JPH0446354A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain the developing solution superior in dispersion stability, redispersibility, and fixability by using disperse resin particles composed of blocks A comprising specific polymer and blocks B comprising polymer unit containing polar group, such as carboxy or sulfo and/or polymer corresponding to monofunctional monomer A. CONSTITUTION:The disperse resin particles are composed of blocks A comprising at least the polymer represented by formula I and blocks B each having at least one of polar groups, such as carboxy or sulfo, and in formula I, V0 is -COO-, -OCO-, -(CH2)y-COO-, -(CH2)y-OCO-, or -O-; R0 is >=10 C alkyl or the like; each of a1 and a2 is independently H, halogen, cyano, alkyl, -COO-R1, or R-COO-R1, thus permitting the obtained developing solution to be superior in dispersion stability, redispersibility, and fixability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial 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 qΩcm or more and a dielectric constant of 3.5 or less. , especially redispersibility, storage stability,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties.

(Prior art) The liquid developer for electrophotography (g) is made of organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic materials such as alkyl resins, acrylic resins, rosins, and synthetic rubbers. The resin is dispersed in a liquid with high insulating properties and low dielectric constant, such as a petroleum aliphatic hydrocarbon, and a polarity control agent such as a polymer containing metal sulfur, lecithin, linseed oil, higher fatty acids, and vinyl pyrrolidone is added. It was added.

In such developers, the resin is dispersed as insoluble latex particles in the form of particles with diameters of several nanometers to several hundred 011, 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 easily diffused into the solution. Therefore, due to long-term storage or repeated use, the soluble dispersion stabilizing resin became insoluble latex particles. particles may settle, aggregate, accumulate,
The drawback was that the polarity was 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 others. However, although these liquid developers have improved the dispersion stability of particles against natural makurazaki 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 addition, 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. Furthermore, it is difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 or more or very fine particles of 0.1 or less are 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 a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components are used. A method of improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A-60-1.79751 and JP-A-62-151868. Also,
In the presence of a polymer using a bifunctional monomer or a polymer using a polymer reaction, insoluble dispersed resin particles are made of a copolymer of 11 units that become insolubilized and a monomer containing two or more polar components. A method for improving the dispersibility, redispersibility, and storage stability of particles by
No. 62, No. 63-66567, etc.

(Problem to be Solved by the Invention) On the other hand, in recent years, a method of printing 500 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.

In addition, the demand for rationalization of electrophotographic engraving systems has increased,
Specifically, efforts are being made to extend the maintenance period for plate-making machines. This creates a need for a liquid developer that can be used for a long period of time without being replaced.

JP-A-60-179751 and JP-A No. 62-15186
No. 8, No. 62-166362, and No. 63-66567, the dispersion resin particles produced according to the method disclosed in No. 8, No. 62-166362, and No. 63-66567 have a tendency to deteriorate when the particles are used for a long period of maintenance or when the development speed is increased. Performance is still not necessarily satisfactory in terms of dispersibility and redispersibility, and in the case of large-sized master plates (for example, A-3 size or larger), in terms of particle dispersibility, redispersibility, and rigidity. It wasn't.

This is especially true when trying to improve operability by extending the maintenance period of the plate-making machine, or when using a large-scale plate-making machine for large-size master plates without staining the developing device and making it possible to improve the quality of copied images. When trying to improve image quality, it has been a major challenge to improve the redispersibility of dispersed resin particles.

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 has excellent dispersion stability, redispersibility, and fixing properties even in an electrophotographic printing system that speeds up the constant development process and uses long maintenance intervals. It is to provide.

Another 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 electrophotographic engraving system using a large-size master plate. It is to provide.

Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of offset printing plates having excellent printing ink oil sensitivity and stiffness 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 perform inkjet recording, inkjet recording, and
It is an object of the present invention to provide a liquid developer that can be used in any system in which a liquid developer can be used, such as m-tube recording and recording of various change processes such as pressure changes or electrostatic changes.

(Means for Solving the Problem) The above-mentioned liquid developer for electrostatic photography is formed by dispersing at least resin particles in a non-aqueous solvent having an electrical resistance of 10'Ωcm or more and a dielectric constant of 3.5 or less. In the above, the dispersed resin particles include (1) a block A containing at least a polymer component represented by the following general formula ([), a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and -P A polymer component containing at least one polar group selected from -Q, group (Q represents a Q+ group, H represents a -OQ group, and Ql represents a hydrocarbon group) and/or -functionality. A dispersion consisting of an A-B type block copolymer which is composed of a block B consisting of a polymer component corresponding to the monomer (A), has a weight average molecular weight of 1X10' to 5X10', and is soluble in the non-aqueous solvent. A stabilizing resin, and ■ a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and -P-ZO group (Z represents H-2 group or -0Z1 group, Z represents hydrocarbon group) and has a number average molecular weight of lXl0 'An oligomer that is less than or equal to (
In the presence of B), the monofunctional monomer (A) is soluble in the non-aqueous solvent but becomes insolubilized by polymerization. This was achieved using a liquid developer for electrostatography.

General formula (1) % formula % In formula (1), vo is -COO--0CO-1[CHzh
COO-1-(CHz h represents OCO-1 or -0- (y represents an integer from 1 to 3).

Ro represents an aliphatic group having 10 or more carbon atoms.

al and G2 may be the same or different from each other and are hydrogen atom, halogen atom, cyano group, hydrocarbon group, C00-
R1 or -C0O-R1 (Ill represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group.

General formula (II) →C)l-C+ E, -G In formula (II), El is -C00 (C)+4 oco-1-〇-2-so2-50CO-
, CH,)zCOO-1 CON)ICOO-2-CONICON)l-2 Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

! represents an integer of 1 to 3;) G1 represents a hydrocarbon group having 1 to 22 carbon atoms; however,
In the carbon chain of G, -0-1-CO-1-COZ-1-
OCO-1 Here, D2 represents the same content as Dl.

el and C2 may be the same or different from each other, and are hydrogen atom, halogen atom, cyano group, hydrocarbon group, C00-
Represents Da or one COO-J via a hydrocarbon (Dz represents a hydrogen atom or a hydrocarbon group which may be substituted).

Furthermore, the oligomer (B) in which a specific polar group is bonded to one end of the polymer main chain provided in the present invention has the following general formula (l
It is preferable to contain at least a repeating unit consisting of la).

General formula (na) el ej -ncH-Cchi- B+-(W+-B+floor-←z Bx)yGz formula (II
In a), els et and El represent the same symbols as in formula (II).

G represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

B1 and B2 may be the same or different from each other, and Ds
Ds l 0-1-CO-1-CO□-1-OCO-1-5O□-
1-N-, -COND.

(represents content).

-1 and -2 may be the same or different from each other, may be substituted, or -C1 (- is the 8 of the main chain, -B,
Chin G.

Represents a hydrocarbon group having 1 to 18 carbon atoms that may be interposed in a bond, where B3 and B4 may be the same or different from each other and have the same content as B1 and B2 above, and -5 is Indicates a hydrocarbon group having 1 to 18 carbon atoms that may be substituted.

m, n and p each independently represent an integer of O to 3.

However, both do not become O at the same time.

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

The carrier liquid having an electrical resistance of 109Ωe11 or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen thereof. Substitutes can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane,
Cyclohexane, cyclooctane, cyclodecane, Hensen, toluene, xylene, mesitylene, Isopar E
, Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon), Shellzol 70, Schelzol 71 (Shellzur; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco;
Spirits Co., Ltd.'s product name) etc. are used alone or in combination.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are the dispersion stabilizing resin which is the A-B type block copolymer of the present invention in a non-aqueous solvent. and polymerizing the -functional monomer (A) in the presence of the 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. For example, hexane, octane, isooctane,
Decane, isodecane, decalin, nonane, dodecane, isododecane, isoparaffin-based petroleum solvents Isopar E5 Isopar G8 Isopar H, Isopar L,
Scherzol 70, Scherzol 71, Amsco OMS
, Amsco 460 solvent, etc. may be used alone or in combination.

Alcohol is a solvent that can be used in combination with these organic solvents! ! (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, propion ethyl acid, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. methylene dichloride, chloroform, carbon tetrachloride, dichloroethane,
methyl chloroform, 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 10''Ωc11 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 monomer (A) in the present invention may be any monofunctional monomer that is soluble in a nonaqueous solvent but becomes insolubilized by polymerization. Specifically, for example, a monomer represented by the following general formula (I[l) may be mentioned.

General formula (I[l) b, b.

CH=C t Rz Formula (I[[), where vl is -COO-1 CH,COO-2-〇-1-CONHCOO-2OCO
-, -CHzOCO-2 CON)IOCO-1-8O□-1 R1 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl L-butyl group, 2-chloroethyl L2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3-methoxy propyl group, etc.).

R1 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 group, 22-dichloroethyl group, 2.2.2 -trifluoroethyl group, 2-bromoethyl group, 2-grindylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2.3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
N-anoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group basis,
trimethoxysilylpropyl 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, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group , 2-carboxamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group,
cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

bl and b2 may be the same or different, and each represents the same content as al or a2 in the general formula (1).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl 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. optionally substituted alkyl esters or amino acids having 1 to 4 carbon atoms (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2- Fluoroethyl group, trifluoroethyl 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-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3
-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); Styrene derivatives (e.g. styrene, vinyltoluene, α- Methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, NN-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinyl benzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; acrylonitrile; methacriconitrile; polymerizable double bond group Containing heterocyclic compounds (specifically, for example, Polymer Society of Japan Hr Polymer Data Handbook Fundamentals Edition J, pp. 175-18
4. Compounds described in Baifukan (published in 1986), for example,
N-vinylpyridine, N-vinylimidazole, N-vinylpyridine, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-
vinylmorpholine, etc.).

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

Next, the oligomer (B) of the present invention will be described in detail.

The oligomer (B) has a number average molecular weight of 1
'The following oligomers.

In general formula (I[), the hydrocarbon groups contained in 01, e2, E+ and G1 each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups are substituted. Good too.

In formula (II), D+ in the substituent represented by El is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, heptyl group,
hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexenyl group,
Octadecyl group, eicosanyl group, docosanyl group, 2-
chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4-1
8 optionally substituted alkenyl groups (e.g. 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group group, decenyl group, dodecenyl group,
tridecenyl group, hexadecenyl group, octadecenyl group, rillyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, 3-
phenylbrobyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group, methylhensyl group, ethylhensyl group, methquinhensyl group, dimethylhensyl group, dimethoxyhensyl group), substituted with 5 to 8 carbon atoms an optionally substituted alicyclic group (e.g., soclohexyl group, 2-cyclohexylethyl group, 2-noclobentylethyl 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, desoloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusoylamidophenyl group, etc.).

It may have a group. 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.).

G1 preferably represents a hydrocarbon group having 1 to 22 carbon atoms, and specifically represents the same content as described above. However, in the carbon chain of G+, -0-1-CO-1-COt-, -0CO-, -5
It may contain Or-, -NDt Dt -CON-, -NGO-, where it represents the same content as 口2hari.

e and B2 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 4-methyl group, an ethyl group, a propyl group, etc.), -
Coo-B3 or -CH,COO[lff (o, is,
Represents a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group having 1 to 18 carbon atoms,
These may be substituted, specifically, the above DI
represents the same content as that described for ).

Furthermore, in the oligomer (B) provided in the present invention, G in general formula (II) is used as a repeating unit.
, but the following B1, B! Preferably, the component of general formula (IIa) is characterized in that it contains at least one specific polar group represented by the formula (IIa) and contains at least two or more specific polar groups in the molecule as a repeating unit component. contains.

In the general formula (na) el ez →C1(-C)-El-(LB+iH-Bt'tyG), el and els El in the formula (Ua) are as described above.

6, and B2 may be the same or different from each other, and JS
Ds 1 [0-5-CO-140g-0-5-CO-140□-1
-N-, -CONNGO- (OS represents the formula (II
) represents the same content as Naka-nori).

Wl and -2 may be the same or different from each other, may be substituted, or -(C)l)- is the main chain ■ B, persimmon, -8,)! 5-G.

A hydrocarbon group having 1 to 18 carbon atoms that may be interposed in the bond (hydrocarbon groups include alkyl groups, alkenyl groups,
Preferred specific examples of these aliphatic groups (representing an aralkyl group or an alicyclic group) include the same content as the preferred aliphatic group of 01 in formula (fl).

However, 81 and B4 may be the same or different, and the above B1,
The same content as B2 is shown, and 6 represents - or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms and having the same content as -2.

Furthermore, concrete examples will be given regarding - and 6.

D.

1+c)-(Dt, Ds is a hydrogen atom, an alkyl group, halogen-(CH)-(Bs, B4, -3, G2 and p have the same meaning as the above Ih (Wz-84-G2 symbol), etc. It is composed of any combination of atomic groups.

Furthermore, m, n and p may be the same or different,
Represents the number 0.1.2.3. However, both do not become 0 at the same time.

G2 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. Preferably, it represents an optionally substituted aliphatic group having 1 to 22 carbon atoms, and specifically represents the same content as Dl in formula (If).

Furthermore, in formula (IIa), El, 1, B1, edge 2
, B2 and G, the total number of atoms of each atomic group is preferably 8 or more.

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

In the following, a represents -H or C1; R represents an alkyl group of CI; P' represents a hydrogen atom or an alkyl group of CI-II; k2 represents an integer from 1 to 12; l represents an integer from 1 to 100. indicates an integer.

One generation H2-C← -(COZ C)- COO(C)I zbusy0COCH=CH-COORCo
o (CH, ya0COI? -(-Cut-CH -ncL-C← C00C)IzC)ICHzOCOR COO(CH2 angry C00R OCOI? (A)-3 -(CH,-c+- -ncH! -C)- cooccoz Anger 0CO(CH1 pigeon 0CORC00((
JIi+1TOCO(CI(Mountain NH-1t(^)-4 (^)-9 ACL CI- 1+ct+t-c← C00(CH2+-0CO(C)lx Pigeon C00RCOO
(CHzCHtO+T-R' (C)I C)I)-Coo (C)I Z)-OCOR ACH-CHhi- COOCLCI(CH2(IcOR coR (A)-12 1 generation H2 l- →CHI CH C00CHCH2COOR OCO(C8 CHICOOR -(C)+2 CH)- (C1, CHICOOR-COO(C)I!HATO0COR(A)-13 →CHZ CI- At least one repeating unit represented by the above general formula (II) Polar -+cHI CI- COO (CH stands for OCO (CH stands for 5OtR), and Z stands for carbonized carbon having 1 to 18 carbon atoms). Represents a hydrogen group.

Preferably, the hydrocarbon group is an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
butenyl group, pentenyl group, hexenyl group, 2-chloroethyl group, 2-anoethyl group, soclopentyl group, nclohexyl group, hensyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), or an optionally substituted aromatic group (For example, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group,
methoxyphenyl group, cyanophenyl group, etc.).

Furthermore, among the polar groups of the present invention, the amino group is -NH, number 1 to
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 above-mentioned hydrocarbon group 2.

Even more preferably Zl, 0. Examples of the hydrocarbon group represented by D+o 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 toad that connects the component of formula (ff) and the polar group includes a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (heteroatoms include, for example, an oxygen atom, a sulfur atom, and a nitrogen atom). , silicon atoms, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

Among the oligomers (B) of the present invention, preferred are 2N
Va) or as shown by the formula (TVb).

General formula (IVa) e, e.

^-z-+cu-C)-E, -T General formula (IVb) e, el -(CH-C)-Z -A E, -T In formula (■a) and formula (IVb), el, e2 , E represents the same symbol as in formula (n), and T represents 61 in formula (II).
or +W + -B ordinal W z - in formula (IIa)
B z - represents G z.

A represents the aforementioned polar group bonded to one end in formula (n).

D-th Z is a simple bond or -+c>-CD++, I)+
2 Each independently represents 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 propyl group) etc.) , -(CH=CH″F-1Sl-(
DIl, Dl< each independently represents a hydrogen atom, a hydrocarbon group having the same content as D1-2 above], or a linking group composed of a single linking group or any combination selected from the following atomic groups. represents.

When the upper limit of the number average molecular weight of the oligomer (B) exceeds 104 times, the stiffness resistance decreases. 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 monopolymer component or a copolymer component remaining from among the repeating units represented by the formula (II) or a unit corresponding to the repeating unit represented by the general formula (U). It is composed of a copolymer component obtained by polymerizing the monomer and other copolymerizable monomers. Examples of other monomers that can be used as a copolymer component together with the polymer component of formula (n) include acrylonitrile, methacrylonitrile, and a heterocyclic compound containing a polymerizable double bond group (specifically, compounds similar to the heterocyclic compound in the monomer (A) described above), compounds containing a carboxamide group or sulfamide group and a polymerizable double bond group (for example, acrylamide, methacrylamide, diacetone acrylamide, 2- carboxyamidoethyl methacrylate, vinylhenzenecarboxamide, vinylbenzene sulfamide, 3-sulfamidopropyl methacrylate, etc.).

The repeating unit represented by the general formula (n) or (IIa) described above is suitably 30% to 100% by weight, preferably 5% by weight in the oligomer (B) used in the present invention.
It is 0% to 100% by weight.

In addition, the main chain of the polymer contains phosphono groups, carboxyl groups, sulfo groups, hydroxyl groups, formyl groups, amino groups, -P
-Zo Those containing no co-electronically synthesized H component containing polar groups are preferred.

The oligomer (B) of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents at the end of a living polymer obtained by conventionally known anionic polymerization 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, Dreyfuss & R,P,
QuirkEncycl, Polyv, Sci,
Eng, + Yu, 551 (1987), Yoshiki Nakajo 1 Yuya Yamashita [Dye and Medicine, J, 232 (1985),
Akira Ueda, Susumu Nagai, "Science and Industry", Hunger, 57 (1986)
It can be produced by the method described in the review article and the literature cited therein.

As a polymerization initiator containing a specific polar group in the above-mentioned molecule, for example, 4,4'-azobis(4-cyanovaleric acid)
, 4,4'-azobis(4-cyanovaleric acid chloride)
, 2.2'-azobis(2-cyatuburobanol L2
．． 2'-azobis(2-cyanopentanol), 2.2
' -Azobis[2-methyl-N-(2-hydroquinethyl)propioamide), 2,2'-Azobis(2methyl-N-[1,1-bis(hydroquinemethyl)ethyl]
Propioamide 1.2.2'-azobis(2-methyl-N-rl, 1-bis(hydroquinomethyl)-2-hydroxoethyl)propioamide 1.2.2'-azobis[2-(5-methyl 2- imidapurin-2-yl)propane], 22'-azobis[2-(4,5,6,7-titrahydroIH-1,3-diazepin-2-yl)propane), 2. 2'-AzobisC2-(3,45,6
-tetrahydrobyrimidin-2-yl)propane], 2
．． 2'-azobis(2-(5-hydroxy-3,4,5
,6-tetrapyrimidin-2yl)propane L 2,2
'-azobis(2(1-(2-hydroxyethyl)-2
-imidazolin-2-yl]propane), 2,2'-azobis(N-(2-hydroxyethyl)-2-methylpropionamidine L 2,2'-azobis(N-(4
-aminophenyl)-2-methylpropionamidine]
Examples include azobis compounds such as.

Examples of chain transfer agents containing a specific polar group in the molecule include mercapto compounds, disulfide compounds, and iodine-substituted compounds, with mercapto compounds being preferred. For example, thioglycolic acid, 2-
Mercaptopropionic acid, thiomalic acid, 2-mercap[-ethanesulfonic acid, 2-mercaptoethanol, 2
Examples include -mercaptoethylamine, thiosalicylic acid, α-thioglycerin, 2-phosphonoethylmercaptan, hydroxythiophenol, and derivatives of these mercapto compounds.

These polymerization initiators and/or chain transfer agents have the general formula (II
) It is used in an amount of 0.5 to 20% by weight, preferably 1 to 141%, based on the total amount of the monomer corresponding to the repeating unit represented by () and other polymerizable monomers.

The oligomer (B) used in the present invention is preferably represented by the general formula (lVa) or (IVb), and in these formulas A-Z is (B)-7 1(0(CHzh - More specific examples of the parts affected are shown below.

deer The scope of the present invention is not limited to these (B)-8 HzN (CHz Moro S do not have.

(B)-9 HOCH-CH2S- In the following, kl is an integer of 1 or 2; 2 is 2IO
CI(t represents an integer of ~16; represents an integer of 1 or 3.

F100C+C)Izhry5 (B)-10 HOOC-CH-5- HOOC-CH2 HOOC(CHzhyOOC+CHz+-rTSHOO
C(CHz)yyNHcO(cHz+-rrs-H(
hS (CHz) ZS- 03tl HOOC(C)lz)-rrcOo(Cf(zbkoc/
C:0 HOOC(C!(z) zC N HO(CHzhgoC- CHfflOH R: [0soCHzh- 1(,C-C- C)I20H R゛0H (B) -29 HOOC(CHz)JH( Hz)TTS-(B)-
26 Z: ICHzh, (CHz)r, -CH,CH
CHtR';-)1, -CHzCHzOtl L CH3 OHC(CH2hC- N (B) I R2-P-0(CHz) 2S- H R2; C1-6 alkyl group (B)-30HOOC(CHz)zcONH(CHz )
Next, the dispersion stabilizing resin of the present invention will be described in detail.

The dispersion stabilizing resin used in the present invention is an A-B type block copolymer, and one block (referred to as block A) is composed of a polymer component consisting of repeating units represented by general formula (1). and the other block (referred to as block B) is a polymer component containing at least one kind of polar group selected from the above-mentioned specific polar groups and/or the above-mentioned functional monomer (A). and has a weight average molecular weight of 1X10' to 5X
It is characterized by being 10'.

The proportion of block A and block B in the AB type block copolymer is preferably 99/l to 50/50 (weight ratio).

The specific polar group-containing polymer component contained in block B is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the dispersion stabilizing resin. In addition, when a specific polar group-containing polymer component is not present in the bronch, the polymer component corresponding to the -functional monomer (A) is preferably 5 to 50 parts by weight based on 100 parts by weight of the resin. and more preferably 10 to 40 parts by weight.

The weight average molecular weight of the AB type block copolymer is preferably 2X10' to 1X10'.

The repeating unit represented by the general formula (1) constituting block A will be explained in detail.

In general formula (1), vo is preferably -COO-1
Represents OCO- or -〇-.

Ro represents an alkyl group or alkenyl group having 10 or more carbon atoms, and these may be linear or branched.

Specific examples include decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decer group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, ryl group, etc. .

al and a2 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 -CIbCOO-R+ (R+ is a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (e.g., an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.) ) represents].

Specifically, R1 is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2- methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl a having 4 to 18 carbon atoms
(Example -Methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group,
octadecenyl group, rillyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group) ethyl group, 2-cyclopentylethyl group, etc.), and optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octyl group, Phenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxyphenyl group , ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

Further, in the block A of the dispersion stabilizing resin used in the present invention, other repeating units may be contained as copolymerization components together with the repeating unit represented by the general formula (I). As the other copolymerization component, any compound may be used as long as it consists of a monomer that can be copolymerized with the monomer corresponding to the repeating unit of general formula (1).

However, it is preferred that no other components are present, and at most no more than 20 parts by weight of block A is used. If it exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles will deteriorate.

In Pro and 7-A, two or more repeating units represented by the general formula (1) may be used in combination.

Next, the polymer component constituting block B of the block copolymer of the present invention will be explained in detail.

Block B is composed of a polymer component corresponding to the -functional monomer (A) and/or a specific polar group-containing polymer component described above.

As the polymer component corresponding to the monofunctional monomer (A),
Examples of the monomer (A) to be insolubilized include those described above.

Preferably, a monofunctional monomer (A) that becomes dispersed resin particles
It is composed of the same monomer as.

-Q represents a group or -OQ represents a group, Ω represents a carbon number of 1 to 1
0 hydrocarbon group. The hydrocarbon group of OI preferably represents an aliphatic group having 1 to 8 carbon atoms which may be monosubstituted, or an aromatic group which may be substituted.

Specifically, the same hydrocarbon groups as the above-mentioned Zl can be mentioned.

Moreover, among the polar groups of the present invention, the amino group is -NH,,1-1
0 hydrocarbon group, preferably a C 1-7 hydrocarbon group, and specifically, the same hydrocarbon groups as the above-mentioned Zl can be mentioned.

Even more preferably, the hydrocarbon group of Q, R, and R5 is an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, or an optionally substituted phenyl group. It will be done.

The monomer corresponding to the above specific polar group-containing polymer component may be any monofunctional monomer containing at least one specific polar group. For example, it is described in "Polymer Data Handbook (Basic Edition)" edited by the Society of Polymer Science and Technology, Baifukan (published in 1986).Specifically,
Acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoquine, α-acetoxymethyl, α-(2
-amino)methyl form, α-chloro form, α-bromo form, α
-fluoro form, α-tributylsilyl form, α-one ano form,
β-chloro form, β-bromo form, α-chloro-β-methquine form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2 ~Alkenylcarboxylic acids (e.g. 2
-Pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2
-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids and ester derivatives of these carboxylic acids or sulfonic acids, compounds containing the polar group in the substituent of amide derivatives, and the like.

Specific examples of these compounds include the following. However, on each side below, e is -H1-C
H,, -CI, -Or, -CN, -CH2COOCI+
3 or CH, COOH, r represents -H or -CHs, n represents an integer of 2 to 10, 1 represents an integer of 1 to 10, and lOH represents an integer of 1 to 4.

-COOH.

0-P-OH.

OH (R1 represents a C+-t alkyl group).

Xl represents -COOI (or -OH).

(C) CH2=C 0OH (C) C.O.

CH=CH 0OH (C) (C) CIl, -C C00 (CHI 斥TX CH2=C C0NH(CHz)fi-X (C) (C) (C) CH2=C C0NHCOO(CHz') TVX CHzmiC C0NHCONII (CHz′)Tv−Xl (C) (C) CH,=C C00(CHz斥rOCO(CHz斥“xlCH,,C C0N1((CHl2)−70CO(CH2)−i7−
X.

(C) (C) C)+2=C CONHCHCHlCOOH CIl□Cool( CCH2= CC00(CHl)7N)ICO(CI(2)-7XI
(+ may be the same or different) (C)-16 CH2,C0)l COOCffzCl(CHz(C!(z')N-Vχ1
(C)-2Of CH2=C C00(CHt)i-7-CON-(C)IzCHz-
Xz)! The AB type block copolymer of the present invention can be produced by a conventionally known polymerization reaction method.

Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is previously protected as a functional group, and an organometallic compound (for example, alkyl lithiums, lithium diisopropylamide, alkyl magnesium A-B type block copolymers are produced by known so-called living polymerization reactions such as halides, etc.) or ionic polymerization reactions using hydrogen iodide/iodine systems, photopolymerization reactions using porphyrin metal complexes as catalysts, or group transfer polymerization reactions. After synthesizing, the functional group with a protected polar group is deprotected by hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, photolysis reaction, etc. to form a polar group. One example is shown in the reaction scheme below (
Shown in 1).

For example, P. Lutz, P. Masson et.
al, Polys.

Bull, 14.79 (1984), B.
C, Anderson, G, D.

Andrews et al, Macromo
lecules+ 14. 1601 (1981
), K, Hatada, K, Ute, et a
l+ Polys, J, + 17+977 (19
85), Dobotsu, 1037 (1986), Hiroshi Migitari-1
Ko Hatada-r Polymer Processing Jn, 366 (1987),
Toshinobu Higashimura, Mitsuo Sawamoto, “Collection of Polymer Papers”, 189 (
(1989), HoKuroki, T., ^ida, J.
, As, Chew, Soc, + Jj19+47
37 (1987), Takuzo Aida, Shohei Inoue, “Organic Synthetic Chemistry JQ, 300 (1985), D, Y, Sog
ah, L R.

Hertler et al, Macrowolec
It is easily synthesized according to the synthesis method described in ules+ -, 2Jl+ 1473 (1987), etc.

Another method for synthesizing A-B type block copolymers is the photoiniferter polymerization method using a monomer with its polar group unprotected and using a dithiocarbament compound as an initiator. .

For example, Yokiyuki Otsu "Polymer" Nail, 248 (1988
), After Test-1 Takashi Otsu-1Poly-1Rep, Ja
p., 33-, 3508 (1988), JP-A-1986-
111, JP-A-1-26619, and the like.

Furthermore, the protecting group that protects the specific polar group of the present invention and the deMation (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. There are various descriptions in ``Reactive Polymers'' by Takao Iwakura and Keisuke Kurita, published by Kodansha (1977).
, T., Il., Greene.

'Protective Groups in Org
anic 5ynthesisJ+John @1l
ey L 5ons (1981), J.
F, -, McOsie.

rProtective Groups in Org
Antc Chemistry”.

The method described in detail in the review article of Plenum Press, (1973) etc. can be appropriately selected and carried out.

The dispersion resin of the present invention comprises a dispersion stabilizing resin and an oligomer (B
), and the important thing is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, the desired dispersion can be achieved. Resin can be obtained.

More specifically, the oligomer (B) represented by the general formula (]I) is added to the monomer (A) to be insolubilized in an amount of 0.05 to
It is preferable to use 10% by weight, more preferably 0.1 to 5% by weight. Even more preferably 0.3~
It is 3% by weight.

Further, the molecular weight of the dispersion resin of the present invention is 101 to 106, preferably 104 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.
) A method of adding a polymerization initiator to a mixed solution of (2), a method of dropping monomer (A) and oligomer CB) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved, or (2) a method of dispersing. A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing the entire amount of stabilizing resin and a part of the mixture of monomer (A) and oligomer (B); There are methods of optionally adding a mixed solution of dispersion stabilizing resin, monomer (A), and oligomer (B) together with a polymerization initiator to an aqueous solvent, and production can be performed using either method. I can do it.

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 511 parts.

The amount of the polymerization initiator is suitably 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 zero 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 dispersed resin particles produced according to the present invention as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, and can be used repeatedly for a long time, especially in a developing device. The dispersibility is good even when the developing speed is increased, and redispersion is easy even when the developing speed is increased, and no stains are observed at all 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.

In particular, JP-A-62-166362 or JP-A-63
In the non-aqueous dispersion resin described in -66567Ji4, in addition to a monomer containing at least two ester bonds, etc. in the molecule, which can be copolymerized with a monomer that is polymerized and made insolubilized, the polymer main chain A random copolymer soluble in the non-aqueous solvent containing a copolymerization component having a polymerizable double bond group bonded to a site separated by a total number of atoms of 8 or more from the non-aqueous solvent was used as a dispersion stabilizing resin to polymerize and granulate it. These particles are resin particles (latex particles), and although the dispersibility and rigidity resistance of these particles have been greatly improved compared to conventional particles, the performance of these particles has been greatly improved compared to conventional particles. (For example, manufactured by Fuji Photo Film Co., Ltd., ELP-560,
ELP-820, etc.), or when the processing speed of the plate making machine is increased, there are still problems with the dispersibility of the particles, resulting in staining of the plate making machine (particularly staining of the developing device) and particle aggregation/sedimentation. Or, when the master plate was printed, the strength of the image area was still insufficient, resulting in a decrease in rigidity. When the resin particles provided by the present invention are used, no problems occur even under such severe conditions.

As described above, the high redispersibility of the latex particles of the present invention is due to
It depends on the soluble A-B type block copolymer used together with the monomer (A) and oligomer (B) to be insolubilized.

That is, the dispersion stabilizing resin of the present invention comprises a block A composed of a polymer component containing a long M aliphatic group that has a high affinity for the non-aqueous solvent, and a monomer that has a low affinity for the non-aqueous solvent and makes it insolubilizable. It is characterized by being an AB type block copolymer in which a block B composed of a polymer component having affinity for the polymer (A) is bonded.

As a result, the block 8 portion is sufficiently adsorbed to the dispersed resin particles through physicochemical interaction during polymerization and granulation, and the block A portion, which has a high affinity for the non-aqueous dispersion medium, is adsorbed to the M solvent. It is presumed that the effects of the present invention have been achieved because it is possible to sufficiently solvate and to have a sufficient steric repulsion effect (so-called tail-like adsorption).

On the other hand, in the conventionally known random copolymer of the polymer component used in block A and the polymer component used in block B, the adsorption part is in the polymer chain composed of the solvated component. Because it is randomly combined with
Adsorption to the dispersed resin particles was not sufficient, and furthermore, the pattern of adsorption was loop-like, so the steric repulsion effect was also negated, resulting in insufficient dispersion stability.

In addition, high rigidity resistance means that the monomer to be insolubilized has good compatibility with the physicochemically bonded oligomer (B), and even under mild fixing conditions, it is sufficiently compatible and forms a uniform film. It is estimated that this will be achieved.

In the liquid developer of the present invention, a coloring agent may be used if desired.6 The coloring agent is not particularly limited, and 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, alkaline flu, 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.

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 components.

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

The toner particles mainly composed of resin (and optionally used colorant) are preferably 0.5 parts by weight to 50 parts by weight based on 1000 parts by weight of the carrier liquid, and image density is improved when the amount is less than 0.5 parts by weight. is insufficient, and if it exceeds 50 parts by weight, fogging tends to occur in non-image areas.Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization is also used if desired, and the amount is 0.00 parts by weight per 1.000 parts by weight of the carrier liquid. About 5 parts by weight to 100 parts by weight can be added.

The load 1 regulator as described above is used in an amount of 0.001 to 1.0 parts by weight per 1000 parts by weight of carrier liquid. 1 part is preferable, and various additives may be added as desired, and the upper limit of the total amount 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 becomes lower than 109 ΩC-, it becomes difficult to obtain a continuous tone image of good quality, so it is necessary to control the amount of each additive added within this limit. is necessary.

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

A mixed solution of 95 g of dodecyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, and -
It was cooled to 78"C. 1.0 g of 1.1-diphenylphthyllithium was added and the reaction was continued for 12 hours. Furthermore, a mixed solution of 5 g of triphenylmethyl methacrylate and 25 g of tetrahydrofuran was added to this mixed solution sufficiently under a nitrogen stream. After degassing, the mixture was added and reacted for further 8 hours. After the mixture was brought to O'c, 10M1 of methanol was added and reacted for 30 minutes to stop the polymerization. The resulting polymer solution was heated to temperature with stirring. 30'C, 30% hydrogen chloride ethanol solution 1sIIi was added thereto and stirred for 1 hour.Next, the solvent was distilled off from the reaction mixture until the total volume was reduced to half under reduced pressure, and then poured back into methanol IN. The precipitate was collected and dried under reduced pressure, and the resulting polymer had a weight average molecular weight of 4.5.
The yield was 70 g at X 10'.

(P)-1 CL CH.

-rcoz-c″hTb -(CI(t -0r (weight ratio)) COOC+□H2S C00H b indicates a block bond (the same applies hereinafter).

Person 27 P-2 A mixed solution of 46 g of octadecyl methacrylate, 0.5 g of aluminum methyl (tetraphenylborufinato), and 60 g of methylene chloride was heated at a temperature of 30°C under a nitrogen stream.
And so. This was irradiated with 300 W xenon lamp light from a distance of 25 cm through a glass filter, and reacted for 12 hours. After further adding 4 g of benzyl methacrylate to this mixture and irradiating it with light for 8 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction.Next, Pd-C was added to this reaction mixture. A catalytic reduction reaction was carried out at a temperature of 25° C. for 1 hour.

After filtering off the insoluble matter, it was reprecipitated into methanol 50011i, and the precipitate was collected and dried. The obtained polymer has a yield of 3
The weight average molecular weight was 3.times.10' at 3 g.

1:P)-2 CH3CH3-(CHz-C)rr-b-1-iCHt-C)
y■ C00C+Jzt(n) A of COOH: P-3 A mixed solution of 90 g of tridecyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream,
Cooled to -78°C. 0.8 g of 1,1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours.

Furthermore, 10 g of 4-vinylphenyloxytrimethylsilane was added to this mixture, and after stirring for 6 hours, 3 g of methanol was added.
was added and stirred for 30 minutes.

Next, add 1 part of 30% hydrogen chloride ethanol solution to this reaction mixture.
After stirring at 25°C for 1 hour, methanol I
It was reprecipitated into Il and the precipitate was collected. The precipitate was washed twice with 300ml of methanol and dried. The obtained polymer is
The yield was 58 g and the weight average molecular weight was 3.5 x 104.

(P) -3 C.B.

Name: P-4 Hexadecyl methacrylate 95g, benzyl N, N-
A mixture of 2.0 g of diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 60°C. This was irradiated with light for 10 hours using a 400 W high-pressure mercury lamp from a distance of 1 oc- through a glass filter for photopolymerization. After adding 5 g of acrylic #1 and 180 g of methyl ethyl ketone to this, the mixture was replaced with nitrogen and irradiated with light for 10 hours again.

The resulting reaction mixture was reprecipitated in 1.5 ml of methanol, collected, and dried. The obtained polymer had a yield of 68 g and a weight average molecular weight of 4 XIO'.

(P)-4 Hs -(CHt -C)v-r-b ---ICHz -C
Hh “C00C+!!3(n) Co([Nomu
: P A mixed solution of 80 g of stearyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, and -
Cooled to 78°C. 1.0 g of 1.1-diphenyl-3-methylpentyl potassium was added and stirred for 10 hours. Further, 20 g of styrene was added to this mixture and stirred for 8 hours, and the reaction mixture was brought to 0°C and 10 m of methanol was added. The polymer obtained by drying had a yield of 68 g and a weight average molecular weight of 3 x 10'.

(P)-5 2,3-diacetoxypropyl methacrylate) 1
00g, 3-mercaptopropion #5g, toluene 1
A mixed solution of 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,
1. 1.5 g of B, N,) was added and reacted for 4 hours. Furthermore,
A.1. 0.4g 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 The number average molecular weight of the 6-polymer obtained was 3,300.

Oligomer B-1: 0COC)I.

2-31 of the first sesame: In Production Example 1 of B-2-B-31, in place of 2,3-diacetoxypropyl methacrylate and 3-mercaptopropyl acid, methacrylates corresponding to Table 1 below are used. Oligomers B-2 to B-31 were produced in the same manner as in Production Example 1, except that the monomer and mercapto compound were used. The number average molecular weight of the obtained oligomer was 2,500 to 5.000.

Table CHl ^-5+cH, -c)- OOR Table-1 (Continued 2) Table (Continued 1) Table■ (Continued 3) 32:B-32 of the first sesame 2-(n-nonylcarbonyloxy)ethyl chloride 100g of nate, 150g of toluene, and 5g of ethanol
While stirring 0 g of mixed solution under a nitrogen stream, the temperature was 75°.
It was heated to C. 4. Add 8 g of 4'-azobis(4-cyanovaleric acid) (abbreviated as A, C, V, ) and react for 5 hours,
Furthermore, 2g of A, C, and ν9 were added and reacted for 4 hours. After cooling the resulting reaction solution, it was reprecipitated into a mixed aqueous solution of methanol/water [(4/1) volume ratio 1], and the aqueous methanol solution was decanted for 1 hour, and then the viscous material was dried. Yield 70. The number average molecular weight of the polymer was 2.600.

Oligomer B-32: In Production Example 32, the azobis compounds shown in Table 2 below were used instead of polymerization initiation sides A, C, and V, and 2-(n-nonylcarbonyloxy)ethyl crotonate was converted to correspond to the structure below. Oligomers B-33 to B-41 were produced in the same manner as in Production Example 32, except that the monomers were changed. The number average molecular weight of the obtained oligomer was 2,000 to 4,000
It was 0.

(Leaving space below) Azobis compound 0 COCzHs (Weight composition ratio) R-N=N (Continued 1) --S 1: D-1 20 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1 oligomer B-
A mixed solution of 1.0 g of 1 and 380 g of Isopar H was heated to 75° C. while stirring under a nitrogen stream. 2
．． 2'-azobis(valeronitrile) (abbreviation: A, B
, V, N, ) was added and reacted for 4 hours.
0.4g of B, V, and N were added and reacted for 2 hours. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88°C. The temperature was raised to 100°C, and the mixture was stirred for 1 hour 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 86% and an average particle size of 0.20a.

--S ~: D-~D-
In production example 1 of latex particles, dispersion stabilizing resin P
Latex particles D-2 to D-4 were produced in the same manner as in Production Example 1, except that -1 and oligomer B-1 were replaced with the resins and oligomers shown in Table 3 below.

--S ~: D-~D-
In production example 1 of latex particles, dispersion stabilizing resin P
Latex particles D-5 to D-15 were produced in the same manner as Production Example 1, except that -1 was replaced with each resin shown in Table 4 below. The polymerization rate of each latex was 83 to 88%.

(The following is a blank space) ---S ~: D-~D-
In Production Example 1 of Latex Particles D-1, each latex particle was produced under the same conditions as Production Example 1, except that the dispersion stabilizing resin P-1 and oligomer B-1 were replaced with the compounds shown in Table 5 below. did. The polymerization rate of each latex particle is 85-9
It was 0%.

Moreover, the average particle diameter of the obtained particles is 0.18 to 0.25, respectively.
-, and the particle size distribution was sharp and monodispersity was good.

Table 5 (Continued) --S: D-vinyl acetate 90
g, N-vinylpyrrolidone 10g1 Oligomer B-37
1.0 g, 2 g of dispersion stabilizing resin P-17 with the following structure
A mixed solution of 0 g and 380 g of n-decane was heated to a temperature of 75° C. while stirring under a nitrogen stream. ^, r, B, N
Add 1.7g of , react for 4 hours, and then add 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 0.26-.

Weight average molecular weight: 7 XIO'--S: D-A mixed solution of 25 g of dispersion stabilizing resin P-7 and 680 g of n-dodecane was heated to a temperature of 60'C while stirring under a nitrogen stream.

To this solution, add 100 g of methyl methacrylate,
-1.5 g of B-36, 1.5 g of n-dodecyl mercaptan.
0g and a mixed solution of 0.8g of A, B, ν, N, 2
It dripped in time. After reacting for 2 hours, A, B, V,
0.3 g of N was added and reacted for 2 hours.

After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.25.

M-X 4: 18g of D-42 dispersion stabilizing resin-16, 95g of vinyl acetate,
A mixed solution of 5 g of Croton H, 1.5 g of Oligomer B-2, and 468 g of Isopar E was heated to a temperature of 70° C. with stirring under a nitrogen stream. 0.8g of A, BJ, N
After adding and reacting for 6 hours, raise the temperature to 100°C and leave it as it is for 1
The mixture was stirred for an hour and the remaining vinyl acetate was distilled off.

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 85% and an average particle size of 0.25x.

--S = D-18g of dispersion stabilizing resin P-18 with the following structure, 94g of vinyl acetate, 4-
A mixed solution of 6.0 g of pentenoic acid, 1.2 g of oligomer B-3, and 380 g of Isopar G was heated to a temperature of 75° C. while stirring under a nitrogen stream. A.8. VJl
, and reacted for 4 hours, further adding A, B, V, 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 a latex with an average particle size of 0.2311 IIl.

Weight average molecular weight: 4.5X10' --S: D-20g of dispersion stabilizing resin P-19 with the following structure, 2g of oligomer B-31
A mixed solution of 680 g of g and n-dodecane was heated to 60° C. while stirring under a nitrogen stream. In this solution,
A mixed solution of 100 g of methyl methacrylate, 1.0 g of Sn-dodecyl mercaptan, and 0.8 g of A, B, V, and N was added dropwise over 2 hours. After reacting for 2 hours, A
, B, V, and N were added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.28.

CH3CL -(CHt -ChlT-b -(CHz -Chl-
COOC+J33 C00CI+3 Weight average molecular weight: 8
.

2. Oligomer B-14. Og and Isopar H380
The mixed solution of g was heated to 45° C. with stirring under a nitrogen stream. Add a hexane solution of n-butyllithium to a solid amount of 1.0 g of n-butyllithium.
Time reacted. After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was a latex with an average particle size of 10.30.

A) In production example 1 of latex particles D-1, 20 g of poly(octadecyl methacrylate), 100 g of vinyl acetate,
Monomers with the following structure (1.0 g of N and 3 g of Isopar H)
The same procedure as in Production Example 1 was carried out except that 85 g of the mixed solution was used.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of '1.2.
It was 0% latex. (Unexamined Japanese Patent Publication No. 60-17975
Latex particles described in No. 1) --S 7: B)
In Production Example 1 of latex particles D-1, the dispersion stabilizing resin R-1 having the following structure was Log, 100 g of vinyl acetate,
Monomers with the following chemical structure (Ig and Isopar H are 3
The same procedure as in Production Example 1 was carried out except that 85 g of the mixed solution was used.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.24.
- latex. (Latex particles described in JP-A-63-66567) Monomer (1) Hs CtI, ;C COO(CIlg)C00 (CI1+w(n) Resin for dispersion stabilization: R-1 (weight composition ratio) Example 1 Dodecyl methacrylate/acrylic acid (copolymerization ratio: 95
15 weight ratio) copolymer, 30 g of Nigrosine 1Og & Scherzol 71 were placed in a paint shaker (Tokyo terminal a) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of Nigrosine.

30g of resin dispersion D-1 of latex particle production example 1
, 2.5 g of the above nigrosine rug, FOC-1400
(Tetradecyl alcohol, manufactured by Nikki Kagaku ■) 15g, [
A liquid developer for electrostatic photography was prepared by diluting 0.08 g of octadecene-half-maleic acid octadecylamide copolymer to 12 parts of Shersol 71.

Two types of liquid developers A and B for comparison were prepared by replacing the resin dispersion in the above production example with the following resin particles.

Comparative liquid developer A Resin dispersion of Nilatex particle production example 46 Comparative liquid developer B Resin dispersion of Nilatex particle production example 47 These liquid developers were prepared using fully automatic plate making 1l ELP-560 (Fuji Photo Film ELF Master type (manufactured by Fuji Photo Film), which is an electrophotographic light-sensitive material, 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.

The blackening rate (Iiii image area) of the copied image was determined using a 30% original.

The results are shown in Table-6.

Table 6 When plates were made using each developer under the above-mentioned plate making conditions, the developer of the present invention did not cause staining of the developing device and the image on the 2000th plate making plate was clear. .

On the other hand, the master plate for offset printing (ELP master) obtained by making the 10th plate using each developer was printed in a conventional manner until the printed image showed missing characters, fading in the solid area, etc. When comparing the number of printed sheets, the master plate obtained using either the developer of the present invention or Comparative Examples A and B did not generate the problem even after 10,000 sheets or more were printed.

As shown in the above results, only the developer made from the resin particles of the present invention was one that did not collect any dirt on the developing device and at the same time significantly increased the number of master plates printed.

On the other hand, in the case of Comparative Example A and Comparative Example B, the plate-making conditions are harsh (conventionally, the blackening rate of the copied image is about 8-10% at a plate-making speed of 2 to 3 sheets/min). Then, the developing device (especially on the back electrode plate) started getting dirty.
After 2,000 copies, the image quality of the copied images on the plate began to be affected (decreased D-ax, blurring of thin lines, etc.). Therefore, in these master plates,
When printed, the image quality of the printed material deteriorated from the beginning of the printing process, and it was no longer usable for practical use.

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 20
A black resin dispersion with an average particle size of 0.24 was obtained by removing the remaining dye by passing it through a 0 mesh nylon cloth.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 20 g of FOC-1600 (manufactured by Nissan Chemical Company, hexadecyl alcohol) to 11 of Shersol 71.

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 single-sheet printing was also very clear.

Example 3 White dispersion 10 obtained in latex particle production example 42
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 to 80°C and stirred for 6 hours. After cooling to room temperature 20
The remaining dye was removed by passing it through a 0 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.26#.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05 g of Isopar H to 11.

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 6
, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-
1400 (manufactured by Nissan Chemical ■, tetradecyl alcohol) 2
0g and 0.02g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 1j! of Isopar G! A liquid developer was prepared by diluting it to .

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

Further, after this developer was left to stand for three months, the same treatment as above was performed, but there was no difference at all from before the aging.

Example 5 Poly(decyl methacrylate) IOg, 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.

White resin dispersion D obtained in latex particle production example 5
-5, 30g of the above Alkali Blue Dispersion 11114.
A liquid developer was prepared by diluting 2 g of Isopar G, 15 g of isostearyl alcohol, and 0.06 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. In addition, 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.

Examples 6 to 29 Liquid developers were prepared in the same manner as in Example 5, except that each latex shown in Table 7 below was used in place of latex particles D-5.

Table 7 When this was developed using the same device as in Example 1, 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.

Further, after this developer was left to stand for three months, the same treatment as above was performed, but there was no difference at all from before the 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 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 (2)

[Claims] (1) Electrical resistance 10^9Ωcm or more and dielectric constant 3.5
In an electrostatographic liquid developer comprising at least resin particles dispersed in the following non-aqueous solvent, the dispersed resin particles contain at least a polymer component represented by [1] the following general formula (I): Block A, carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and ▲numerical formula, chemical formula, table, etc.▼ group (Q_0
represents a -Q_1 group or -OQ_1 group, and Q_1 represents a hydrocarbon group] A polymer component and/or a monofunctional monomer (A) containing at least one polar group selected from
Block B consisting of a polymer component corresponding to
and a dispersion stabilizing resin consisting of an A-B type block copolymer soluble in the non-aqueous solvent, and [2] only at one end of the main chain of the polymer consisting of a repeating unit represented by the following general formula (II). , carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ group [Z
_0 represents -Z_1 group or -OZ_1 group, Z_1 represents a hydrocarbon group. ) in the presence of a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization. A liquid developer for electrostatic photography. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), V_0 is -COO-, -OCO-, ■C
It represents H_2■_yCOO-, ■CH_2■_yOCO-, or -O- (y represents an integer from 1 to 3). R_0 represents an aliphatic group having 10 or more carbon atoms. a_1 and a_2 may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R_1 or -COO-R_1 via a hydrocarbon group
(R_1 represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (II), E_1 is -COO-, -OCO-, ■CH
_2■_lCOO-, ■CH_2■_l-OCO-, -
O-, -SO_2, -CONHCOO-, -CONHC
ONH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (D_1 is a hydrogen atom or a carbon number of 1 to 22 G_1 represents a hydrocarbon group having 1 to 22 carbon atoms. However, in the carbon chain of G_1, -O-, -CO-, -CO_2
-, -OCO-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ may be included. Here, D_2 represents the same content as D_1. e_1 and e_2 may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-D_3 or -COO-D_3 via hydrocarbon (
D_3 represents a hydrogen atom or a hydrocarbon group which may be substituted. (2) The electrostatic photograph according to item (1), wherein the repeating unit represented by the general formula (II) of the oligomer (B) contains at least a repeating unit represented by the following general formula (IIa). liquid developer. General formula (IIa) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In formula (IIa), e_1, e_2, and E_1 represent the same symbols as in formula (II). G_2 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B_1 and B_2 may be the same or different from each other,
-O-, -CO-, -CO_2-, -OCO-, -SO
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (D_5 represents the same content as D_1 in formula (II)). W_1 and W_2 may be the same or different from each other,
Represents a hydrocarbon group having 1 to 18 carbon atoms, which may be substituted or have a ▲ mathematical formula, chemical formula, table, etc. ▼ interposed in the main chain bond, where B_3 and B_4 are mutually They may be the same or different and have the same content as B_1 and B_2 above, and W_3 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. m, n and p each independently represent an integer of 0 to 3. However, both do not become 0 at the same time.