrylate, 4 g of 
thioglycolic acid, and 200 g of toluene was heated to 70.degree. C. with 
stirring under nitrogen gas stream, and, after adding thereto 1.0 g of 
2,2'-azobis(isobutyronitrile) (A.I.B.N.), the reaction was carried out for 
8 hours. Then, 8 g of glycidyl methacrylate, 1.0 g of 
N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to 
the reaction mixture, and the resulting mixture was stirred for 12 hours 
at 100.degree. C. After cooling, the reaction mixture was re-precipitated 
from 2 liters of methanol to obtain 82 g of an oily product. The number 
average molecular weight of the polymer obtained was 5,600. 
##STR45## 
In the above formula as well as the formulae of macromonomers described 
below, the group represented by -- -- means a recurring unit. 
EXAMPLES 10 TO 29 OF MACROMONOMER: M-10 TO M-29 
By following the same procedure as Production Example 9 of macromonomer 
except that each of the compounds shown in Table 7 below was used in place 
of 2-(n-hexylcarbonyloxy)ethyl methacrylate only, each of the 
macromonomers having the following formula was produced. The number 
average molecular weights of the macromonomers thus obtained were in the 
range of from 5,000 to 7,000. 
TABLE 7 
______________________________________ 
##STR46## 
Production 
Example of 
Macro- 
Macromonomer 
monomer R 
______________________________________ 
10 M-10 (CH.sub.2).sub.2 OCOCH.sub.3 
11 M-11 (CH.sub.2).sub.2 OCOC.sub.4 H.sub.9 
12 M-12 (CH.sub.2).sub.2 OCOC.sub.11 H.sub.23 
13 M-13 (CH.sub.2).sub.2 OCO(CH.sub.2).sub.2 COOC.sub.2 
H.sub.5 
14 M-14 (CH.sub.2).sub.2 OCO(CH.sub.2).sub.3 COOCH.sub.3 
15 M-15 (CH.sub.2).sub.2 OCOCHCHCOOC.sub.5 H.sub.11 
16 M-16 
##STR47## 
17 M-17 
##STR48## 
18 M-18 
##STR49## 
19 M-19 
##STR50## 
20 M-20 
##STR51## 
21 M-21 
##STR52## 
22 M-22 
##STR53## 
23 M-23 
##STR54## 
24 M-24 
##STR55## 
25 M-25 
##STR56## 
26 M-26 
##STR57## 
27 M-27 ((CH.sub.2).sub.2 OCO(CH.sub.2).sub.2 SO.sub.2 C.sub.4 
H.sub.9 
28 M-28 (CH.sub.2).sub.2 OCO(CH.sub.2).sub.2 SO.sub.2 C.sub.8 
H.sub.17 
29 M-29 (CH.sub.2).sub.6 OCOC.sub.2 H.sub.5 
______________________________________ 
PRODUCTION EXAMPLE 30 OF MACROMONOMER: M-30 
A mixture of 96 g of 2,3-diacetoxypropyl methacrylate, 4 g of thioethanol, 
and 200 g of toluene was heated to 70.degree. C. with stirring under 
nitrogen atom stream and after adding thereto 1.0 g of A.I.B.N., the 
reaction was carried out for 4 hours. Furthermore, after adding thereto 
5.0 g of A.I.B.N., and the reaction was further carried out for 3 hours 
and, after further adding thereto 0.3 g of A.I.B.N., the reaction was 
carried out for 3 hours. The reaction mixture was cooled to room 
temperature and, after adding thereto 9.6 g of 2-carboxyethyl 
methacrylate, a mixture of 12.7 g of dicyclohexylcarbodiimide (D.C.C.) and 
50 g of methylene chloride was added dropwise to the mixture. Then, 1.0 g 
of t-butylhydroquinone was added to the mixture followed by stirring for 4 
hours. Crystals formed were removed by filtration and the filtrate 
obtained was re-precipitated in 2 liters of methanol. An oily product thus 
precipitated was collected by decantation, dissolved in 150 ml of 
methylene chloride, and the solution was re-precipitated again from one 
liter of methanol to obtain an oily product. The product was then 
collected by filtration and dried under reduced pressure to obtain 54 g of 
a polymer having a number average molecular weight. 
##STR58## 
PRODUCTION EXAMPLES 31 TO 37 OF MACROMONOMER: M-31 TO M-37 
By following the same procedure as Production Example 30 of macromonomer 
except that 2,3-diacetoxypropyl methacrylate and the unsaturated 
carboxylic acid (corresponding to 2-carboxyethyl methacrylate) in Example 
30 were changed, each of the macromonomers shown in Table 8 below was 
produced. The number average molecular weights of the macromonomers thus 
obtained were in the range of from 3,000 to 6,000. 
TABLE 8 
__________________________________________________________________________ 
Production 
Example of 
Macromonomer 
Macromonomer 
Chemical Structure of Macromonomer 
__________________________________________________________________________ 
31 M-31 
##STR59## 
32 M-32 
##STR60## 
33 M-33 
##STR61## 
34 M-34 
##STR62## 
35 M-35 
##STR63## 
36 M-36 
##STR64## 
37 M-37 
##STR65## 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 38 OF MACROMONOMER: M-38 
A mixture of 96 g of 2-(3-methoxycarbonylpropylcarbonyloxy)ethyl 
methacrylate, 4 g of 2-mercaptoethylamine, and 200 g of tetrahydrofuran 
was heated to 70.degree. C. under a nitrogen gas stream. Then, after 
adding thereto 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 4 hours. Then, the reaction mixture was cooled to 
20.degree. C. in a water bath, and, after adding thereto 6.3 g of 
triethylamine, 5.6 g of acrylic acid chloride was added dropwise to the 
mixture with stirring at a temperature below 25.degree. C. Thereafter, the 
resulting mixture was stirred for one hour as it was. Then, after adding 
thereto 0.5 g of t-butylhydroquinone, the mixture was heated to 60.degree. 
C., followed by stirring for 4 hours. After cooling the reaction mixture, 
the operation for re-precipitating the reaction mixture from 2 liters of 
methanol was carried out twice to obtain 54 g of a pale yellow viscous 
product. The number average molecular weight of the product was 4,300. 
##STR66## 
PRODUCTION EXAMPLE 39 OF MACROMONOMER: M-39 
A mixture of 95 g of 2,3-dihydroxypropyl methacrylate, 150 g of 
tetrahydrofuran, and 50 g of isopropyl alcohol was heated to 75.degree. C. 
under a nitrogen gas stream. Then, after adding thereto 4.0 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 re-precipitated from 1.5 liters of water and, the oily product formed 
was collected by filtration and dried under reduced pressure. The amount 
of the product was 85 g. 
To 50 g of the oily product (oligomer) 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 mixture was stirred for 15 
hours at 100.degree. C. After cooling, the reaction mixture was 
re-precipitated from one liter of petroleum ether to obtain 36 g of a 
transparent viscous product. The number average molecular weight of the 
product was 3,600. 
##STR67## 
PRODUCTION EXAMPLE 40 OF MACROMONOMER: M-40 
To a mixture of 50 g of the oligomer (oily product) obtained in Production 
Example 39 of macromonomer as an intermediate, 5.6 g of 2-hydroxymethyl 
methacrylate, and 100 g of methylene chloride was added dropwise a mixture 
of 9.0 g of D.C.C., 0.5 g of 4-dimethylaminopyridine, and 20 g of 
methylene chloride with stirring at room temperature over a period of one 
hour. The mixture was further stirred as it was. The precipitated crystals 
were filtered, and the operation for re-precipitating the filtrate 
obtained from one liter of petroleum ethanol was carried out twice and an 
oily product was dried under reduced pressure. The amount of the product 
was 28 g and the number average molecular weight was 3,000. 
##STR68## 
PRODUCTION EXAMPLE 41 OF MACROMONOMER: M-41 
A mixture of 95 g of 2-(n-nonylcarbonyloxy)ethyl crotonate and 200 g of 
tetrahydrofuran was heated to 75.degree. C. under a nitrogen gas stream 
and, after adding thereto 5 g of 2,2'-azobis(cyanobutanol), the reaction 
was carried out for 8 hours. 
After cooling the reaction mixture to 20.degree. C. in a water bath, 1.0 g 
of triethylamine and 21 g of methacrylic acid anhydride were added to the 
reaction mixture followed by stirring for one hour, and the mixture was 
further stirred for 6 hours at 60.degree. C. 
Then, after cooling the reaction mixture, an operation for re precipitating 
the reaction mixture in 2 liters of methanol was repeated twice to obtain 
62 g of a colorless transparent viscous product. The number average 
molecular weight of the product was 6,200. 
##STR69## 
PRODUCTION EXAMPLES 42 TO 49 OF MACROMONOMER: M-42 TO M-49 
By following the same procedure as Production Example 9 of macromonomer 
except that the methacrylate monomer (2-(n-hexylcarbonyloxy)ethyl 
methacrylate), the mercapto compound (thioglycolic acid), and the epoxy 
group containing monomer (glycidyl methacrylate) were changed, each of the 
macromonomers shown in Table 9 below was prepared. 
TABLE 9 
__________________________________________________________________________ 
Number 
Production Average 
Example of 
Macro- Molecular 
Macromonomer 
monomer 
Chemical Structure of Macromonomer Weight 
__________________________________________________________________________ 
42 M-42 
##STR70## 6,200 
43 M-43 
##STR71## 5,800 
44 M-44 
##STR72## 6,100 
45 M-45 
##STR73## 5,800 
46 M-46 
##STR74## 6,600 
47 M-47 
##STR75## 6,500 
48 M-48 
##STR76## 5,300 
49 M-49 
##STR77## 7,000 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 1 OF LATEX GRAINS: LATEX D-1 
A mixture of 12 g of the resin P-1 obtained in Production Example 1 of 
dispersion stabilizing resin, 100 g of vinyl acetate, 1.0 g of the 
macromonomer M-1 obtained in Production Example 1 of macromonomer, and 380 
g of Isopar H was heated to 75.degree. C. with stirring under nitrogen gas 
stream and, after adding thereto 1.7 g of A.I.B.N., the reaction was 
carried out for 6 hours. Twenty minutes after the addition of the 
polymerization initiator, the reaction mixture became white-turbid, and 
the reaction temperature raised to 88.degree. C. The temperature of the 
system was raised to 100.degree. C., and the reaction mixture was stirred 
for 2 hours to distil off unreacted vinyl acetate. After cooling, the 
reaction mixture was passed through a 200 mesh nylon cloth to provide a 
latex having a mean grain size of 0.20 .mu.m with a polymerization ratio 
of 90% as a white dispersion. 
PRODUCTION EXAMPLES 2 TO 11 OF LATEX GRAINS: D-2 TO D-11 
By following the same procedure as Production Example 1 of latex grains 
except that the compounds shown in Table 10 below were used in place of 
the dispersion stabilizing resin P-1 and the macromonomer M-1, each of 
white dispersions was obtained with polymerization ratios of from 85 to 
90%. 
TABLE 10 
______________________________________ 
Mean Grain 
Production Dispersion Size of 
Example of 
Latex Stabilizing 
Macro- Latex Grains 
Latex Grains 
Grains Resin monomer (.mu.m) 
______________________________________ 
2 D-2 P-2 M-1 0.19 
3 D-3 P-2 M-3 0.22 
4 D-4 P-2 M-4 0.23 
5 D-5 P-2 M-5 0.20 
6 D-6 P-2 M-6 0.21 
7 D-7 P-3 M-1 0.18 
8 D-8 P-4 M-7 0.19 
9 D-9 P-5 M-8 0.20 
10 D-10 P-8 M-2 0.19 
11 D-11 P-9 M-1 0.20 
______________________________________ 
PRODUCTION EXAMPLE 12 OF LATEX GRAINS: D-12 
A mixture of 13 g of the resin P-2 obtained in Production Example 2 of 
dispersion stabilizing resin, 100 g of vinyl acetate, 5 g of crotonic 
acid, 1.0 g of the macromonomer M-1 obtained in Production Example 1 of 
macromonomer, and 468 g of Isopar E was heated to 70.degree. C. with 
stirring under nitrogen gas stream and, after adding thereto 1.3 g of 
2,2'-azobis(isovaleronitrile) (A.I.V.N.), the reaction was carried out for 
6 hours. Thereafter, the temperature of the mixture was raised to 
100.degree. C., and the reaction mixture was stirred at the temperature 
for one hour to distill off remaining vinyl acetate. After cooling the 
reaction mixture was passed through a 200 mesh nylon to obtain a latex 
having a mean grain size of 0.25 .mu.m with a polymerization ratio of 85 
as a white dispersion. 
PRODUCTION EXAMPLE 13 OF LATEX GRAINS: D-13 
A mixture of 14 g of the resin P-1 obtained in Production Example 1 of 
dispersion stabilizing resin, 100 g of vinyl acetate, 6.0 g of 4-pentenoic 
acid, 1.5 g of the macromonomer M-7 obtained in Production Example 7 of 
macromonomer, and 380 g of Isopar G was heated to 75.degree. C. with 
stirring under nitrogen gas stream. After adding thereto 0.7 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 2 
hours. After cooling, the reaction mixture was passed through a 200 mesh 
nylon cloth to obtain a latex having a mean grain size of 0.26 .mu.m as a 
white dispersion. 
PRODUCTION EXAMPLE 14 OF LATEX GRAINS: D-14 
A mixture of 14 g of the resin P-2 obtained in Production Example 2 of 
dispersion stabilizing resin, 85 g of vinyl acetate, 15 g of 
N-vinylpyrrolidone, 1.2 g of the macromonomer M-1 obtained in Production 
Example 1 of macromonomer, and 380 g of n-decane was heated to 75.degree. 
C. with stirring under nitrogen gas stream. After adding thereto 1.7 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 2 
hours. After cooling, the reaction mixture was passed through a 200 mesh 
nylon cloth to obtain a latex having a mean grain size of 0.23 .mu.m as a 
white dispersion. 
PRODUCTION EXAMPLE 15 OF LATEX GRAINS: D-15 
A mixture of 18 g of the resin P-1 obtained in Production Example 1 of 
dispersion stabilizing resin, 100 g of methyl methacrylate, 1.5 g of the 
macromonomer M-2 obtained in Production Example 2 of macromonomer, 0.8 g 
of n-dodecylmercaptan, and 470 g of n-octane was heated to 70.degree. C. 
with stirring under nitrogen gas stream and after adding thereto 1.0 g of 
A.I.V.N., the reaction was carried out for 2 hours. Few minutes after the 
addition of the polymerization initiator, the reaction mixture began to 
become blue turbid, and the reaction temperature raised to 90.degree. C. 
After cooling, the reaction mixture was passed through a 200 mesh nylon 
cloth to remove coarse grains, whereby a latex having a mean grain size of 
about 0.27 .mu.m was obtained as a white dispersion. 
PRODUCTION EXAMPLE 16 OF LATEX GRAINS 
Comparison Example A 
By following the same procedure as Production Example 1 of latex grains 
except that the macromonomer M-1 was not used, a latex having a mean grain 
size of 0.20 was obtained with a polymerization ratio of 85% as a white 
dispersion. 
PRODUCTION EXAMPLE 17 OF LATEX GRAINS 
Comparison Example B 
By following the same procedure as Production Example 1 of latex grains 
except that 1.0 g of octadecyl methacrylate was used in place of the 
macromonomer M-1, a latex having a mean grain size of 0.22 .mu.m was 
obtained with a polymerization ratio of 85% as a white dispersion. 
PRODUCTION EXAMPLE 18 OF LATEX GRAINS 
Comparison Example C 
By following the same procedure as Production Example 1 of latex grains 
except that 1 g of a monomer (I) having the structure shown below was used 
in place of the macromonomer M-1, a latex having a mean grain size of 0.22 
.mu.m was obtained with a polymerization ratio of 86% as a white 
dispersion. 
##STR78## 
PRODUCTION EXAMPLE 19 OF LATEX GRAINS: D-16 
A mixture of 8 g of the dispersion-stabilizing resin P-1, 100 g of vinyl 
acetate, 0.8 g of the macromonomer M-18, and 380 g of Isopar H was heated 
to 75.degree. C. with stirring under nitrogen gas stream. Then, after 
adding thereto 0.8 g of A.I.B.N., the reaction was carried out for 4 hours 
and, after further adding thereto 0.4 g of A.I.B.N., the reaction was 
carried out for 2 hours. After 20 minutes since the addition of the 
polymerization initiator, the reaction mixture became white-turbid and the 
reaction temperature raised to 88.degree. C. Then, after raising the 
temperature of the system to 100.degree. C., the reaction mixture was 
stirred for one hour at the temperature to distil off unreacted vinyl 
acetate. After cooling, the reaction mixture was passed through a 200 mesh 
nylon cloth to obtain a latex having a mean grain size of 0.23 .mu.m with 
a polymerization ratio of 88% as a white dispersion. 
PRODUCTION EXAMPLE 20 OF LATEX GRAINS: D-17 
A mixture of 7 g of the dispersion stabilizing resin P-62, 100 g of vinyl 
acetate, 0.6 g of the macromonomer M-19, and 385 g of Isopar H was heated 
to 70.degree. C. with stirring under nitrogen gas stream. Then, after 
adding thereto 1.0 g of 2,2'-azobis(isovaleronitrile) (A.I.V.N.), the 
reaction was carried out for 2 hours and, after further adding thereto 0.4 
g of A.I.V.N., the reaction was carried out for 2 hours. Thereafter, the 
temperature of the system was raised to 100.degree. C. and the reaction 
mixture was stirred at the temperature to distil off remaining vinyl 
acetate. After cooling, the reaction mixture was passed through a 200 mesh 
nylon cloth to obtain a latex having a mean grain size of 0.22 .mu.m with 
a polymerization ratio of 86% as a white dispersion. 
PRODUCTION EXAMPLE 21 OF LATEX GRAINS: D-18 TO D-46 
By following the same procedure as Production Example 20 of latex grains 
except that each of the compounds shown in Table 11 below was used in 
place of the dispersion stabilizing resin and the macromonomer, each of 
latex grains was produced. The polymerization ratios of the latex grains 
obtained were from 85 to 90%. 
TABLE 11 
__________________________________________________________________________ 
Mean Grain 
Production Dispersion Size of 
Example of 
Latex 
Stabilizing 
Amount Amount 
Latex Grains 
Latex Grains 
Grains 
Resin (g) Macromonomer 
(g) (.mu.m) 
__________________________________________________________________________ 
21 D-18 
P-2 7 M-12 0.8 0.20 
22 D-19 
P-3 8 M-20 1.0 0.21 
23 D-20 
P-4 10 M-25 1.0 0.20 
24 D-21 
P-5 10 M-26 0.7 0.23 
25 D-22 
P-8 9 M-14 1.0 0.20 
26 D-23 
P-9 9 M-18 0.6 0.19 
27 D-24 
P-10 10 M-21 1.2 0.18 
28 D-25 
P-11 9 M-16 1.0 0.24 
29 D-26 
P-12 10 M-11 1.2 0.23 
30 D-27 
P-13 9 M-30 0.8 0.21 
31 D-28 
P-14 9 M-42 0.8 0.20 
32 D-29 
P-15 11 M-43 0.5 0.22 
33 D-30 
P-16 12 M-10 1.2 0.25 
34 D-31 
P-17 12 M-15 1.0 0.24 
35 D-32 
P-18 10 M-17 1.5 0.23 
36 D-33 
P-19 8 M-38 0.7 0.22 
37 D-34 
P-20 12 M-40 1.2 0.18 
38 D-35 
P-23 12 M-41 1.3 0.20 
39 D-36 
P-24 6 M-18 1.0 0.17 
40 D-37 
P-25 8 M-12 1.5 0.18 
41 D-38 
P-27 8 M-18 1.0 0.17 
42 D-39 
P-29 8 M-32 1.0 0.17 
43 D-40 
P-31 7 M-48 2.0 0.17 
44 D-41 
P-41 6 M-27 0.5 0.20 
45 D-42 
P-50 7 M-29 1.2 0.18 
46 D-43 
P-25 8 M-26 2.0 0.20 
47 D-44 
P-58 8 M-46 1.4 0.20 
48 D-45 
P-59 8 M-47 2.0 0.21 
49 D-46 
P-63 9 M-49 0.8 0.20 
__________________________________________________________________________ 
PRODUCTION EXAMPLE 50 OF LATEX GRAINS: D-47 
A mixture of 9 g of the dispersion stabilizing resin P-7, 100 g of vinyl 
acetate, 5 g of crotonic acid, 0.8 g of the macromonomer M-38, and 468 g 
of Isopar H was heated to 70.degree. C. with stirring under nitrogen gas 
stream and after adding thereto 1.3 g of A.I.V.N., the reaction was 
carried out for 6 hours. After raising the temperature of the system to 
100.degree. C., the reaction mixture was stirred for one hour at the 
temperature to distill off remaining vinyl acetate. After cooling, the 
reaction mixture was passed through a 2100 mesh nylon cloth to obtain a 
latex having a mean grain size of 0.19 .mu.m with a polymerization ratio 
of 85% as a white dispersion. 
PRODUCTION EXAMPLE 51 OF LATEX GRAINS: D-48 
A mixture of 10 g of the dispersion stabilizing resin P-63, 100 g of vinyl 
acetate, 6.0 g of 4-pentenoic acid, 0.6 g of the macromonomer M-16, and 
380 g of Isopar G was heated to 75.degree. C. with stirring under nitrogen 
gas stream. After adding thereto 0.7 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 2 hours. After cooling, the 
reaction mixture was passed through a 200 mesh nylon cloth to obtain a 
latex having a mean grain size of 0.20 .mu.m with a polymerization ratio 
of 86% as a white dispersion. 
PRODUCTION EXAMPLE 52 OF LATEX GRAINS: D-49 
A mixture of 10 g of the dispersion stabilizing resin P-62, 85 g of vinyl 
acetate, 15 g of N-vinylpyrrolidone, 0.7 g of the macromonomer M-18, and 
380 g of n-decane was heated to 75.degree. C. with stirring under nitrogen 
gas stream. After adding thereto 1.7 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 2 hours. After cooling, the 
reaction mixture was passed through a 200 mesh nylon cloth to obtain a 
latex having a mean grain size of 0.21 .mu.m with a polymerization ratio 
of 88% as a white dispersion. 
PRODUCTION EXAMPLE 53 OF LATEX GRAINS: D-50 
A mixture of 14 g of the dispersion stabilizing resin P-43, 100 g of 
isopropyl methacrylate, 0.9 g of the macromonomer M-31, and 470 g of 
n-decane was heated to 70.degree. C. with stirring under nitrogen gas 
stream and, after adding thereto 1.0 g of A.I.V.N., the reaction was 
carried out for 2 hours. Few minutes after the addition of the 
polymerization initiator, the reaction mixture began to become blue-turbid 
and the reaction temperature raised to 90.degree. C. After cooling, the 
reaction mixture was passed through a 200 mesh nylon cloth to remove 
coarse grains, whereby a latex having a mean grain size of 0.25 .mu.m with 
a polymerization ratio of 89% was obtained as a white dispersion. 
PRODUCTION EXAMPLE 54 OF LATEX GRAINS: D-51 
A mixture of 13 g of the dispersion stabilizing resin P-45, 100 g of 
styrene, 0.5 g of the macromonomer M-33, and 380 g of Isopar H was heated 
to 60.degree. C. with stirring under nitrogen gas stream. After adding 
thereto 0.6 g of A.I.V.N., the reaction was carried out for 4 hours and, 
after further adding thereto 0.3 g of A.I.V.N., the reaction was carried 
out for 3 hours. After cooling, the reaction mixture was passed through a 
200 mesh nylon cloth to obtain a latex having a mean grain size of 0.24 
.mu.m with a polymerization ratio of 83% as a white dispersion. 
PRODUCTION EXAMPLE 55 OF LATEX GRAINS 
Comparison Example D 
By following the same procedure as Production Example 19 of latex grains 
except that the macromonomer M-18 was not used, a latex having a mean 
grain size of 0.25 .mu.m was obtained with a polymerization ratio of 85% 
as a white dispersion. 
PRODUCTION EXAMPLE 56 OF LATEX GRAINS 
Comparison Example E 
By following the same procedure as Production Example 19 except that a 
mixture of 8 g of a resin having the structure shown below produced 
according to the method described in JP-A-61-43757, 100 g of vinyl 
acetate, and 392 g of Isopar H was used, a latex having a mean grain size 
of 0.18 .mu.m was obtained with a polymerization ratio of 86% as a white 
dispersion. 
##STR79## 
PRODUCTION EXAMPLE 57 OF LATEX GRAINS 
Comparison Example F 
By following the same procedure as Example 19 except that a mixture of 18 g 
of poly(octadecyl methacrylate), 100 g of vinyl acetate, 1 g of a monomer 
(II) having the chemical structure shown below, and 385 g of Isopar H was 
used, a latex having a mean grain size of 0.24 .mu.m was obtained with a 
polymerization ratio of 86% as a white dispersion. (The latex obtained 
corresponds to the latex grains disclosed in JP-62-151868). 
##STR80## 
EXAMPLE 1 
In a paint shaker (manufactured by Tokyo Seiki K.K.) were placed 10 g of a 
dodecyl methacrylate/acrylic acid copolymer (95/5 by weight ratio), 10 g 
of nigrosine and 30 g of Shellsol 71 together with glass beads and they 
were dispersed for 4 hours to obtain a fine dispersion of nigrosine. 
Then, by diluting 30 g of the resin dispersion D-1 obtained in Production 
Example 1 of latex grains, 2.5 g of the aforesaid nitrosine dispersion, 15 
g of a higher alcohol FOC-1400 (trade name made by Nissan Chemical 
Industries, Ltd.), and 0.08 g of an octadecyl vinyl ether/semi-maleic 
octadecylamide copolymer with one liter of Shellsol 71, a liquid developer 
for electrostatic photography was prepared. 
Comparison Liquid Developers A, B, AND C 
Three kinds of comparison liquid developers A, B, and C were prepared in 
the same manner as the aforesaid production example of liquid developer 
except that each of the following resin dispersions was used in place of 
the resin dispersion D-1. 
Comparison Liquid Developers A 
The resin dispersion obtained in Production Example 16 of latex grains was 
used. 
Comparison Liquid Developers B 
The resin dispersion obtained in Production Example 17 of latex grains was 
used. 
Comparison Liquid Developers C 
The resin dispersion obtained in Production Example 18 of latex grains was 
used. 
An electrophotographic light-sensitive material, ELP Master II Type (trade 
name, made by Fuji Photo Film Co., Ltd.) was image-exposed and developed 
by a full-automatic processor, ELP 404V (trade name, made by Fuji Photo 
Film Co., Ltd.) using each of the liquid developers thus prepared. The 
processing (plate-making) speed was 5 plates/minute. Furthermore, after 
processing 2,000 plates of ELP Master II Type, the occurrence of stains of 
the developing apparatus by sticking of the toner was observed. The 
blackened ratio (imaged area) of the duplicated images was determined 
using 20% original. The results obtained are shown in Table 10 below. 
TABLE 10 
______________________________________ 
Stains of 
Test Liquid Developing Image of the 
No. Developer Apparatus 2,000th Plate 
______________________________________ 
Developer of 
No toner Clear 
Example 1 residue 
adhered 
2 Developer A Toner residue Letter part 
greatly adhered 
lost, density 
of solid black 
lowered, back- 
ground portion 
fogged 
3 Developer B Toner residue Density of fine 
adhered slightly 
lines slightly 
lowered, Dmax 
lowered 
4 Developer C Toner residue Density of fine 
adhered lines slightly 
lowered, Dmax 
lowered 
______________________________________ 
As is clear from the results shown above, when printing plates were 
produced by the aforesaid processing condition using each liquid 
developer, the liquid developer of this invention only caused no stains of 
the developing apparatus and gave clear images of the 2,000th plate. 
Then, the offset printing master plate (ELP Master) prepared by processing 
using each of the liquid developers was used for printing in a 
conventional manner, and the number of prints obtained before occurrences 
of defects of letters on the images of the print, the lowering of the 
density of the solid black portions of the image, etc., was checked. The 
results showed that the master plate obtained by using each of the liquid 
developer of this invention and the liquid developers of Comparison 
Examples A and C gave more than 10,000 prints without accompanied by the 
aforesaid failures, while the master plate prepared using the comparison 
liquid developer B resulted in the failures after 8,000 prints. 
As is clear from the aforesaid results, only the liquid developer of this 
invention could advantageously be used for preparing a large number of 
prints by the master plate without causing stains of the developing 
apparatus. 
In the case of using Comparison Liquid Developer A, there was no problem on 
the number of prints, but the developing apparatus was too stained to 
further use continuously. 
Also, in the cases of Comparison Liquid Developers B and C, the developing 
apparatus was stained (in particular), on the back surface of the 
electrode plate) when the developer was used under the condition of a 
rapid processing speed as 5 plates/minute (an ordinary processing speed 
was 2 or 3 plates/minute) and after the formation of about 2,000 plates, 
the image quality of the duplicated images on the plate was reduced (the 
reduction of Dmax, lowering of the density of fine lines, etc.). There was 
no problem on the number of prints by the master plate in the case of 
using the Comparison Liquid Developer C, but the number thereof was 
lowered in the case of using the Comparison Liquid Developer B. 
These results show that the resin grains of this invention are clearly 
excellent. 
EXAMPLE 2 
A mixture of 100 g of the white resin dispersion D-100 obtained in 
Production Example 1 of latex grains and 1.5 g of Sumikalon Black was 
heated to 100.degree. C. with stirring for 4 hours. After cooling to room 
temperature, the reaction mixture was passed through a 200 mesh nylon 
cloth to remove the remaining dye, thereby a black resin dispersion having 
a mean grain size of 0.20 .mu.m was obtained. 
A liquid developer was prepared by diluting 32 g of the aforesaid black 
resin dispersion and 0.05 g of zirconium naphthenate with one liter of 
Shellsol 71. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1, no occurrence of stains of the developing apparatus by 
sticking of the toner was observed even after developing 2,000 plates. 
Also, the quality of the offset printing master plate obtained was clear 
and also the image quality of the 10,000 print formed using the master 
plate was very clear. 
EXAMPLE 3 
A mixture of 100 g of the white resin dispersion obtained in Production 
Example 36 of latex grains and 3 g of Victoria Blue B was heated to a 
temperature of from 70.degree. C. to 80.degree. C. with stirring for 6 
hours. After cooling to room temperature, the reaction mixture was passed 
through a 200 mesh nylon cloth to remove the remaining dye, thereby a blue 
resin dispersion having a mean grain size of 0.25 .mu.m was obtained. 
A liquid developer was prepared by diluting 32 g of the aforesaid blue 
resin dispersion, 0.05 g of zirconium naphthenate and 10 g of a higher 
alcohol, FOC-1600 (trade name, made by Nissan Chemical Industries, Ltd.) 
with one liter of Isopar H. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1, no occurrence of stains of the developing apparatus by 
sticking of the toner was observed even after developing 2,000 plates. 
Also, the image quality of the offset printing master plate obtained was 
clear and also the image quality of the 10,000th print was very clear. 
EXAMPLE 4 
By diluting 32 g of the white resin dispersion obtained in Production 
Example 2 of latex grains, 2.5 g of the nigrosine dispersion obtained in 
Example 1, and 0.02 g of a semi-docosanylamidated product of a copolymer 
of diisobutyrene and maleic anhydride with one liter of Isopar G, a liquid 
developer was prepared. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1, no occurrence of stains of the developing apparatus by 
sticking of the toner was observed even after developing 2,000 plates. 
Also, the image quality of the offset printing master plate obtained and 
also the image quality of the 10,000th print obtained using the master 
plate were very clear. 
Furthermore, when the same processing as above was applied after allowing 
to stand the liquid developer for 3 months, the results were the same as 
above. 
EXAMPLE 5 
In a paint shaker were placed 10 g of poly-(decylmethacrylate), 30 g of 
Isopar H, and 8 g of Alkali Blue together with glass beads followed by 
dispersing for 2 hours to provide a fine dispersion of Alkali Blue. 
A liquid developer was prepared by diluting 30 g of the white resin 
dispersion D-11 obtained in Production Example 11 of latex grains, 4.2 g 
of the aforesaid Alkali Blue dispersion, and 0.06 g of a 
semidocosanylaminated product of a copolymer of octadecyl vinyl ether and 
maleic anhydride with one liter of Isopar G. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1, no occurrence of stains of the developing apparatus by 
sticking of the toner was observed even after developing 2,000 plates. 
Also, the image quality of the offset printing master plate obtained and 
the image quality of the 10,000th print obtained using the master plate 
were very clear. 
EXAMPLES 6 TO 13 
By following the same procedure as Example 1 except that each of the latex 
grains D-3 to D-10 shown in Table 13 below was used in place of the latex 
grains D-1, each of liquid developers was prepared. 
TABLE 13 
______________________________________ 
Example Latex Grains 
______________________________________ 
6 D-3 
7 D-4 
8 D-5 
9 D-6 
10 D-7 
11 D-8 
12 D-9 
13 D-10 
______________________________________ 
When each of the liquid developers was applied to the same developing 
apparatus as in Example 1, no occurrence of stains of the developing 
apparatus by sticking of the toner was observed even after developing 
2,000 plates. Also, the image quality of the 10,000th print obtained using 
each of the master plates were very clear. 
EXAMPLE 14 
In a paint shaker (manufactured by Tokyo Seiki K.K.) were placed 10 g of a 
dodecyl methacrylate/acrylic acid copolymer (95/5 by weight ratio), 10 g 
of nigrosine and 30 g of Shellsol 71 together with glass beads followed by 
dispersing for 4 hours to provide a fine dispersion of nigrosine. 
A liquid developer was prepared by diluting 30 g of the resin dispersion 
D-16 obtained in Production Example 19 of latex grains, 2.5 g of the 
aforesaid nigrosine dispersion, 15 g of a higher alcohol, FOC-1400 (trade 
name, made by Nissan Chemical Industries, Ltd., tetradecyl alcohol), and 
0.08 g of a copolymer of octadecene and semi-maleic octadecylamide with 
one liter of Shellsol 71. 
Comparison Liquid Developers D, E, and F 
Three kinds of comparison liquid developers D, E, and F were prepared using 
the following resin dispersions shown below in the aforementioned 
production method. 
Comparison Liquid Developers D 
The resin dispersion obtained in Production Example 55 of latex grains was 
used. 
Comparison Liquid Developers E 
The resin dispersion obtained in Production Example 56 of latex grains was 
used. 
Comparison Liquid Developers F 
The resin dispersion obtained in Production Example 57 of latex grains was 
used. 
An electrophotographic light-sensitive material, ELP Master II Type (trade 
name, made by Fuji Photo Film Co., Ltd.) was image exposed and developed 
by a full-automatic processor, ELP 404V (trade name, made by Fuji Photo 
Film Co., Ltd.) using each of the liquid developers. The processing speed 
(plate-making speed) was 5 plates/minute. Furthermore, the occurrence of 
stains of the developing apparatus by sticking of the toner after 
processing 2,000 plates of ELP Master II Type was checked. The blackened 
ratio (imaged area) of the duplicated image was determined using 30% 
original. 
The results obtained are shown in Table 14 below. 
TABLE 14 
______________________________________ 
Stains of 
Test Developing Image of the 
No. Developer Apparatus 2000th Plate 
______________________________________ 
1 Developer No toner Clear 
of the residue 
example adhered 
2 Developer D Toner Letter parts lost, 
residue density of solid 
greatly black part lowered, 
adhered background fogged 
3 Developer E Toner Density of fine 
residue lines slightly lowered, 
adhered Dmax lowered 
4 Developer F Toner Density of fine 
residue lines slightly lowered, 
adhered Dmax lowered 
______________________________________ 
When each of the liquid developers was used for plate making under the 
aforesaid processing conditions, only the liquid developer of this 
invention caused no stains of the developing apparatus and gave clear 
images on the 2,000th plate. 
Then, the offset printing master plate (ELP Master) prepared by processing 
using each of the liquid developers was used for printing in a 
conventional manner and the number of prints obtained before the 
occurrences of defects of letters on the images of the print, the lowering 
of the density of the solid black portions of the images, etc., was 
checked. The results showed that the master plate obtained by using each 
of the liquid developer of this invention and the liquid developers in 
Comparison Examples D and F gave more than 10,000 prints without 
accompanied by the aforesaid failures, while the master plate prepared 
using the comparison liquid developer E results in the failures after 
8,000 prints. 
As is clear from the aforesaid results, only the liquid developer of this 
invention could advantageously be used for preparing a large number of 
prints by the master plate obtained without causing stains of the 
developing apparatus. 
In the case of using the comparison developer D, there was no problem on 
the number of prints, but the developing apparatus was too stained to 
further use continuously. 
Also, in the cases of Comparison Liquid Developers E and F, the developing 
apparatus was stained (in particular, on the back surface of the electrode 
plate) when the developer was used under the condition of a rapid 
processing speed of 5 plates/minute (an ordinary processing speed was 2 or 
3 plates/minute) and after the formation of about 2,000 plates, the image 
quality of the duplicated images on the plate was reduced (the reduction 
of Dmax, lowering of the density of fine lines, etc.). There was no 
problem on the number of prints by the master plate in the case of using 
Comparison Liquid Developer F, but the number thereof was reduced in the 
case of using Comparison Liquid Developer E. 
These results show that the resin grains of this invention are clearly 
excellent. 
EXAMPLE 15 
A mixture of 100 g of the white dispersion obtained in Production Example 
20 of latex grains and 1.5 g of Sumikalon Black was heated to 100.degree. 
C. with stirring for 4 hours. After cooling to room temperature, the 
reaction mixture was passed through a 200 mesh nylon cloth to remove the 
remaining dye, thereby a black resin dispersion having a mean grain size 
of 0.25 .mu.m was obtained. 
A liquid developer was prepared by diluting 32 g of the aforesaid black 
resin dispersion, 20 g of a higher alcohol, FOC-1600 (trade name, made by 
Nissan Chemical Industries, Ltd., hexadecyl alcohol), and 0.05 g of 
zirconium naphthenate with one liter of Shellsol 71. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1 for development, no occurrence of stains of the developing 
apparatus by sticking of the toner was observed even after developing 
2,000 plates. 
Also, the image quality of the offset printing master plate obtained was 
clear and the image quality of the 10,000th print obtained using the 
master plate was very clear. 
EXAMPLE 16 
A mixture of 100 g of the white resin dispersion obtained in Production 
Example 51 of latex grains and 3 g of Victoria Blue was heated to a 
temperature of from 70.degree. C. to 80.degree. C. with stirring for 6 
hours. After cooling to room temperature, the reaction mixture obtained 
was passed through a 200 mesh nylon cloth to remove the remaining dye, 
thereby a blue resin dispersion having a mean grain size of 0.25 .mu.m was 
obtained. 
A liquid developer was prepared by diluting 32 g of the aforesaid blue 
resin dispersion, and 0.05 g of zirconium naphthenate with one liter of 
Isopar H. 
When the liquid developer was applied to the same developing apparatus as 
in Example 1 for development, no occurrence of stains of the developing 
apparatus by sticking of the toner was observed even after developing 
2,000 plates. Also, the image quality of the offset printing master plate 
obtained was clear and the image quality of the 10,000th print obtained 
using the master plate was very clear. 
EXAMPLE 17 
A liquid developer was prepared by diluting 32 g of the white resin 
dispersion obtained in Production Example 21 of latex grains, 2.5 g of the 
nigrosine dispersion obtained in Example 14, 15 g of a higher alcohol, 
FOC-1800 (trade name, made by Nissan Chemical Industries, Ltd., octadecyl 
alcohol) and 0.02 g of a semi-docosanylamidated product of a copolymer of 
diisobutyrene and maleic anhydride with one liter of Isopar G. 
When the liquid developer was applied to the same developing apparatus as 
in Example 14 for development, no occurrence of stains of the developing 
apparatus by sticking of the toner was observed. Also, the image quality 
of the offset printing plate obtained and the image quality of the 
10,000th print obtained using the master plate were clear. 
Furthermore, when the same processing was performed after allowing to stand 
the liquid developer for 3 months, the results were the same as above. 
EXAMPLE 18 
A liquid developer was prepared by following the same procedure as Example 
5 except that 30 g of the white resin dispersion obtained in Production 
Example 41 of latex grains was used in place of the white resin dispersion 
D-11. 
When the liquid developer was applied to the same developing apparatus as 
in Example 14 for development, no occurrence of stains of the developing 
apparatus by sticking of the toner was observed. Also, the image quality 
of the offset printing master plate obtained and the image quality of the 
10,000th print obtained using the master plate were very clear. 
EXAMPLES 32 TO 53 
By following the same procedure as Example 18 except that each of the 
latexes shown in Table 15 below was used in place of the latex D-38 
obtained in Production Example 41 of latex grains, each of liquid 
developers was prepared. 
TABLE 15 
______________________________________ 
Example Latex Grains Example Latex Grains 
______________________________________ 
19 D-16 30 D-30 
20 D-17 31 D-31 
21 D-19 32 D-32 
22 D-20 33 D-33 
23 D-21 34 D-36 
24 D-22 35 D-37 
25 D-23 36 D-39 
26 D-24 37 D-40 
27 D-25 38 D-44 
28 D-26 39 D-45 
29 D-27 40 D-46 
______________________________________ 
When each of the liquid developers was applied to the same developing 
apparatus as in Example 14 for development, no occurrence of stains of the 
developing apparatus for development by sticking of the toner was observed 
even after developing 2,000 plates. 
Also, the image quality of the offset printing master plate obtained was 
clear and the image quality of the 10,000th print obtained using the 
master plates was very clear. 
Furthermore, when the aforesaid processing was repeated after allowing to 
stand each of the liquid developers for 3 months, the results were the 
same as above. 
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 modifications can be made therein without 
departing from the spirit and scope thereof.