JPH02204754A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve the dispersion stability, redispersibility and fixability of the developer by using resin particles formed by copolymerizing a prescribed monomer and specific oligomer in the presence of a specific resin for dispersion stabilization. CONSTITUTION:This developer is formed by dispersing at least the resin particles in a prescribed nonaq. solvent. The resin formed by copolymerizing the prescribed monomer and the oligomer which combines a polar group such as carboxyl group only to one terminal of the main chain of the polymer consisting of the unit expressed by formula III in the presence of the resin for dispersion stabilization which is formed by bonding the polar group, such as carboxyl, only to one terminal of the main chain of the polymer contg. the repeating unit expressed by formula I, has >=1X10<4> weight average mol. wt. and consists of the terminal part of, for example, formula II and the repeating unit is used for the above-mentioned particles. In the formula, X<1> denotes -COO-, -O-, etc.; Y<1> denotes 6 to 32C aliphat. group, a<1>, a<2> denote H, halogen, etc.; T<1> denotes -COO-, -O-, etc.; R<2> denotes 1 to 22C hydrocarbon; b<1>, b<2> denote H, halogen, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10"Ω1 or more and a dielectric value of 13.5 yen or less. In particular, redispersibility, storage stability,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties.

(Prior art) -1 Liquid developer for electrophotography is made by combining organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue with natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. It is dispersed in a liquid with high insulating properties and low dielectric constant, such as aliphatic hydrocarbons, and a polarity control agent such as metal soap, lecithin, linseed oil, higher fatty acids, or a polymer containing vinyl pyrrolidone is added. be.

In such developers, the resin is dispersed as insoluble latex particles with a diameter of several nanometers to several hundred nanometers, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, there is a drawback that the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, causing the particles to settle, aggregate, or accumulate, and the polarity to become unclear. Furthermore, since particles that have aggregated and accumulated are difficult to redisperse, they remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed 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 the like. 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. This has the disadvantage that redispersion stability is insufficient for practical use, such as solidification, making redispersion difficult, and furthermore causing equipment failure and smudging of copied images. In the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle size distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized; The particles had a wide particle size distribution containing a large amount of coarse particles, or the particles had a polydisperse particle size with two or more average particle sizes. or,
It was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of -> or more or very fine particles of 0.1 μ or less were formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and an eHt form containing a long-chain alkyl moiety or a monomer containing two or more types of polar components are used. A method of improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A-60-179751 and JP-A-62-151868.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing 5,000 or more sheets using a master plate for offset printing using an electrophotographic method has been attempted, and improvements in the master plate in particular have been progressing. It has become possible to print more than 10,000 sheets in plate size. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixation process.

JP-A-60-179751 and JP-A No. 62-15186
Dispersed resin particles produced according to the method disclosed in No. 8, when the development speed increases, the dispersibility of the particles,
In terms of redispersibility, when the fixing time is shortened, or in the case of large-sized master plates (for example, A-3 size or larger), the performance is still not necessarily satisfactory in terms of rigidity resistance.

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

An object of the present invention is to provide a liquid developer that can speed up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in an electrophotolithography system using a large-sized master plate. That's true.

Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of off-cent printing plates having excellent printing ink oleaginous durability.

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 that can be used in any system where a liquid 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. That's true.

(Means for Solving the Problems) The above aspects of the present invention are an electrophotographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 109 Ωcm or more and a dielectric constant of 3.5 or less. In this case, the dispersed resin particles contain a repeating unit represented by the following general formula (+), and only one end of the main chain of the polymer is selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group, and a phosphono group. A monofunctional monomer that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization in the presence of a dispersion stabilizing resin that has at least one polar group bonded to it and has a weight average molecular weight of 1X10' or more. A carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, and ■ is an -OR' group at one end of the main chain of the polymer consisting of repeating units represented by the compound (A) and the following general formula (n). (R1 represents a hydrocarbon group) A solution containing at least one type of oligomer (B) having a number average molecular weight of 104 or less, which is formed by bonding at least one type of polar group selected from the following, is subjected to a polymerization reaction. This was achieved by an electrostatographic liquid developer characterized by copolymer resin particles obtained by.

General formula (I) %formula% In general formula (I), XI is -coo--oc.

-C)i,0CO-1-CIhCOO-2-〇- or-
3o! - represents.

vl represents an aliphatic group having 6 to 32 carbon atoms.

al and R2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Zl, or a hydrocarbon group having 1 to 8 carbon atoms. -COO-Z'(Z' represents a hydrocarbon group having 1 to 22 carbon atoms).

General formula (II) C1120CO-5-C)12COQ-1-o-, -3
O, -ρJ C0N- represents a hydrocarbon group having 1 to 18 carbon atoms.

R2 represents a hydrocarbon group having I to 22 carbon atoms.

b' and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyan group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-R', or a hydrocarbon group having 1 to 8 carbon atoms. -Coo-R'(R' represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

Hereinafter, the liquid developer of the present invention will be explained in detail.

Electrical resistance used in the present invention: 109ΩcIm or more, dielectric constant: 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, Hensen, toluene, xylene, mesitylene, isopar E1
Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon), Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Co.)
, Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Inc.), etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are made of a polymer containing repeating units represented by the general formula (I) in a non-aqueous solvent. Presence of a dispersion stabilizing resin having at least one polar group selected from carboxyl, sulfo, hydroxyl, amino and phosphono groups bonded to only one end of the main chain and having a weight average molecular weight of lXl0' or more Below, it is produced by polymerizing the above-mentioned -functional monomer (A) and oligomer (B) (so-called polymerization granulation method).

Here, as the non-aqueous solvent, basically any solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer.

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. and halogen-substituted products thereof, etc. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane,
Isododecane, isoparaffin-based petroleum solvent Isopar E1 Isopar G1 Isopar H5 Isopar L
1 Sherzol 70. Sherzoll 71, Amsco○M
S, Amsco 460 solvent, etc. are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.) , carboxylic acid esters (e.g. methyl acetate, ethyl acetate,
propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. methylene dichloride, chloroform, carbon tetrachloride, etc.) , dichloroethane, methylchloroform, etc.).

It is preferable that the non-aqueous solvent used in the mixture be removed by heating or distillation under reduced pressure after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, it will not affect the liquid in the developer. There is no problem as long as the resistance is within a range that satisfies the condition of 109 Ωcm or more.

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of resin dispersion production, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated Examples include hydrocarbons.

The dispersion stabilizing resin of the present invention used for making a stable resin dispersion of the solvent-insoluble copolymer produced by polymerizing monomer (A) and oligomer (B) in a non-aqueous solvent teeth,
A resin that does not contain a graft group that polymerizes with a monomer,
At least one polar group selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group, and a phosphono group is bonded only to one end of the polymer main chain containing at least one type of repeating unit represented by general formula (I). It is a polymer made of

The repeating unit represented by the general formula (N) will be explained in more detail below.

In the repeating unit represented by general formula (I), aliphatic groups and hydrocarbon groups may be substituted.

In general formula (I), 1 is preferably -COO-1
OCO--CHzOCO-1-CHlCOo- or -〇-, more preferably -COO--CHzCO0
- or -〇-.

Yl preferably has 8 to 22 carbon atoms and may be substituted,
represents an alkyl group, alkenyl group or aralkyl group,
The substituent may be any substituent other than the polar group bonded to one end of the main chain of the polymer, such as halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), -0-Z "-COO-Z"-0(:O-Z"
(Z" represents an alkyl group having 6 to 22 carbon atoms,
Examples include substituents such as hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.

More preferably, YI represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, such as an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a docosani group, an octenyl group, Decenyl group, dodecenyl group, tetradecenyl group,
Examples include hexadecenyl group and octadecenyl group.

al and a2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, -coo-z 'or-CIhCOO-Z'
(Z' represents an aliphatic group having 1 to 22 carbon atoms), more preferably al and at may be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (
For example, methyl group, ethyl group, propyl group, etc.), -C
OO-Z' or -CHtCOO-Z'(Z' more preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
Examples include butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc. These alkyl groups and alkenyl groups may have the same substituent as shown above for yl).

Furthermore, a polar group bonded only to one end of the polymer main chain has a chemical structure in which it is bonded directly to one end of the polymer main chain or via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (petero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and petro atoms-hetero atoms. Monoatomic atoms, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), cyano groups, hydroxyl groups, alkyl groups (e.g., methyl groups, ethyl groups), which are composed of any combination of atomic groups of atomic bonds. ,
-(CH・CH)-1Z& or a hydrocarbon group having the same meaning as 2+ shown in the general formula (I)]. Examples include a linking group or a linking group composed of any silk combination.

The polymer component of the dispersion stabilizing resin of the present invention corresponds to a homopolymer component or a copolymer component selected from the repeating units represented by general formula (24) or a repeating unit represented by general formula (I). It is composed of a copolymer component obtained by polymerizing a monomer that can be copolymerized with another monomer that can be copolymerized. In addition to the copolymer component of the general formula (I), other monomers that become the copolymer component include, for example, those of the general formula (Ill) described below.
Examples include compounds represented by:

The repeating unit represented by the above general formula (I) accounts for 30% by weight or more in the dispersion stabilizing resin polymer used in the present invention.
100% by weight is suitable, preferably 50111%
~100% by weight.

Further, it is preferable that the main chain of the polymer does not contain a copolymer component containing a polar group such as a carboxyl group, a sulfo group, a hydroxyl group, an amino group, or a phosphono group.

The dispersion stabilizing resin of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by: (1) reacting various reagents with the ends of living polymers obtained by conventionally known anionic or cationic polymerization; method (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or 0 or more ions. It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a polymerization method or a radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, Drey4uss & 11. P
, Quirk.

Rncycle, Polym, Sci, Eng, +
1.551 (I9B?), Yoshiki Nakajo, Yuya Yamashita, "Dye and Medicine J, 30.232 (I985)," Akira Ueda, Susumu Nagai, "Science and Industry", Utsubo, 57 (I986), etc. Reviews and references cited therein. It can be produced by methods described in literature.

The dispersion stabilizing resin of the present invention has a weight average molecular weight of 1×to'~
3x10' is preferred, more preferably 1.5x104
When the zero weight average molecular weight of ˜lXl0′ is less than 1×10 4 , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5 μ) and the particle size distribution becomes wide. Moreover, when it exceeds 3 XIO', the average particle diameter of the resin particles obtained by polymerization granulation becomes large,
2~0.4J! It may be difficult to align the average particle size within the preferred range of Ig.

Specific examples of the dispersion stabilizing resin used in the present invention are shown below, but the present invention is not limited thereto.

(■ day of the week N C00CIJzs CH.

N C00C+@Hst (+-8) C11゜ (+-10) Ha L CH.

Hz 11I CH3 Hff C](.

CHl CH.

c! ooc, mountain.

JOOC+mountain) It can be distinguished into a polymer (A) and an oligomer (B) that undergoes copolymerization.

The monomer (A) in the present invention may be any monofunctional monomer that is soluble in a non-aqueous solvent but becomes insolubilized by polymerization.
Examples include monomers represented by [I].

General formula (I[l) In the general formula (I[l), T2 is -C00-5-〇C0 The monomer used in producing the non-aqueous dispersion resin is soluble in the non-aqueous solvent, but polymerizable A monofunctional monomer (A) that is made insolubilized by 2-bromoethyl Ts, 2-cyanoethyl group, 2-hydroxyethyl group, penzyl group, chlorobenzyl group, methylbenzyl group,
Methoxybenzyl group, phenethyl group, 3-phenylfurohyl group, dimethylbenzyl group, phlolobenzyl group, 2-
methoxyethyl group, 3-methoxypropyl group, etc.).

R5 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl L2゜2-dichloroethyl group, 2,2.2 -trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2.3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
Cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group , l・
Rimethoxysilylbrobyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-Thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2phosphoethyl group, 3-sulfopropyl L4-sulfobutyl group, 2
-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

dt and dt may be the same or different, and each represents the same content as bl or b2 in the general formula (n).

As a specific monomer (A), for example, a carbon number of 1 to 6
Frequently vinyl esters or furyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Acid C1-4 optionally substituted alkyl esters or amides [(alkyl groups such as methyl, ethyl, propyl, butyl, 2-chloroethyl!, 2-bromoethyl, 2-fluoroethyl, I
, llyfluoroethyl group, 2-hydroxyethyl group, 2-
Cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylamino)
Ethyl group, 2-(N,N-diethylamino)ethyl group,
2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carpoxyamidoethyl group, etc.)
; Styrene derivatives (e.g. styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, (N,N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfamide, etc.); Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid: cyclic anhydrides of maleic acid and itaconic acid Acryliconitrile; methacriconitrile: Heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook - Basic Edition" edited by The Society of Polymer Science and Technology, pp. 175-184,
Compounds described in Baifukan (published in 1986), for example, N-
vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

Two or more types of monomers (A) may be used in combination.

Oligomer CB) is an oligomer with a number average molecular weight of 104 or less, which is formed by bonding the above-mentioned specific polar group only to one end of the main chain of a polymer consisting of repeating units represented by general formula (II). .

In the general formula (n), the hydrocarbon groups contained in bl, bl, T1 and R8 each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but even if these hydrocarbon groups are substituted, good.

In general formula (n), R3 in the substituent represented by 7+
In addition to hydrogen atoms, preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group). , decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group,
2-bromoethyl group, 2-cyatuyuthyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 8 carbon atoms (for example, 2 to Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, l-pentenyl group, l-hexenyl group, 2-hexenyl! , 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2 to naphthylethyl group) ,
chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxyhensyl group, dimethylhensyl group, dimethoxybenzyl group, etc.), carbon number 5-8
an optionally substituted alicyclic group (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , bromophenyl group, cyanophenyl group,
acetylphenyl group, methoxycarbonylphenyl group,
(ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

When TI represents ζ)', the benzene ring may have a substituent. Examples of the substituent include halogen atoms (for example, chlorine atom, bromine atom, etc.), alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.).

Hz preferably represents a hydrocarbon group having 1 to 18 carbon atoms, and specifically represents the same content as described for R1 above.

bl and b! 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 propyl group, etc.), -
Coo-R' or -CIlICOOR'(R' is
Preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,
represents an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, and specifically represents the same content as described for R3 above.

It is more preferable that either one of bl and bl in general formula (II) is a hydrogen atom.

Among the polar groups bonded only to one end of the polymer main chain containing at least one repeating unit represented by the general formula (II) and having a number average molecular weight of 1Xl0' or less, -P-R'
In the group, R6 represents a hydrocarbon group having 1 to 18 carbon atoms or an -OR' group. The hydrocarbon group of Re is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group group, bromobenzyl group, etc.), or an optionally substituted aromatic group (e.g.,
phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

When Ro represents 1011'i, ill preferably represents the same content as the hydrocarbon group of Re.

Moreover, among the polar groups of the present invention, the amino group is -NH,, prime number 1
-18 hydrocarbon group, preferably carbon number 1-8
represents a hydrocarbon group, and specifically represents the same content as the hydrocarbon group for R1+ described above.

Even more preferably, RO, R1, R? , R6 and R'
Examples of the hydrocarbon group include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, and 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 chain or bonded via an arbitrary linking group. The group connecting the general formula (II) component and the polar group includes a carbon-carbon bond (-multiple bond or double bond),
Carbon-1teroatom bond (heteroatoms include, for example,
(oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatoms, and heteroatom-bonded atomic groups.

Among the oligomers (B) of the present invention, preferred are those represented by general formula (IVa) or general formula (rVb).

General formula (IVa) T'-R'' General formula (rVb) ?1 91 General formula (IVa) and general formula (IV b i, bl,
b2.71 and RZ represent the same contents as the symbols in general formula (II).

Q represents the aforementioned polar group bonded to one end of general formula (It).

is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (for example, a methyl group, an ethyl group, a hydrocarbon group having the same content as I2 R3, etc.) represents a single linking group or a linking group composed of any combination selected from atomic groups such as

If the upper limit of the number average molecular weight of the oligomer (B) exceeds 1 x 10', the rigidity resistance will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so it is preferably 1XIO3 or more.

The oligomer (B) of the present invention is a homopolymer component or a copolymer component selected from the repeating units represented by the formula (It) or a unit corresponding to the repeating unit represented by the general formula (If). Formula 0 (II
Examples of other monomers that become the copolymer component together with the polymer component of compounds similar to the heterocyclic compounds described in A), compounds containing a carboxamide group or sulfamide group and a polymerizable double bond group (e.g., acrylamide, methacrylamide, diacetone acrylamide, 2-carboxyamidoethyl methacrylate, vinylbenzenecarboxamide, vinylbenzene sulfamide, 3-sulfamidopropyl methacrylate, etc.).

In the oligomer (B) used in the present invention, the repeating unit represented by the general formula (n) is 30 to 10% by weight.
0% by weight is suitable, preferably 50% to 100% by weight
It is heavy.

Further, it is preferable that the main chain of the polymer does not contain a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, or a hydroxyl group.

The oligomer (I3) of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, is obtained by reacting various reagents to the end of a polymer obtained by conventionally known anionic or cationic polymerization. method (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or 0
A polymer containing a terminal reactive group obtained by the above ionic polymerization method or radical polymerization method can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end is converted into the specific polar group of the present invention by a polymer reaction. be able to.

Specifically, P, Dreyfuss & R,P,
Quirk.

Rncycle, Polym, Sci, tang,
, 7, 551 (I987), Yoshiki Chujo 1 Yuya Yamashita, ``Dye and Medicine,'' 30.232 (I985), Akira Ueda, Susumu Nagai, ``Science and Industry'', Utsubo, 57 (I986), etc. Reviews and references cited therein. It can be produced by methods described in literature.

More specifically, the oligomer (B) of the present invention can be exemplified by the following compounds. However, the scope of the present invention is not limited to these.

(Margin below) an integer from n-1 to 10, R: -CaHza, +(m: Along the lines of 1 to 18.

I CN C00R (X=H, CI, Br, CHz, -0CI(3)(
8) CH.

HO(C1h'')rS(C1h-Ch 0OR CH.

p: integer from i to 4 (I2) C113 CH.

HO(CIll>-rccH,-CHi q: 1 or 4 N 0OR CI! .

Basket+1033-CH2C)I! -5-(cuz-o-0O
R C10゜11□N (C1h)TS(CH2C)-0OR fb cH, cOOll しHtL, 1lzUtl C11゜0OR (Hereinafter, blank) The dispersion resin of the present invention has a monomer (A) and an oligomer (B).
What is important is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, for the monomer (A) to be insolubilized, general formula (II)
It is preferable to use the oligomer (B) represented by 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.

Even more preferably it is 0.3 to 3% by weight. Further, the molecular weight of the dispersion resin of the present invention is 103 to 106, preferably 10' to 5X10'.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and oligomer (B) are mixed in a non-aqueous solvent with benzoyl peroxide, azo The polymerization may be carried out by heating in the presence of a polymerization initiator such as bisisobutyronitrile or butyllithium. Specifically, ■Dispersion stabilizing resin, monomer (A) and oligomer (B)
) A method of adding a polymerization initiator to a mixed solution of (2) A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing the entire amount of the dispersion stabilizing resin and a portion of the mixture of monomer (A) and oligomer (B); ■There are methods of optionally adding a mixed solution of a dispersion stabilizing resin, monomer (A), and oligomer (B) together with a polymerization initiator to a non-aqueous solvent; production can be achieved using either method. be able to.

The total amount of monomer (A) and oligomer (B) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent.

The soluble resin which is the dispersion stabilizing resin is 1 to 100 parts by weight based on 100 parts by weight of the total monomers used above,
Preferably it is 5 to 50 parts by weight.

The appropriate amount of the polymerization initiator is 0.1 to 5% by weight based on the total monomer amount.

Further, the polymerization temperature is about 50 to 180'C, preferably 60 to 120'C. The reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers, and esters is used in combination with the nonaqueous solvent used in the reaction, or when unreacted monomers (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 distilling it off under reduced pressure.

The non-aqueous dispersion 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 extremely stable dispersibility. Even if the developing speed is increased, the dispersibility is good (and re-dispersion is easy even when the development speed is increased), and no stains are observed on various parts of the device.

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-sized 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 resin particles of the present invention are used as a liquid developer are unknown, in the polymerization granulation method of the resin particles of the present invention, Even when oligomer (B) was added as a post-addition after polymerization granulation without using oligomer (B), the above-mentioned effect was 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, because the polar group is specifically bonded to only one end of the polymer main chain and is polymerized and granulated 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 moiety modifies the surface of the resin particles and improves the affinity with the dispersion medium.

A coloring agent may be used in the liquid developer of the present invention if desired. The coloring agent is not particularly specified; various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. There is. Examples include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hanzai Elo, quinacridone red, and phthalocyanine blue.

Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
There is a method of dyeing the dispersed resin with a preferred dye, as described in No. 8 and others. Alternatively, as another method, there is a method of chemically bonding a dispersion resin and a dye, as disclosed in JP-A No. 53-54029, or as described in JP-B No. 44-22955, etc. There is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance during production by a polymerization granulation method.

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.

For example, di-2-ethylhexyl sulfosuccinate metal salt,
Examples include naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), and copolymers containing half-maleic acid amide components.

The amounts of each main component of the liquid developer of the present invention are explained below.

The toner particles 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 to 50 parts by weight are preferred. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fogging will tend to occur in non-image areas. Furthermore, the carrier liquid soluble resin for dispersion stabilization described above may be used as desired, and the carrier liquid 10
About 0.5 parts by weight to 100 parts by weight can be added to 00 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 1000 parts by weight of the carrier liquid.Additionally, various additives may be added as desired. Its upper limit is regulated by the electrical resistance of That is, if the electrical resistance of the liquid developer with toner particles removed becomes lower than IO'ΩcI11, it becomes difficult to obtain a high-quality continuous tone image, so the amount of each additive added is controlled within this limit. It is necessary.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Separation ``-''° 1: (Resin P-1) octadecyl methacrylate) 100g,!・Luene 150g
A mixed solution of 50 g of isopropanol was heated to a temperature of 70° C. while stirring under a nitrogen stream. 5.0 g of 2゜2'-azobis(cyanovaleric acid) (abbreviation A, C, V)
The mixture was added and reacted for 8 hours. After cooling, it was reprecipitated in methanol 21, and a white powder was collected by filtration and dried to obtain a powder with a weight average molecular weight of 26,000 in a yield of 85 g.

1' Report 2: (Resin P-2) A polymerization reaction was carried out in the same manner as in Production Example 1, except that a mixed solution of 100 g of dodecyl methacrylate, 150 g of toluene and 50 g of isopropanol was used.

After cooling, it was reprecipitated into methanol 22 to obtain 83 g of a colorless and transparent viscous substance. The weight average molecular weight was 27,000.

1 "aJjLL: (Resin P-3) A mixed solution of octadecyl methacrylate loog and 300 g of toluene was heated to a temperature of 70°C while stirring under a nitrogen stream. 4,4'-azobis(4 cyanopentanol) 6 g was added and reacted for 8 hours.

After cooling, it was reprecipitated into methanol 21 to obtain 86 g of a white powder with a zero weight average molecular weight of 28,000.

18'1゛4: (Resin P-4) 70 g of dodecyl methacrylate 1 30 g of butyl methacrylate, 150 g of toluene and 50 g of isopropanol
The mixed solution was heated to a temperature of 70°C while stirring under a nitrogen stream. 6g of A, C, and v were added and reacted for 8 hours. The weight average molecular weight of the copolymer was 23.000.

11!15 of I2: (Resin P-5) Tridecyl methacrylate 98.5 g, thioglycolic acid 1.5 g
A mixed solution of 200 g of toluene was heated to 65°C. After adding 1.0 g of 2,2'-azobis(isobutyronitrile) (abbreviations A, 1.B, N,) and stirring for 5 hours, ^, 1. 0.3 g of B and N were added and further stirred for 4 hours. The weight average molecular weight of the obtained polymer was 24,000.

No. 8-6: (Resin P-6) A mixed solution of 98.0 g of octadecyl methacrylate, 2.0 g of 2-mercaptoethanesulfonic acid, 200 g of toluene, and 100 g of methanol was heated to 65° C. under a nitrogen stream. A.1. After adding 0.8g of B and N and reacting for 5 hours, A and 1. 0.3g of B and N were added and reacted for 2.5 hours. This reaction solution was reprecipitated in acetonitrile 22 to obtain 88 g of white powder.The weight average molecular weight was 25,000.
Met.

(Resin P-7) 90 g of hexadecyl methacrylate, 8 g of 2-chloroethyl methacrylate, 2.0 g of thiomalic acid, 15 g of toluene
A mixed solution of 0 g and 50 g of isopropanol was heated to a temperature of 75
Warmed to °C. 1.0g of 1,1'-azobis(cyclohexane-1-carbonitrile) was added and reacted for 6 hours.
Furthermore, 0.4 g of the above-mentioned initiator was added and reacted for 6 hours. After cooling, it is re-precipitated in methanol 22 to form a colorless and transparent viscous substance 86.
I got g. The weight average molecular weight was 23,000.

1' of 1'' 8: (Resin P-8) A mixed solution of 100 g of tetradecyl methacrylate, 100 g of tetrahydrofuran, and 100 g of methanol was heated to a temperature of 70''C while stirring under a nitrogen stream. 2.
5 g of 2''-azobis(2-methyl-N(I,l-bis(hydroxymethyl)-2-hydroxyethyl)propioamide) was added and reacted for 8 hours. After cooling, methanol/
It was reprecipitated into a mixed solution 22 of water (7/3 volume ratio) to obtain 80 g of a colorless viscous substance. The weight average molecular weight was 28,000.

'W Example 9: (Resin P-9) A mixed solution of 95 g of dodecyl methacrylate and 200 g of toluene was heated to a temperature of 70° C. under a nitrogen stream.

4.5 g of 4'-azobis(4-cyanopentanol)
Then, 1.0 g of N,N-dimethylaniline and 10 g of glutaconic anhydride were added to this reaction solution and stirred at a temperature of 90° C. for 12 hours.

After cooling, it was re-precipitated in methanol 21 to form a pale yellow viscous substance 88
The weight average molecular weight obtained was 28.000.

0 to 7; (Resin P-10 to P-17) In Production Example 1, in place of octadecyl methacrylate and the initiators A, C, and V, each of the compounds in Table 1 below was replaced with a dispersion. Each stabilizing resin was produced.

(The following is a blank space) P-9: P 10: H: P-12: Contains the polar group of the dispersion stabilizing resin P-, 1-P-17 obtained in Production Example 1-17 of the above dispersion stabilizing resin The terminal portion and the repeating unit of the main chain are shown below.

5: P-6: P-2: P-7: 3: 8: 4: (Weight ratio) P-13: P-14: P-15: Work 6: (Weight ratio) 17: (Hereafter the margin) No. A mixed solution of 100 g of 1 sesame sesame B-1 methyl methacrylate, 5 g of thioglycolic acid, 150 g of toluene, and 50 g of methanol was heated to a temperature of 70'C while stirring under a nitrogen stream. 2.2'
-Azobis(isobutyronitrile) (abbreviation A, 1.B,
1.5 g of N, ) was added and reacted for 4 hours. Furthermore ^, 1.
0.4 g of B and N were added and reacted for 4 hours. After cooling, this reaction solution is reprecipitated into methanol/water ((4/1) volume ratio) mixed solution 22, the methanol solution is separated by decantation, the viscous substance is dried, and the colorless viscous substance is 75g
Obtained. The number average molecular weight of the polymer was 2.800.

In Oligomer Production Example 1, 5 g of thioglycolic acid
Each oligomer B-2 to
B-12 was manufactured. The obtained oligomer had a number average molecular weight of 2.500 to 3,500.

1st Sesame ゛” 13-23 Nioh I Sesame B-1
3 to B-23 Oligomers B-13 to B-23 were produced in the same manner as in Production Example 1, except that the monomers shown in Table 3 were used instead of methyl methacrylate in Oligomer Production Example 1. Manufactured. The number average molecular weight of the obtained oligomer was 2.500
It was ~3.500.

Table-3 Table-4 R-N=N-R: A mixed solution of 100 g of azobis compound 1st sesame (24: 1st sesame B-24 methyl methacrylate), 150 g of toluene, and 50 g of ethanol under a nitrogen stream. While stirring, the mixture was heated to a temperature of 75°C. 2. 8 g of 2'-azobis(cyanovaleric acid) (abbreviated as A, C, V) was added and reacted for 5 hours, and further 2 g of A, C, V was added and reacted for 4 hours. After cooling the obtained reaction solution, methanol/water ((4/l)
Volume ratio] After reprecipitation in a mixed aqueous solution and separating the methanol aqueous solution by decantation, the viscous substance was dried. Yield 70
The number average molecular weight of the polymer was 2,600.

In Oligomer Production Example 24, polymerization initiators A, C,
Each oligomer B-25 to
B-33 was manufactured. The number average molecular weight of the obtained oligomer was 2,000 to 4,000.

Table 4 (Continued) A mixed solution of 20 g of Cus D-1 dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1.0 g of Oligomer 8-1, and 380 g of Isopar H was heated under nitrogen. The mixture was heated to a temperature of 70'C while stirring under a stream of air. 0.8 g of 2'-azobis(valeronitrile) (abbreviated as A, B, V, N) was added and reacted for 6 hours.

20 minutes after the addition of the initiator, clouding occurred and the reaction temperature rose to 88°C. The temperature was raised to 100'C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate.

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 88% and an average particle size of 0.24.

M-X's 2~21 Nice D-2~D-2
1 In production example 1 of latex particles, oligomer B-1
A white dispersion was obtained in the same manner as in Production Example 1, except that the oligomer shown in Table 5 below was used instead. The polymerization rate of each white dispersion was 85 to 90%. Moreover, the average particle size of each latex was in the range of 0.23 to 0.27.

Table 5 (continued) In production example 1 of latex particles, dispersion stabilizing resin P
A white dispersion was obtained in the same manner as in Production Example 1, except that the dispersion stabilizing resins and oligomers listed in Table 6 below were used in place of Oligomer B-1 and Oligomer B-1. The polymerization rate of the obtained dispersion was 85 to 90%.

Table 5 Table 6 - 36:-- 20g of Cus D-3 dispersion stabilizing resin P-1, 100g of vinyl acetate, 5g of crotonic acid, 1.0g of oligomer B-3 and 468g of Isopar E. The mixed solution was heated to a temperature of 70°C while stirring under a nitrogen stream. A, B, 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, the resulting white dispersion was passed through a 200 mesh nylon cloth, with a polymerization rate of 85% and an average particle size of 0.23.
It was μ latex.

--S 37: --S D-3 20g of dispersion stabilizing resin P-1, 100g of vinyl acetate'-4-
6.0 g of pentenoic acid, 0.8 g of oligomer B-15
A mixed solution of 380 g of G and Isopar G was heated to 70° C. while stirring under a nitrogen stream.

0.7 g of benzoyl peroxide was added and reacted for 4 hours, and further 0.5 g of benzoyl peroxide was added and reacted for 2 hours.

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, with an average particle size of 0.24 I! It was latex of m.

m-x 38;--18 g of Kus D-38 dispersion stabilizing resin P-3, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of oligomer B-9, and n
- A mixed solution of 380 g of decane was heated to a temperature of 75°C while stirring under a nitrogen stream.

A.1. Add 7g of B and N, react for 4 hours, and then add A and 1
．． B.N.

0.5g of was added and reacted for 2 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.20 nm.

-1x 39=-20g of 1x D-39 dispersion stabilizing resin P-6, 1 methyl methacrylate
A mixed solution of 00g of oligomer B-19, 1.0g of oligomer B-19, and 470g of n-decane was heated to a temperature of 70°C while stirring under a nitrogen stream. A.1. B, N, 1. Og was added and the mixture was reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had an average particle size of 0.45t! It was latex of m.

In Production Example 1 of M-X's 40A latex particles, except for excluding oligomer B-1,
The operation was carried out in the same manner as in Production Example 1. The obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.25 μm.

In Production Example 1 of Old B Latex Particles, the same procedure as in Production Example 1 was carried out except that a mixed solution of 8 g of poly(octadecyl methacrylate H, 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate, and 385 g of Isopar H was used). .

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.22.
- latex.

In Production Example 1 of 42C latex particles, except that a mixed solution of 8 g of poly(octadecyl methacrylate H, 100 g of vinyl acetate, 1 g of monomer (I) having the following chemical structure, and 385 g of Isopar H) was used. It was operated in the same manner as in Preparation Example I.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.24.
- latex.

Monomer (I) C) In CHJCOCJI+s Example 1 Dodecyl methacrylate/acrylic acid copolymer [copolymerization ratio (9515) weight ratio) log, 10 g of nigrosine and 30 g of Shell Silua 1 were mixed with glass peas in a paint shaker (Tokyo Seiki ■) ) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30g of latex D-1 of latex particle production example 1
, 2.5 g of the above nigrosine dispersion, 0.08 g of octadecene-half-maleic acid octadecylamide copolymer, and 1. A liquid developer for electrostatic photography was prepared by diluting it to .

(Comparative Developer A-C) In the manufacturing example of the liquid developer described above, latex D-1 was replaced with the following latex, and comparative liquid developers A, B,
Three types of C were produced.

Comparative liquid developer A; Latex comparative liquid developer B of latex particle production example 40 Comparative liquid developer C latex of Nilatex particle production example 41 Latex of Nilatex particle production example 42 These liquid developers II!, an electrophotographic photosensitive material, was used as a developer in a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film ■). LP master 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 ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. Darkening rate of copied image (
(image area) was performed using 20% of the manuscript. The results are shown in Table-7.

Table 7 When each developer was plate-made under the above-mentioned plate-making conditions, the developer of the present invention was the only one that did not cause staining of the developing device and provided a clear image on the 2000th plate-making plate.

On the other hand, the off-cent printing master plate (ELP master) obtained by plate making using each developer was printed using the 8 method, and the number of prints was compared until the printed image showed missing characters, fading in solid areas, etc. However, with the master plates obtained using the developers of the present invention, Comparative Example A, and Comparative Example C, the problem did not occur even after 10,000 sheets or more, but with 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 staining of the developing device and at the same time significantly increased the number of master plates printed.

That is, in the case of Comparative Example A, there was no problem with the number of prints, but the developing device was extremely dirty and 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 high plate-making speeds such as sheets/minute (conventionally, the plate-making speed was 2 to 3 sheets/minute), the developing device (especially on the back electrode plate) becomes dirty, and after 2,000 sheets, the plate becomes dirty. The quality of the copied image is affected! ? (Decrease in Dmax, fading of thin lines, etc.) started to appear. The number of master plates printed was not a problem in Comparative Example C, but 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 latex particle production example 2
A mixture of 1.5 g and Sumikaron black was heated to 10 g.
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 0.201 m was obtained by removing the remaining dye through a 0.00 mesh nylon cloth.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 15 g of higher alcohol F OC-1400 (manufactured by Nissan Chemical Company) to 12 of Shell Silua 1.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

Moreover, 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.

Example 3 White dispersion 10 obtained in latex particle production example 36
A mixture of 0 g and 3 g of Victoria Blue B was heated to a temperature of 70
The mixture was heated to ~80°C and stirred for 6 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth and the average particle size was 0.16t! A blue resin dispersion of m was obtained.

32g of the above blue resin dispersion, zirconium naphthenate o
A liquid developer was prepared by diluting 15 g of higher alcohol F OC-1600 (manufactured by Nissei Kagaku ■) to 11 of Isopar H.

When this was developed using the same device as in Example 1, 20
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 4 32 g of white resin dispersion obtained in latex particle production example 3
A liquid developer was prepared by diluting 2.5 g of the nigrone dispersion obtained in Example 1 and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 12 of Isopar G.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Furthermore, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were both 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.

Example 5 Poly(decyl methacrylate HOg), 30 g of Isopar H, 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.

30 g of white resin dispersion D-13 obtained in latex particle production example 13, and the above alkali blue dispersion 4.2.
A liquid developer was prepared by diluting 15 g of Isopar G, 0.06 g of a semi-docosanylamidate of a copolymer of octadecyl vinyl ether and maleic anhydride, and 15 g of higher alcohol F OC-1400 to 12 g of Isopar G.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Moreover, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were very clear.

Examples 6 to 26 Each liquid developer was produced in the same manner as in Example 5, except that resin particles shown in Table 8 below were used instead of resin particles D-13.

Table 8 When this was developed using the same device as in Example 1, 200
Even after developing 0 sheets, little or no toner adhesion was observed on the device.

Moreover, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were very clear.

(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 did not become contaminated, and both the image quality of the obtained offset printing master plate and the image quality of the printed matter after printing 10,000 sheets were very clear. Ta.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: At least one polar group selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group, and a phosphono group is bonded to only one end of the main chain of the polymer containing the repeating unit represented by the general formula (I). The weight average molecular weight is 1×
In the presence of a dispersion stabilizing resin having a molecular weight of 10^4 or more, a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization and a monofunctional monomer represented by the following general formula (II) There are carboxyl groups, sulfo groups, hydroxyl groups, formyl groups, amino groups, phosphono groups, and ▲mathematical formulas, chemical formulas, tables, etc.▼ groups [R^0 is a hydrocarbon group or -
OR^1 group (R^1 represents a hydrocarbon group)] At least one type of oligomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding at least one type of polar group selected from 1. A liquid developer for electrostatic photography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing the developer. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), X^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O- or -SO_2-. Y^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-Z^1 or -COO-Z^1 via a hydrocarbon group having 1 to 8 carbon atoms (Z^1 is
~22 hydrocarbon groups). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), T^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O-, -
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 ▼. R^3 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. R^2 represents a hydrocarbon group having 1 to 22 carbon atoms. b^1 and b^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-R^4 or -COO-R^4 via a hydrocarbon group having 1 to 8 carbon atoms (R^4 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms) represents.