JPH03170952A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve redispersibility, preservable property and stability by using specific polymer resin particles to form the dispersion resin particles of the liquid developer for electrostatic photography formed by dispersing the resin particles into a specific nonaq. solvent. CONSTITUTION:The dispersion resin particles of the nonaq. system are formed by polymerizing a monomer A and oligomer B, in the presence of a soluble resin for stabilizing dispersion, with the nonaq. solvent obtd. by copolymerizing the monomers expressed by formulas I and II. The nonaq. solvent having >=109OMEGAcm electric resistance and <=3.5 dielectric constant is used. The monomer A is a monofunctional monomer which is soluble in this nonaq. solvent and is insolubilized by polymn. The oligomer B is formed by bonding a polar group, such as sulfo group, only to one terminal of the main chain of the polymer consisting of the repeating unit expressed by formula III and has <=10<4> number average mol. wt. In the formula I, L denotes >=8C aliphat. group; a<1>, a<2> denote a hydrogen atom or alkyl group. In the formula II, A denotes -COO-, etc.; B denotes a group connecting the functional group A and atom group D by a carbon atom; D denotes -COO-, etc. The particulars with the formula III are omitted. The dispersion stability and redispersibility are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field for FLL) The present invention provides an electrostatic material for use in electrostatic materials, comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10" Ωcm or more and a dielectric constant of 3.5 or less. The present invention relates to a body developer, and particularly to a body developer having excellent redispersibility, retention, stability, image reproducibility, and fixing properties.

(Conventional technique 141) General liquid developers for electrophotography are organic or inorganic II such as carbon black, black, nigrosine, and phthalocyanine blue.
II material or dyeing paste and alkynodic resin, acrylic resin,
Rosin, natural or synthetic resin of Gokai Rubber Hat, stone yuzu-based fat lI
Frame control agents that separate into liquids with high insulating properties and low chargeability such as JJ group hydrocarbons, and also include metal separators, lecithin, linseed oil, higher fatty acids, and polymers containing vinyl vinyl n-lithones. The power is increased by 11.

In such a developer, the resin is broken down into particles with a diameter of several nm to several hundred nm as insoluble latex particles, but in conventional liquid developers, the resin is broken down into particles with a diameter of several nm to several hundred nm. Due to insufficient bonding with the insoluble latex particles, the fusible dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, resulting in the particles settling, agglomerating, forming lit-up deposits, and becoming unclear in polarity. Furthermore, once the particles have aggregated and accumulated, it is difficult to redisperse them, so the particles remain attached to various parts of the developing machine, leading to malfunctions of the developing machine such as staining of the image area and clogging of the liquid pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised, and is disclosed in US Pat. No. 3,990,980 and others. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. The redispersion becomes stable, which makes it difficult to redisperse and furthermore causes equipment failure and smearing of copied images.
1 had the disadvantage of being insufficient. In addition, in the method for producing resin particles described above, in order to produce particles with a narrow particle size distribution and a ν dispersion, there are significant restrictions on the combination of the dispersion stabilizer used and the Q'IFJ body to be insolubilized. ,
In general, particles with a wide particle size distribution containing a large amount of cat particles, or particles with a thousand gradient particle diameter of 2 or more were formed. In addition, it is difficult to obtain a desired average tM diameter with monodisperse particles having a narrow particle size distribution, and large particles of 1ρ or more or J of 0.11 or less always form fine particles. However, there were problems in that the partitioning stabilizer used had to be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the drawbacks mentioned in section 2, Graph IJJ was incorporated using the 2'II functional polymer to reduce the amount of co-11 that becomes insolubilized by polymerization in the presence of 7f- of the 2'II functional polymer. A method of polymerizing the body to form insoluble dispersed resin particles;
(Japanese Patent Application Laid-open No. 185962), or No. L In the presence of the dispersion stabilizing polymer, a monomer that becomes insolubilized by polymerization and a monomer containing a long-chain alkyl moiety or a monomer containing two or more types of polar components are copolymerized to form an insoluble component. A method for improving the dispersibility, redispersibility, and storage stability of particles is disclosed.

(Problem to be solved by the invention) On the other hand, in recent years, attempts have been made to print a large number of 5,000 or more sheets using an electrophotographic offset printing master plate, and improvements in the master plate in particular have been made. It has become possible to print over 10,000 large-sized sheets. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixing process.

Old records JP 60-185962 and JP 60-1859 (
The disintegrating resin TF produced according to the method disclosed in No. i3 has advantages in terms of development speed, particle dispersion and redispersibility, as well as shortening of the fixing time or large size printing. In the case of master plates of a size (for example, A-3 size or larger), the performance was not always satisfactory in terms of printing durability. Also, the aforementioned Unexamined Patent Publication No. 62-
In the case of a large size master plate, it is possible to separate more than 10,000 sheets of separated resin particles according to u; Performance has not always been satisfactory in terms of particle dispersibility and C-dispersibility when the development speed is at its upper limit, and in terms of printing durability when the fixing time is shortened.

The present invention solves the problems of conventional liquid developers as described above.

An object of the present invention is to speed up the development and fixation process and to achieve n. Even in an electrophotolithography system using a master plate of one plate size, the stability of dispersion, redistribution, and fixation t'
It is an object of the present invention to provide a 7-night body developer with excellent t.

Another object of the present invention is to provide a liquid developer that enables the production of the Offsesoto Seal stamp Kawagen plate by electrophotography, which has excellent oil sensitivity and discrimination resistance.

Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various transfer applications in addition to the above-mentioned applications.

Still another object of the present invention is to provide a liquid developer which can be used in any system in which a 7-night developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. It is to provide. (Means for Solving the Problems) The above-mentioned objects of the present invention are as follows:
A liquid developer for electrostatic photography in which at least resin particles are dispersed in a non-aqueous solvent having a dielectric constant of 3.5 or less, wherein the dispersed resin particles are a monomer represented by the following general formula (I). and the following general formula (b)
In the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent obtained by copolymerizing with the monomer represented by Monomer (Δ) and the following general formula (In)
A carboxyl group, a sulfo group, a hydroxyl group,
An oligomer (B This has been achieved by a liquid developer for electrophotography, which is characterized in that it is polymer resin particles obtained by polymerizing a solution containing at least one of the following. General formula (I) "CII=C-COO-L In formula (I), L represents an aliphatic group having 8 or more carbon atoms, a1 and at may be the same or different, and each represents a hydrogen atom or an alkyl group. Represent. General formula (n) bl In formula (II), A represents -COO- -CONI1- or -CON (zl represents an aliphatic group), B represents the above functional group A and atomic group D, and represents a hetero atom. D is a group connected through a carbon atom bt b3 which may be via
-COO- -C00CI1! −
,-COOCIICI. ? - -SO■1 or 10-, respectively.

11 0 However, when 8 represents -COO-, B and D are replaced by b"
1,! It may be directly bonded to 1C=CI1 without intervening. Also b1
,b! and b1 may be the same or different and each represents a hydrogen atom or an alkyl group.

General formula ([[I) dl dt ■ E-CIl-C)-V'-(-R'-X'}-{R"-X"}H-Y' In the general formula (I), v0 is -O- -S?OO-
-OCO- -CIl■OCO- or -ClhCO
Represents O-.

Y0 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

XI and ×2 may be the same or different from each other, and 0-
-S- -CO-, -COt- -OCO-
, SO, v v' y N- represents -CON- or one NGO- (Y' represents the same content as yo above).

R2 and R3 may be the same or different from each other, may be substituted, or -(Jl-)
{R'-X'}pY'' bond [x3, x4 may be the same or different from each other, and have the same content as xi, x! above, and R4 may be substituted. Indicates a good hydrocarbon having 1 to 18 carbon atoms, and Y2 has the same content as YO] 1 to 18 carbon atoms
18 hydrocarbon groups.

d1 and d2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an ano group, a hydrocarbon group, COO-R
' or one COO-R' via a hydrocarbon (R' represents a hydrogen atom or a hydrocarbon group that may be substituted). m, n and p may be the same or different, and are O~4
represents an integer. However, m+n is 1 or more.

The liquid developer of the present invention will be explained in detail below. Electrical resistance used in the present invention: 10! Ωcm or more, lightning dielectric rate 3.
5 or less, preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, and halogen-substituted products thereof. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isovar E1 Isopar G1 Isopar I+, Isovar L (Isopar; trade name of Exxon) ), Ciel Sol 70, Ciel Sol 7l (Ciel Sol; trade name of Ciel Oil Co., Ltd.)
, Amsco OMS, Amsco 460? Agent 8 (Amsco; a trade name of Spirits Inc.) is used alone or in combination.

Non-aqueous dispersion 4, the most important component in this introduction
: A fat particles (hereinafter sometimes referred to as latenox particles) are composed of a monomer represented by the general formula (+) and the general formula ([) in a non-aqueous solvent.
Monomer (A) and oligomer (B) are polymerized under the 7I flower of a dispersion stabilizing resin that is soluble in the J1 aqueous solvent obtained by copolymerizing with the monomer shown by thing(
It is manufactured by the so-called polymerization granulation method.

Here, as the 31 water solvent, basically any solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic t(l-body developer).

That is, the medium used in producing the dispersed resin granules may be any medium as long as it is miscible with the body fluids mentioned above, and preferably linear or segmented aliphatic hydrocarbons, alicyclics, etc. Examples include formula hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoparaffin petroleum solvents Isopar E, Isopar G1, Isopar H, Isopar I, Sielzol 70, Sielzol 71, Amsco OMS, Amsco 460 A welding agent or the like is used alone or in combination.

Solvents that can be used in combination with these solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, proyl alcohol, butyl alcohol, fluorinated alcohol, etc.), getones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.). etc),
Carboxylic acid esters (e.g. methyl acetate, ethyl acetate, probyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (For example, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methylchloroform, etc.). After polymerization and granulation, the non-aqueous solvent used in combination with these
Although it is preferable to remove the particles by heating or under reduced pressure, there is no problem even if they are carried into a liquid developer as a Latinx particle dispersion, as long as the liquid resistance of the developer satisfies the condition of 10 9 Ωcm or more.

In general, it is preferable to use the same solvent as the carrier liquid at the stage of producing the resin dispersion, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogens, etc. Examples include hydrogenated hydrocarbons.

The dispersion stabilizing resin used to make a stable resin dispersion of the solvent-insoluble polymer obtained by polymerizing the monomer (A) and the oligomer (B) in a non-aqueous solvent is as described above. This is a copolymer resin soluble in the non-aqueous solvent obtained by copolymerizing a monomer represented by general formula (I) and a monomer represented by general formula (II).

There are no particular restrictions on the solvent used when copolymerizing the monomers of general formulas (I) and (II) to form a dispersion stabilizing resin, but the copolymer can be used in the following manner without removing the solvent. In order to apply it to polymerization granulation, it is desirable to use one that is miscible with the solvent used in polymerization granulation. For example, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof may be used alone or in combination. The monomers represented by general formulas (I) and (If) will be explained in more detail below.

In general formula (I), preferably L is an optionally substituted alkyl group having 10 to 32 carbon atoms or 1. 0-32
the optionally substituted anolekenyl group of a' and a2
represents a hydrogen atom or a methyl group. More specifically, the monomer of general formula (I) is an alkyl ester of acrylic acid or methacrylic acid (the alkyl group is, for example,
octyl group, decyl group, 2-ethylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, etc.) or alkenyl esters of acrylic acid or meccrylic acid (for example, octenyl group, decenyl group, octadecenyl group, oleyl group, linoleyl group, etc.). On the other hand, in general formula (n), preferably A is -COOZ CONII- or -CON- (Z' is a carbon number of 1 to
(representing an alkyl group or alkenyl group of 22),
D is COO- -COOCIIZ- or -0-, 8
b1, b2 and b'' are each a hydrogen atom or methyl represents a group.

Z2 Further, to give a specific example of 8, {C}-Z3 (Z2, Z3 are hydrogen atoms, alkyl groups, Nokawa's hydrogen atoms NIICO-, NIISOz NIICONI+, -NIICOO SO2 CO-, 0 S N (zJ is composed of any combination of atomic groups such as a hydrogen atom, an alkyl group, etc.).

General 2 (II) More specifically, as a single object, The following compounds may be mentioned by way of example.

(I) CH3 CI+. =C COOCR=Cll* (2> 11 CH.=C C00CH!COOCII=CIlZ (3) CH. CIlt=C ?00C11■COOCII・C11, (4) Cll, CH.2C ?00CIhClhCOOC■・CI+■( 5) CH3 CIlyo・C ?00(Cth)scOOcll・CI+■(6) I] ?I+■ C ?oo (CIlz) zcOOcll■COOCIl
=CHz(7) C11, ? Il■=C? OOCI! ■COOCll2CI? I1■ (8) ]1 Clh. C? OO (Cll t> zcOOclI■Cl+?I
+■ (9) Clh CI12 C CONtl (CHz) zcOOcH CI12 (lO) Cll:1 CII2 C CONII (CHz) acOOctlCH2 (I1) Clh (l2> Clh CI!2 C ?ON+1 (C!1■) 1.COOC }IzCHC}+
2 (Eng. 3) H cut=c? OO(CI■)2 0 CI1? ll■ (I4) CHff cth-c CONII (Cll z) a 0-CI+ CH2 (l5) Cll3? ll■ C CON (JIzCIIzCOOCll CI+2 C.I1. ?16) Cllz CI+2=C CONCI1xCHzCOOCII■CIl. CH,C
&Hl3 The soluble copolymer resin used in the present invention described above (
To produce a dispersion stabilizing resin), one gram of the general formula (I
) and the monomer represented by the general formula (n), dispersed resin particles! ! ! In the same solvent as used for the production, in the presence of a polymerization initiator such as benzyl peroxide or abbisbutyronitrile, the reaction temperature is 50 to 100'.
The reaction may be carried out at C for a reaction time of 2 to 1011.7 hours.
Under the above polymerization conditions, gelation due to crosslinking reaction of the copolymer does not occur at all, and a copolymer containing a desired double bond in the side chain can be obtained.

In the present invention, a ternary or more copolymer can be obtained by further adding other monomers to the reaction system and performing a polymerization reaction. In any case, the monomer of formula (I) and the formula (If
) has a monomer composition ratio of 50:50 to 99.5:
0.5 (weight ratio) is preferable, and the weight average molecular weight of the copolymer is preferably 5,000 to 500,000. Specific examples of the dispersion stabilizing resin prepared as described above are shown below, but the content of the present invention is not limited thereto.

(a) Cll. C11, (b) CI1, CI+, ? (CIl■-C} -( Cll t -
C)-COOC+slhv COOCII・CI+. (c) C11, ? C II■1C}-(CI1 .-CI+)-co
oc Z II t S? 00C11. CII■COOCll2COOCII=
CIl2(d) C11, ? (Ch-CIl-%Cli-C)-COO
C+aHzq? OOOCll2COOCll=CI+■C11, ? 011■ 0-111 { C I1 2 CH)- COOC+alh! ? oo(CH2)acOOcII■CH? L + ■ C113 CI13 ｛CLL Z CLL, CH3 1 C + (CIL -CI + COOC + ALLZT? ON! 1 (CIL ■) I, OCII CI! - C II) - COO
C1all3t? O O C II■CtlzOCllCI! , (j) CI+, C s If q Furthermore, when obtaining dispersed resin particles comprising the monomer (A) and oligomer (B) of the present invention, conventionally known dispersion methods may be used together with the dispersion stabilizing resin of the present invention. Stabilizers can also be used.

That is, various synthetic resins or natural resins soluble in aqueous solvents can be used alone or in combination of two or more. For example, an alkyl chain having a total of 4 to 30 carbon atoms (which may contain substituents such as a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, etc.) or a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. alkyl esters of acrylic acid or methacrylic acid, vinyl esters of fatty acids, or vinyl alkyl ethers, or olefins such as butadiene, isoprene, diisobutylene, etc. Polymers of monomers or copolymers formed by combining two or more types of monomers, furthermore, monomers that form polymers soluble in organic solvents as described above and various monomers 111 as shown below. A copolymer with the above and using the following lit form can also be used as long as the obtained copolymer is soluble in the medium.

For example, methyl, ethyl, n-probyl or i
so-propylester: styrene, vinyltoluene,
Styrene conductors such as α-methylstyrene: Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, monotonic acid, maleic acid, and itaconic acid, or their anhydrides: hydroxydiethyl methacrylate, hydroxydiethyl acrylate, diethylaminoedyl methacrylate, N-vinylpyrrolidone, acrylamide, acryloni-1-lyl, 2-
Hydroxy group, amino group, such as chloroethyl methacrylate, 2 2, 2 trifluoroethyl methacrylate,
Examples include monomers containing various polar groups such as an amito group, a cyano group, a sulfonic acid group, a carbonyl group, a halogen atom, and a heterocycle. Alternatively, in addition to the above synthetic resins, natural resins such as alkyd resins, alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can also be used.

Of the total dispersion stabilizing resin used to obtain the dispersed resin particles of the present invention by polymerization granulation, the proportion of the dispersion stabilizing resin of the present invention is 50% by weight or more, preferably 80% by weight or more of the total weight. be.

The components used in producing the non-aqueous decomposable resin are soluble in the non-aqueous solvent, but become insolubilized by polymerization.They can be distinguished into functional monomers (A) and oligomers (B). can.

The monomer (A) in the present invention may be any functional monomer that is soluble in a non-aqueous medium but becomes insolubilized by polymerization. Specifically, for example, the general formula (
Examples include monomers represented by rV).

Represents the general formula (TV) e I e Z Cll=C T-U. Here, " is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, butyl group, butyl group, 2-chloroethyl group, 2
-Promoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorohenzyl group, methylbenzyl group, methoxyhenzyl group, phenethyl group, 3-phenylp1cobyl group, dimethylhenzyl group, fluorohendyl group, 2- methoxyethyl group, 3-methoxypropyl group, etc.

U is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, proyl group, butyl group, 2-chloroethyl group, 22-dichloroethyl group,
2,2.2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group,
2-hydroxybrobyl group, 2,3-dihydroxybutyrovir group, 2-hydroxy-3-chloroprobyl group, 2-cyanoethyl group, 3-cyanobutyl group, 2-nitroethyl group, 2-methoxyethyl group, 2 -methanesulfonylethyl group, 2-ethoxyethyl group, NN-dimethylaminoethyl group, N,N-diedylaminoethyl group, trimethoxysilylbutyl group, 3-promopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-chenylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carpoxyethyl group, 3-carpoxyprobyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3- Sulfopyl group, 4-sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group,
(2-N-methyl rupoxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

e1 and e2 may be the same or different, and each represents the same content as d' or d2 in the general formula (III).

Specific -rLffi forms (A) include, for example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, brobionic acid, acetic acid, monochloroacetic acid, trifluoroprobionic acid, etc.); Carbon in unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid! 1 to 4 substituted alkyl esters or acotos (alkyl groups such as methyl group, ethyl group, proyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-chloroethyl group,
1 [:1 ethyl group, trifluoroethyl group, 2-human l
I xyethyl history, 2-cyanoethyl group, 2-nit I. I
Ethyl group, 2-mel xyethyl group, 2-methanesulfonylethyl group, 2-henzenesulfonylethyl group, 2-
(N,N-dimethylamino)ethyl group, 2(N,N-diethylamino)ethyl group, 2-carboxyethyl group, 2
-phosphoethyl group, 4-carboxybutyl group, 3-sulfobrobyl group, 4-sulfobutyl group, 3-chloroprobyl group, 2-hydroxy-3-chloroprobyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-chenylethyl group, trimethoxysilylbropyl group (2-carboxyamidoethyl group, etc.); styrene derivatives (e.g., styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene,
promostyrene, vinylhenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethylstyrene, vinylbenzene rupoxyamide, vinylbenzenesulfonamide, etc.); acrylic acid, Unsaturated carboxylic acids such as meccrylic acid, crotonic acid, maleic acid, and ichonic acid; cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile; methacrylonitrile; heterocyclic compounds containing polymerizable double bond groups (specifically For example, Polymer Science Hall "Polymer Data Handbook Basic Edition 1", pp. 175-184, Baifukan (published in 1986)
(eg, N-vinylpyridine, N-vinyligodazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.). Two or more types of monomers (A) may be used in combination.

The oligomer (B) has only one end of the main chain of the polymer consisting of repeating single units (I't) represented by the 1M formula (It),
By bonding the above-mentioned specific polar groups, a certain number-average molecule becomes 1
It is an oligomer of 0' or less.

In general formula (I), d1, d2, Y0, Y1 and Y2
The hydrocarbon groups contained in each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted.

Formula (Ill) Niite v0 is -o- -s- -
cooOCO- -C11zOCO- or -C}l.
Represents cOo-.

Y0 preferably represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms in total. Preferred aliphatic groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, proyl group, butyl group, hebutyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxylponylethyl group, 2-methoxyethyl group, 3-bromopropyl group], substituted with 4 to 18 carbon atoms optional alkenyl groups (e.g., 2-methyl-1
-7''ropenyl 3,2-butenyl group, 2pentenyl group,
3-methyl-2-pentenyl group, 1-bentenyl group, l
-hexenyl group, 2-hexenyl group, 4-methyl-2-
hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., ethyl group, benzyl group, phenethyl group, 3
- phenylprobyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, promobenzyl group, methylhenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group),
Examples include optionally substituted alicyclic groups having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexylethyl L2-cyclobentylethyl group, etc.).

x1 and x2 may be the same or different, and O-
-S- -CO-, -COO- -OCO-
-502Y'Y' Y N- -CON- or -NCO- (V' indicates the same content as "2" YO). More outrageously,
-0V CO-, -coo- -oco- or -N-.

Rl and llt may be the same or different, and 1
A hydrocarbon group (hydrocarbon Examples of the group include aliphatic groups such as an alkyl group, an alkenyl group, an aralkyl group, and an alicyclic group.Specific examples of these aliphatic groups include the above-mentioned preferred aliphatic nJ4 group group of Y0. The same contents are mentioned. 41Xshi, X3, x4 may be the same or different,
'' indicates the same content as x1 and x2, R4 indicates an optionally substituted alkylene group, alkenylene group, or aralkyl group having 1 to 18 carbon atoms, and yt indicates the same content as Yl' above. .

Furthermore, regarding R2 and R3, to give a specific example, R
1 R7 or an alkyl group having 1 to 6 carbon atoms, a halogen atom (X co, x4, Y!, R4, and P have the same meanings as the above symbols), etc. It is something that will be destroyed.

d′ and d2 may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a probyl group, etc.), -
Coo-R' or -CIhCOOR'(R' is a hydrogen atom or a C1-18 alkyl group, alkenyl group,
represents an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, and specifically represents the same content as described for YO above.

m, n and P may be the same or different, and are 0 to 4.
represents an integer. However, m+n≧l.

Further specific examples of the repeating unit represented by the general formula (Ill) as described above are given below. However, the content of the present invention is not limited to these.

In the following, a is -11 or -0113; R is CI
-I1 alkyl group; R' is a hydrogen atom or C1-. an alkyl group; k2 is an integer from 1 to l2; i,, 1
2 represents an integer from 1 to 100.

(＾〉-18 1 -(CI+. - C}- Coo (Cllt}ii--, OCOR(A)-2 -{CH, C}- Coo(Clldb, COOR (A) 3 {CHz CF ?00( C11■←OCO(Cll2厠OCf)I?k
+ (A) 4 a C −{−C I1 2 − C}−? 00(CIl■buOCO(Cllzi COOR(A
)-5 (8) 6 -+CH2-C}- COO(CI12buOCOCI1 CI+ COOR (A) 7 a 1 →CHt-C)- Coo(JItCllCtlzOCORC OCOR (8) 8 ?(C11■ C)~ ?OO( CI+■)-b, OCO (Cllz) z
NllR (A) 9 (Cll2 C)-? 00(CI12CII■O},-111'(A) 10 ?{CI+■ C}- C113 ?00(Cll■CIIO},rl?'(c) 11 (8) l2 A CI+ 2 CTOOCIICIl2COOR CHzCOOR ( A)-13 -{C H z C-}- ?OOCHCIIzCOO(Cll■97COOR?I
l■COO(Cll■7COOR?{CI1■C)-? oo(CI[zbuOCO (CH z) 2S(J■
RC]13 1 -{CIl-Cll}- Coo(Cllz)-i,, OCOR(A)16 Cll3 →CH CI+}-? OOCII■[:llCll zOcOROCOR -{CIl f - CI1}- OCO(Clh}f'OCOR (A)-18 -(CIIZ-Cl+}-(CIl
g) -coo (CI+ .buCOORk. In addition, in the oligomer (B) provided for the present invention, other repeating units may be contained as a copolymerization component together with the repeating unit represented by general formula (II). good.

As the other copolymerizable component, any compound may be used as long as it is a monomer copolymerizable with the monomer corresponding to one repeating wheel of the general formula (III). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4-pentene fl, and esters or amides of these unsaturated carboxylic acids; carbon number 1 to
22 fatty acid vinyl esters or allyl esters; vinyl ethers; styrene and styrene derivatives;
Examples include heterocyclic compounds containing unsaturated bonds.

Examples include, for example, the compounds exemplified as monomer (A) above, but are not limited thereto. In the total number of repeating units in oligomer (8), repeating units represented by the general formula ([[I] account for 40% of the total
It is preferable that the content is 6 or more, more preferably 6
It is 0 to 100% by weight.

If the component represented by the general formula [[I] is less than 40% by weight of the total, the mechanical strength of the image area formed by the minute fit resin particles will not be maintained sufficiently, and therefore it will not be used as an off-cent original plate. The effect of improving printing durability over time is no longer visible.

R1 represents a polarity 0 1 0 {1 that is bonded only to one end of the main chain of a polymer having a molecular weight of several thousand or less and having a molecular weight of IXIQ' or less and containing at least one type of repeating unit represented by the general formula (III) described above; preferably represents a hydrocarbon group having 1 to 18 carbon atoms. More preferably, the hydrocarbon group of Rl is
An optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, proyl group, butyl group, hentyl group,
hexyl carbon, butenyl group, pentenyl group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, noclobentyl group, cyclohexyl group, henzyl group, phenethyl group, chlorobenzyl group, promohenzyl group, etc.), or may be substituted. Represents an aromatic group (eg, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, promophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Moreover, among the polar groups of the present invention, the amino group is -Nl1! , 1~
It represents a hydrocarbon group having 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically represents the same content as the hydrocarbon group of R'' mentioned above.

Even more preferably, the hydrocarbon groups of Rl, RII and R9 include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, or an optionally substituted phenyl group.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main frame of the oligomer (B) or bonded via an arbitrary linking group. Examples of the group connecting the component of formula (In) and the polar group include a carbon-carbon bond (single bond or double bond), a carbon-carbon heteroatom bond (heteroatoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, (silicon atom, etc.), a heteroatom-heteroatom bond, and any combination of atomic groups.

Among the oligomers (B) of the present invention, preferred ones are
Va) or as shown by formula (Vb).

General formula (Va) dl dl Low W-{CI-C)- ν'-CR"-X')i-<R'-X")-yY' General formula (Vb) d1 dffi VaCll-C)- W-Q V'4R"-X'), -(R'-X">ri-Y' formula (
Va) and 2 (Vb), d1, d2, at, n3,
×1, x2, v6, Y6, m and n represent the same contents as the symbol 2 (III). Q represents the aforementioned polar group bonded to one end in formula (III).

RI6 W is a simple bond or -fC}-CR'', R1
R1 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alwyl group (e.g., a methyl group, an ethyl group, a probyl group), -{CH =CH}-, 10) (Il mouth, 171
1 each independently represents a single linking group selected from a hydrogen atom, a hydrocarbon group having the same content as Y0 above, or a linking group flanked by an arbitrary combination. If the upper limit of the average molecular weight of the oligomer (B) exceeds 1 x 10', printing durability will decrease. On the other hand, if the molecular weight is too small, there is a tendency for staining to occur, so it is preferably IXIO' or higher. In addition, the main chain of the oligomer (B) contains covalent groups containing polar groups such as a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, and a -P-110 group. Preferably, it does not contain polymeric components. The oligomer (B) of the present invention, in which a specific polar group is bonded to one terminal ζ of the polymer main chain, is obtained by: (Method using ionic polymerization method), ■ Method of radical polymerization using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (Method using radical polymerization method), or ■
It can be easily produced by a synthetic method such as a method in which a polymer containing a terminal reactive group obtained by the above-mentioned ionic polymerization method or radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction. can. Specifically, P. Dreyfuss, R. P. Qui
rk, Encycle. Polym. Sci. En
g. ．． 7, 55H1987), Yuya Yamashita, Yoshiki Chujo, “Dye and Medicine.” Co., 232 (I985), Akira Ueda, Susumu Nagai "Science and Industry". It can be produced by the method described in the review article such as ``Nami, 57 (I986)'' and the literature by Hikikawa. Examples of the above-mentioned polymerization initiators containing a specific polar group in the molecule 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-methyl-N-(2-hydroxyethyl)propioamide), 2.2'-azobis(2methyl-N-(I,1-bis(hydroxymethyl)ethyl)probioamide 1, 2.2'-Azobis(2-methyl-N-(I.1-bis(hydroxydimethyl)-2-hydroxydiethyl)propioamide 1,2.2
'-azobis(2-(5-methyl 2-imitasoline-2
-yl)propane), 2,2'-azobis(2-(4
5.6.7-tetrahydro-LH-1.3-diazepin-2-yl)propane), 2.2'-azobis(2-
(3,4,5.6-tetrahydrobyrimidin-2-yl)propane), 2,2'-azobis(2-(5-hydroxy-3.4,5.6-tetrapyrimidin-2yl)
propane), 2,2'-azobis{2-(I-(2-hydroxyethyl)-2-imidazolin-2-yl]proban}, 2,2'-azobis(N-(2-hydroxyethyl)-2- Mediloop oral bioamidine), 2.2
Examples include azobis-based compounds such as '-azobis(N-(4-aminophenyl)-2-methylpropionamidine). In addition, examples of chain transfer agents containing a specific polar group in the molecule include merkabut compounds, disulfide compounds,
Examples include iodine-substituted compounds, preferably mercapto compounds. For example, thioglycolic acid,
2-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol,
Examples include 2-mercaptoethylamine, thiosalicylic acid, α-thioglycerin, 2-phosphonoethylmercabutane, hydroxythiophenol, and derivatives of these mercapto compounds. These polymerization initiators and/or chain transfer agents are used in a proportion of 0.5 to 20% by weight based on the total amount of the monomer corresponding to the repeating unit represented by general formula (III) and other polymerizable monomers. used, preferably 1-1
It is 0% by weight. Preferred oligomers (B) according to the present invention are represented by the general formula (Va) or (Vb), and the moieties represented by QW- in these two are more specifically exemplified below. However, the scope of the present invention is not limited to these. In the following, k1 is an integer of l or 2; k! represents an integer from 2 to 16; k represents an integer of l or 3. (B) −1: II00CfCHx
h+S(B)-2: IIOOC-CO-Su
ooc-cH. (B)-3: II00c (Cll z}yzooC(CII Jy
rS00 4: HOOC(CL}vyNIIco{Cold h-T-S-(
B) 7: 110 (CH zh+-rs (B) 8: tl,N(CL)-rfs (B) 9: ?10CII-CIl■S 110cH. (B) lO: 0 11 !10 - P - 0 ( CIIg)1τS-011 (B) ll: 0 11 R-0-P-0(CHth-ys 011 R: C. Alkyl group (B) 12: +10,S (CI!2) ,S-C11, ( B) 17: 1100C{Ch)tC- CN Clh (B) 18: 110 (Cllz}yrC= CN CI+. (B) I9: ?10(Clz}iio(Ic(CI!■)-TC~C
N C11, (B) 20: ? 100C(CI■}rycOO(Cll■}rs C
CN Cll, C11, 011 CN CL (B) 23: R-NIICO-C C}13 Cll. DHR: IIMcII! )T, LC-C-CIl,
O}I R 0H Z: -{Cllr}y, ICIIJi, CHzCllCllz R: {1, -CH! CIl. OH (R1; ■ ?ll■ 01l) Clls (B) 26: 011C (Cll r}rC 100 27: R-P-0(CL)ts-0■ R; C 6 alkyl group (B)-29 : HOOC(Cllg)!NH(C
JIt}rrs(B)-30: IIOOc(CH
z}yxcONtl(CL)-TTS The dispersion resin of the present invention is composed of at least one of each of the monomer (A) and the oligomer (B). If the resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, it is preferable to use the oligomer (B) represented by the general formula ([[) in an amount of 0.05 to 10 weight percent, more preferably 0. .1 to 5% by weight.

Even more preferably it is 0.3 to 3% by weight. In addition, the molecular weight of the dispersion resin of the present invention is 10'' to 101, preferably 10' to 5XIO'. In order to produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stability is required. If the resin, intermediate (8), and oligomer (B) are heated and polymerized in a nonaqueous solvent in the presence of a trivial initiator such as henzoyl peroxide, azobisisobutyronitrile, butyllithium, etc. Good.Specifically, ■dispersion stabilizing resin, monomer (A) and oligomer (8
) Method of adding a polymerization initiator to the 'Ill mixture solution, ■
A method in which the monomer (A) and the oligomer (B) are dropped together with a polymerization initiator into a solution in which the dispersion stabilizing resin is dissolved; In a mixed solution containing a part of the mixture of (B),
A method of intentionally adding the remaining monomer mixture together with a polymerization initiator, and a method of adding a mixed solution of a dispersion stabilizing resin, a monomer (A), and an oligomer (B) in a nonaqueous solvent, There are methods of optionally adding it together with a polymerization initiator, and it can be produced using either method. The total amount of monomer (A) and oligomer (B) is about 5 to 801 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent.

The soluble resin as the dispersion stabilizing resin is used in an amount of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the total amount of the monomer (A) and oligomer (B) used above. It is.

The polymerization initiator is monomer (A) and oligo"7-(B
) of the total amount is appropriate. Further, the polymerization temperature is about 50 to 180°C, preferably 60 to 180°C.
It is 20°C. The reaction time is preferably 1 to 15 hours. When the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used together in the non-aqueous solvent used in the reaction, or unreacted substances of the monomer (A) to be polymerized and granulated are If it remains, it is preferable to remove it by heating it to a temperature above the boiling point of the solvent or monomer or by distilling it off under freezing pressure. The non-aqueous splitting resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and at the same time exhibits very stable dispersibility, especially when used repeatedly in a developing device for a long time. Even after use, it has good dispersibility and is easy to redisperse even when the development speed is increased, and no stains are observed on various parts of the equipment. Furthermore, when fixed by heating or the like, a strong film was formed and exhibited excellent fixing properties.

Furthermore, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-size master plate is used. Although the details of the reason why the redispersion and toner image fixing properties are significantly improved as described above when the 4M resin particles of the present invention are used as a liquid developer are not known, the method for polymerizing and granulating resin particles of the present invention Even if oligomer (B) was added as a post-addition after polymerization granulation without using oligomer (B), the above effects were not observed. This is considered to be because the oligomer (B) used in the resin particles of the present invention modifies the surface of the resin particles.

In other words, since the polar group is specifically bonded to only one end of the polymer main chain and is granulated by polymerization in a non-aqueous solvent, it is bonded to the resin particle by an anchor effect, and the polar group is bonded to only one end of the polymer main chain. One of the main factors is presumed to be that the particles modify the surface of the resin particles and improve their affinity with the dispersion medium. Furthermore, in the non-aqueous dispersion resin described in JP-A-60-185963, monomers that polymerize and become insolubilized,
These resin particles are obtained by coexisting monomers containing long-chain alkyl group components that can be copolymerized, and as mentioned above, these particles have excellent dispersibility, but they are difficult to print on large-size plates. The number of sheets printed was about 5,000 to 8,000 when printing on a large printing press using a 1-size master plate, or using an offset master plate obtained by increasing the processing speed of a plate-making machine. .

When the particles obtained in the present invention are used, it is possible to print on a large printing machine with a large plate size as described above, or to print a master plate obtained on a plate-making machine with an accelerated plate-making speed. In some cases, it was possible to print more than 10,000 sheets. In addition, the non-aqueous decomposable resin described in JP-A No. 62-166362 contains at least two or more ester bonds, etc., which are copolymerized and copolymerized, with a monotoner that polymerizes and becomes insolubilized. This is a resin particle obtained by coexisting with tJ1m body, which has greatly improved particle dispersibility and rigidity resistance compared to conventional particles, but it is not suitable for master plates for large size offset printing. A plate making machine using a plate making machine (for example, ELP-560, ELP- manufactured by Fuji Photo Film)
820, etc.), or when the processing speed of the plate making machine was increased, there was still a problem with the separation of particles. However, when the resin particles provided by the present invention are used, no problems occur even under such harsh conditions. A coloring agent may be used in the liquid developer of the present invention if desired. The coloring agent is not particularly limited, and any conventionally known IJrin materials or dyes may be used. When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse it in the dispersion resin using pigments or dyes, and there are many known pigments or dyes. ing. Examples include magnetic iron oxide powder, powdered lead iodide, carbon brassoc, nigrosine, alkali blue, Hanzaiero, quinacridone resin, and phthalocyanine blue. Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
As described in No. 8, etc., there is a method of dyeing a dispersed resin with a preferred dye. Alternatively, as another method, there is a method of chemically bonding the dispersion resin and dyeing material 4 as disclosed in JP-A No. 53-54029, or as described in JP-B No. 44-22955, etc. When manufacturing by polymerization granulation method, 0 containing pigment in advance is used.
There is a method of using a monomer to form a copolymer containing a dye. If desired, various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics.
No., page 44, those specifically described are used. Examples include di-2-ethylhexylsulfosuccinic acid metal salts, naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), and copolymers containing half-maleic acid amide. The amounts of each main ingredient in the liquid developer of the present invention are explained below. The toner particles, which are mainly composed of a resin and an optional colorant, are used in an amount of 0.00 parts by weight based on 1000 parts by weight of the carrier liquid.
5 parts by weight ~ 50! ! Parts by weight are preferred. If it is less than 0.5 part by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fogging will easily occur in non-image areas. Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and the carrier liquid 1
Approximately 0.5 parts to 1 part of too I can be added to 000 parts by weight. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on iooo parts by weight of the carrier liquid. Furthermore, various additives may be added as desired, and the upper limit of the &21 of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed is lower than 10 qΩC, it will be difficult to obtain a high-quality continuous tone image, so the amount of each additive added should be controlled within this limit. is necessary.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited to these. The l:
A lauryl methacrylate 96.7 g
, vinyl mech acrylate 2. 2g and isodecane 4
00g of the mixed solution was heated to a temperature of 70'C under a nitrogen stream. While stirring, add 1.2'-azobis(putyronitrile) to 1. After adding Og and reacting for 3 hours, 1.0 g of 2,2'-azobis (petite nitrile) was added and reacting for 4 hours. The solid content concentration of the obtained solution was 19.4%. The weight average molecular weight of a colorless and transparent viscous substance obtained by pouring a part of the above reaction solution into 10 times the amount of methanol solvent measured by high performance liquid chromatography is 3.8 × 1
It was 0'. 2: 8 b Stearyl meccrylate 128.7g, vinyl meccrylate 2.2
A mixed solution of 300 g of isodecane and 300 g of isodecane was heated to a temperature of 75°C under a nitrogen atmosphere. Then, 2,2'-azobis(
1.3 Ili of petyronitrile) was added thereto, and the mixture was stirred for 3 hours. Furthermore, 2.2'-azobis(putyronitrile) was added to 1.
3g was added and reacted for 5 hours. The solid content concentration of the obtained solution was 30.0%. The weight average molecular weight of the white solid, treated and measured as in Preparation Example 1, was 3.5 x 10'. Out of 3: 80 lauryl methacrylate 71.0g, vinyloxycarbonylmethyloxy carbonylethyl acrylate 2
．． A mixed solution of 2g and 293g of Isobar H was heated to 70°C under a nitrogen stream. Thereafter, 1.1 g of 2,2'-azobis(putyronitrile) was added and stirred for 3 hours. Furthermore, 1 2,2'-azobis(putyronitrile)
．． 1 g was added and reacted for 5 hours. The solid content concentration of the obtained solution was 19.6%. The average molecular weight of a colorless and transparent viscous material treated and measured as in Production Example 1 was 3.5×10
'Met.゜″ 4: Person h
A mixed solution of 159.0 g of hexadecyl acrylate, 3.1 g of allyloxymethyl methacrylamide, and 145 g of n-dodecane was heated under a nitrogen stream at a temperature of 7.
It was heated to 5°C. Thereafter, 0.9 g of 2,2'-azobis(putyronitrile) was added and stirred for 3 hours.

Furthermore, 0.9 g of 2.2'-azobis(butyronitrile)
The mixture was added and reacted for 4 hours. The solid content of the obtained solution was 29.4%. The weight average molecular weight of the white solid, treated and measured as in Production Example 1, was 4. It was IX10'. Part 5, A. A mixed solution of 45 g of stearyl methacrylate, 1.7 g of vinyl 4-ethyl acrylate, and 109 g of Isovar G was heated to 75° C. under a nitrogen stream.

To this, 0.7 g of henzoyl peroxide was added and stirred for 3 hours. Furthermore, 0.7 g of benzoyl peroxide was added and the mixture was allowed to react for 4 hours. The solid content concentration of the obtained solution was 29.0%. The weight average molecular weight of the white solid, treated and measured as in Preparation Example 1, was 3.8 x 10'.

Gates 6 to 12: Entry table below-
A predetermined amount of each single member described in 1 and 250 isobar G.
g of the mixed solution was heated to a temperature of 65°C under a nitrogen stream. To this, 2,2'-azobis(invaleronitrile)
1.0 g of was added and stirred for 4 hours, and further, 0.5 g of 2,2'-azobis(isovaleronitrile) was added and reacted for 3 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, and the precipitate was collected by filtration and dried under reduced pressure at room temperature. 1! The weight average molecular weight of each resin was in the range of 4X10' to 8XIO'. (Left below) Oligomer's ゛6 1: Oligomer B-1'' is also 2
3-diacetoxypropyl methacryly} 100
g, 3-mercaptopropionic acid 5g, toluene 150
A melt containing 50 g of methanol and 50 g of methanol was heated to 70° C. while stirring under a nitrogen stream.

2.2'-azobis(isobutyronitrile) (abbreviation A.
I. B. N. ) was added and reacted for 4 hours. Furthermore, A. l. B. N. 0.4g of was added and reacted for 4 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol/water ((4/1) volume ratio) mixed solution, the methanol solution was separated by decantation, the viscous substance was dried, and a colorless viscous substance of 75
I got g. The number average molecular weight of the polymer was 3.300. Oligomer B-1 = ococH. Oligomer ″ 2 to 13; Oligomer tl2 to Production Example 1, except that the mercapto compound shown in Table 2 below was used instead of 5 g of 3-mercaptopropionic acid.
Each oligomer B-2 to B-1 was prepared in the same manner as in Production Example 1.
3 was manufactured. The number average molecular weight of the obtained oligomer is 2
．． 500 to 5,000.

(Leaving space below) Table 2 Table 2 (Continued) O1 gomer ``14~33: In Ogomer 8-14~Production example 1, instead of 2,3-diacetoxypropyl methacrylate, the corresponding to Table 3 Oligomers B-14 to B-33 were produced in the same manner as in Production Example 1, except that the ilj l form was used.The number average content of the obtained oligomers was 2,500 to 3,500. Met.

Table 3 Coo-R Table 3 (Continued) 2 - A mixed solution of 100 g of (n-octyloxy)ethyl crotonate, 150 g of toluene, and 50 g of ethanol was heated to a temperature of 7 while stirring under a nitrogen stream.
8 g of 2,2'-azobis(cyanovaleric acid) (abbreviation ^.C.V.) heated to 5°C was added and reacted for 5 hours, and then A. C. ν. 2g of was added and reacted for 4 hours. After cooling the obtained reaction solution, it was reprecipitated into a methanol/water ((4/1) volume ratio) mixed aqueous solution, and after separating the methanol aqueous solution by decantation, the viscous substance was dried. Yield: Lt70
The number average molecular weight of the polymer was 2,600.

Oligomer B-34: CI! ．． CL In Production Example 34, polymerization initiator A. C. V. Production Example 34 except that the azobis compound shown in Table 4 below was used instead of
Oligomers B-35 to B43 were produced in the same manner as above. The number average molecular weight of the obtained oligomer was 2,000
~4,000.

(Leaving space below) Table 4 R N = N R: Azobis Compound Table 4 (vl) 8 g of dispersion stabilizing resin (a), 100 g of vinyl acetate, 0.8 g of oligomer B-1, and 380 g of Isovar H
While stirring 1 volume of the yR solution in g under a nitrogen atmosphere, bring it to a degree of 7
Add 0.8 g of 2.2'-azobis(isovaleronitrile) (abbreviated as A.I.V.N.) heated to 0°C and react for 2 hours, and then add A.I.V.N. 0.3g was added and the reaction was carried out for 2 hours. 20 minutes after the addition of the initiator, a cloudy state appeared and the reaction temperature reached 88'C.The temperature was raised to 100°C and the reaction was carried out for 2 hours a! Unreacted vinyl acetate was distilled off. After cooling, the mixture was passed through a 200-mm nylon cloth, and the resulting white dispersion was latex with a polymerization rate of 85% and an average grain size of 0.201!m.

... Kusu's ゛1 2~17: D-2~D-U type Latinx particle 58! In Example 1, except that the dispersion stable river fat and oligomer were replaced with each compound in Table 5 below,
5 of each latex particle with the same strip as in production example l! Built. The polymerization rate of each Latinx R child was 85-90%.

(Left below) 11. 18: 10 g of Di8 dispersion stabilizing resin (o), 100 g of vinyl acetate, 5 crotonic acids
g, Oligomer B-1 at 1, Og and Isopar E at 4
While stirring 68 g of the mixed solution under a nitrogen stream, the temperature was 70°C.
It was heated to °C. A. I. V. N. After 6 hours of reaction, the temperature was raised to 100°C and the mixture was stirred for 1 hour to distill off the remaining vinyl acetate. After cooling, it was passed through a 200-menosh nylon cloth, and the obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.20 μm.

9: D-19 dispersion stabilizing resin (C) 9g, vinyl acetate 100g, 4-pentenoic acid 6
．． 0 g of oligomer B-34 and 380 g of Isopar G was heated to a temperature of 75° C. while stirring under a nitrogen stream. A. I. B. N. 0.
7g was added and reacted for 4 hours, and further A. l. B. N. 0
．． 5g was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth, and the polymerization rate was 86.
%, and the average particle size of the latex was 0.21 Ilm.

20: A mixed i8 solution of 10 g of D-20 dispersion stabilizing resin (c), 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 0.8 g of oligomer B-40, and 380 g of n-decane was heated in a nitrogen stream. The mixture was heated to 75°C while stirring. A. I. B. l1. 1.7
g was added, reacted for 4 hours, and further ^. l. B. N. 0.5
g and reacted for 21:'i. The autochromic dispersion obtained by passing through a cooled i&200 menosh nylon cloth had a polymerization rate of 85% and a Latinx average particle size of 0.22-.

21: 14 g of D-21 dispersion stabilizing resin (a), isobutylene methacrylate IO
'Og, oligo? -1.5g of B-25 and n deca 74
70g of mixed solution was heated to temperature 7 while pressing PR under nitrogen stream.
0' (J: Warmed. 1.0g of A.I.V.N. was added and reacted for 2 hours. A pale blue color started several minutes after adding the initiator and the reaction temperature rose to 90°C. Cooled. Coarse particles were removed by passing through a 200 mm thick nylon cloth, and the resulting white separated product was latex with a polymerization rate of 83% and an average particle size of 0.25 mm.

? 1 x 22: 14 g of D-22 dispersion stabilizing resin (p), 100 g of styrene, oligomer B-
A mixture of 1.0g of 7 and 380g of Isopar H? The 8 liquid was heated to a temperature of 60°C while stirring under a nitrogen stream.

A. I. V. N. Add 0.6g of and react for 4 hours, then further ^
．． I. V. N. 0.3 g was added to the mixture and the mixture was incubated for 3 hours. After cooling, it was passed through a 200-menosh nylon cloth, and the resulting white dispersion had a polymerization rate of 80% and a Latinx particle size of 0.23 μm on average. No. ■ (T = S particles 11 Tatsumi Betsu - 23 (.i.I example - In production example 1 of Δ-latex particles, oligomer B-1 was omitted, and the rest was the same as production example 1. The white dispersion obtained had a polymerization rate of 85% and an average particle size of 0.
It was a 25μ Latinx. (Unexamined Japanese Patent Publication No. 6018596
Equivalent to latex particles No. 2) &2
4.8 g of dispersion stabilizing resin (a), 100 g of vinyl acetate, 1.0 g of occudecyl methacrylate
and Isopar-H were used as a mixed solution of 395 g, and the other operations were carried out in the same manner as in Production Example 1. The obtained white dispersion had a polymerization rate of 8.
It was a Latinx with an average particle size of 0.22ρ at 5%. (Latinx equivalent to JP-A No. 60-185963) 8 g of 1250 dispersion stabilizing resin (a) of Lostecox, too much vinyl acetate,
395g of Ig and Isopar I+ were used as a mixed i8 solution for the ttNtt body (]) with a lower 3-dimerization''7 structure, and the other operations were carried out in the same manner as in Preparation Example 1.The obtained white dispersion had a polymerization rate of 8.
The latex was 6% and had an average particle size of 0.241 m. (
Latenox intermediate (I) corresponding to JP-A-62-166362 CI+3 1 0 COCII1 Example 1 1 decyl methacrylate/acrylic acid (copolymerization ratio: 95
/5 weight ratio) 10 g of copolymer, 10 g of nigrosine, and 30 g of 7 liters of Citrus were placed in a paint shaker (Tokyo Kiku) along with glass beads, and a minute dispersion of nigrosine was obtained after passing 4, +f times. .

30 g of resin dispersion D-1 of Production Example 1 of Latenox particles
, 2.5 g of the above nigrosine fraction, FOC-14
00 (manufactured by Nissan Chemical ■: Tetradenyl alcohol) 15g
A liquid developer for electrostatic photography was prepared by diluting 0.08 g of [octadecene-half-maleic acid octadecylamide copolymer] in 1 liter of Schersol 7I.

1 [-Top L] Rari mvhi Ok≦A call, So Lko: 2-ri1 In the above production example, the resin dispersion was replaced with the following resin particles, and comparative liquid developers A, 13, and C were used. Three types were created.

Hikiro L body 41 image agent Δ; Resin dispersion of production example 23 of latex particles "T comparison and attack retardant image agent" 12 Resin dispersion of production example 24 of latex particles, ratio, property fatigue Resin dispersion of Manufacturing Example 25 of Sumikai Statue Latex Particles These liquid developers were used as a developer in a fully automatic plate making machine ELI'404V (manufactured by Fuji Photo Film ■) to produce ELP Master ■, an electrophotographic photosensitive material. Type (manufactured by Fuji Photo Film) was exposed and developed. The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELI' Master ■ type, it was observed whether there was any toner adhesion to the developing device. ? ! The y conversion rate (image iT1i product) of the given image is 3
This was done using 0% of the manuscript.

The results are shown in Table-6.

(Hereinafter, the remainder []) When each developer was plate-made under the above-mentioned plate-making conditions, the developer that did not stain the developing device and gave a clear image on the 2000th plate-making plate was found only in the case of the present invention. Met.

On the other hand, print the master plate for offsetting stamps (ELP master) obtained by plate making using each developer using a conventional method, and calculate the number of prints until missing characters, fading at the edges, etc. occur in the image of the printed matter. When compared, the present invention and Comparative Example A
In the master plate obtained using the developer of Comparative Example C, the problem did not occur even after 8000 sheets or more, and in the case of the mask plate using Comparative Example B, the problem occurred after 8,000 sheets.

As can be seen from the above results, only the developer made from the resin particles of the present invention caused no tearing of the developing device at all, and at the same time, the number of prints of the master plate was significantly increased.

That is, in the case of Comparative Example 8, there was no problem with the number of prints, but the developing device was so dirty that it could not withstand continuous use. In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 5.
When used at a fast speed of 2 to 3 sheets per minute (conventionally, the plate making speed was 2 to 3 sheets per minute), the developing device (especially on the back electrode plate) becomes dirty, and after 2000 sheets, , affects the image quality of the copied images of play 1 and 2 (decrease in D, ,
(fine line smudges, etc.) started to appear. There was no problem in the number of printed master plates in Comparative Example C, but it decreased in Comparative Example B.

These results demonstrate that the resin particles of the present invention are clearly superior. Example 2 White dispersion 100 obtained in Production Example 2 of Latinx particles
A mixture of 1.5 g of Sumikaron Buranok and
The mixture was heated to 0°C and stirred for 4 hours. After cooling to room temperature 2
A black resin dispersion with an average particle size of 0.24 m was obtained by passing the dye through a 00 Menosh nylon cloth to remove the remaining dye. The above black resin dispersion 32 [, FOC-1600
A liquid developer was prepared by diluting 20 g of hexadecyl alcohol (manufactured by Kuchisan Kagaku Wa Co., Ltd.) and 0.05 g of zirconium naphthenate to the tg of Cielsol 7I. When this was developed using the same apparatus as in Example 1, no toner staining occurred on the apparatus even after 2000 sheets were developed.

In addition, the image quality of the obtained offset printing master plate was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear. Example 3 White dispersion 10 obtained in latex particle production example 19
A mixture of 0 g and 3 g of Victoria Blue B was heated to a temperature of 7.
The mixture was heated to 0°C to 80°C and stirred for 6 hours. After cooling to room temperature, it was passed through a 200-mesh nylon cloth to remove the remaining 7'f-dye and the average particle size was 0.25I. A blue resin material of m was obtained. 32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 0.05g to 11 of Isopar 1. When this was developed using the same apparatus as in Example 1, 20
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Furthermore, the image quality of the obtained offset printing master plate was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 4 32 g of white fat dispersion obtained in Production Example 3 of Latenox particles
, 2.5 g of nigrosine fraction obtained in Example 1 FOC-1
A liquid developer was prepared by diluting 15 g of 800 (manufactured by Ikosan Kagaku ■, octadecyl alcohol) and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and hydromaleic acid to 1j2 of Isobar G. .

When this was developed using the same apparatus as in Example 1, it was found that 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Moreover, the MW of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 copies were always ζY bright.

Furthermore, after allowing this developer to stand for 3 months, the same treatment as above was performed, but there was no difference at all from before. Example 5 10 g of poly(decyl methacrylate), 30 g of Isonokuichi 11 and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

White resin dispersion D obtained in Production Example 3 of Latinx particles
30g of -3, 4.2g of the above alkaline benolay dispersion
, and 0.06 g of a semi-docosanylamidated copolymer of diisobutylene and maleic anhydride were added to Isopar 6-11.
A liquid developer was prepared by diluting it to . When this was developed using the same apparatus as in Example 1, it was found that 200
Even after developing 0 sheets, no toner stains were observed on the device. In addition, the image quality of the obtained master plate for off-set/ink printing and the image quality of the printed matter after printing 10,000 sheets were both very clear.

Examples 6 to 20 In Example 5, D-3 of latex particle production example 3
A developer was prepared in the same manner as in Example 5, except that each latenox particle shown in Table 7 below was used instead. When each liquid was developed using the same apparatus as in Example 1, 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device. In addition, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear. Furthermore, after leaving this developer for 3 months, the same treatment as above was carried out, but there was no difference at all from before aging.

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device does not run out, and the image quality of the obtained master plate for offset printing is improved.
After printing 10,000 copies, the image quality of the printed matter was very clear.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least resin particles dispersed in a nonaqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, the dispersed resin particles comprising: A monomer represented by the following general formula (I) and the following general formula (II)
) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent obtained by copolymerizing with the monomer represented by monomer (A) and the following general formula (III)
A carboxyl group, a sulfo group, a hydroxyl group,
There are formyl groups, amino groups, phosphono groups, and ▲mathematical formulas, chemical formulas, tables, etc.▼ groups (R^0 is -R^1 group or -
OR^1 group, R^1 represents a hydrocarbon group), each containing at least one oligomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding at least one polar group selected from A liquid developer for electrostatic photography, characterized in that it is polymer resin particles obtained by subjecting a solution containing seeds to a polymerization reaction. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), L is an aliphatic group with 8 or more carbon atoms, a^1
and a^2 may be the same or different and each represents a hydrogen atom or an alkyl group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (II), A is -COO-, -CONH- or -C
ON- (Z^1 represents an aliphatic group), B is a group connecting the above functional group A and atomic group D with a carbon atom which may be via a hetero atom, and D is the above atomic group B. A group that connects and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COO-, -
COOCH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, -O-, -SO_2- or -C-, respectively. However, when A represents -COO-, it may be directly bonded to -C=CH without going through B and D. Also b^1, b
^2 and b^3 may be the same or different and each represents a hydrogen atom or an alkyl group. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (III), V^0 is -O-, -S-,
-COO-, -OCO-, -CH_2OCO- or -C
Represents H_2COO-. Y^0 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. X^1 and X^2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2, -OCO-,
-SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables, etc. Represents ▼ (Y^1 represents the same content as Y^0 above). R^2 and R^3 may be the same or different from each other,
It may be substituted, or ▲There is a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [X^3, X^4 may be the same or different from each other, and the above X^1 , X^2, R^4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, Y^2 has the same content as Y^0] C1 to 18 hydrocarbon groups. d^1 and d^2 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-R^5 or -COO-R^5(R
^5 represents a hydrogen atom or a hydrocarbon group that may be substituted. m, n and p may be the same or different, and are 0 to 4
represents an integer. However, m+n is 1 or more.