JPH03113466A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To enhance dispersion stability, redispersibility, and fixability by heat polymerizing a dispersion stabilizing resin and monomers A and B in a nonaqueous solvent in the presence of a polymerization initiator. CONSTITUTION:The dispersion stabilizing comb-polymer resin is prepared by polymerizing a monofunctional macromonomer M having structural units represented by formula I having a polymerizable double bond group on one end of the polymer chain and a weight average molecular weight of 1X10<3> - 2X10<4> in the nonaqueous solution comprising a nonaqueous solvent, a soluble dispersion-stabilizing resin, the monofunctional monomer A soluble in said solvent but insolubilized by polymerization and the monomer B having one or more polar groups, and the polymerization initiator. In formula I, X0 is -COO- or the like; Q0 is 1 - 22 C aliphatic group or the like; and each of b1 and b2 is H or the like and optionally same or different, thus permitting dispersion stability and redispersibility and fixability to be all enhanced.

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 109 Ωam 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) General electrophotographic liquid developers are petroleum-based organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and 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 hydrocarbon, and further contains a polarity control agent such as a metal soap, lecithin, linseed oil, higher fatty acid, or a polymer containing vinyl pyrrolidone. be.

In such developers, the resin is dispersed as insoluble latex particles in the form of particles with diameters ranging from several nanometers to hundreds of thousands of 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. Therefore, due to long-term storage or repeated use, the soluble dispersion stabilizing resin is detached from the insoluble latex particles, causing the particles to settle, aggregate, or accumulate.
This had the disadvantage 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 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, which makes redispersion difficult, and furthermore causes equipment failure and smearing 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 061 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, the degree of dispersion and redispersion of the particles can be improved by forming insoluble dispersion resin particles of a co-electric material of a monomer to be insolubilized and a monomer containing two or more types of polar components. A method for improving the properties and storage stability is disclosed in Japanese Patent Application Laid-Open No. 62-1518.
It is disclosed in No. 68, etc.

In addition, in the presence of a polymer using a bifunctional monomer or a polymer using a polymer reaction, insoluble dispersed resin particles of a monomer that becomes insolubilized and a coelectric material with a monomer containing two or more types of polar components. A method for improving the dispersity, redispersibility, and storage stability of particles by
No. 62, No. 63-66567, etc.

(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.

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-62-151868 and JP-A No. 62-16636
2, No. 63-66567, the dispersion resin particles produced according to the method disclosed in No. 2, No. 63-66567, can be used when the development speed is increased or when the maintenance period is lengthened.
In terms of particle dispersibility and redispersibility, and in the case of shortened fixing time or in the case of large-sized master plates (for example, A-3 size or larger), rigidity resistance is still not necessarily satisfactory. It wasn't about performance.

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 production of an offset printing original plate having excellent printing ink lubricating properties and printing durability by electrophotography.

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) An object of the present invention is to provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10'Ωcm or more and a dielectric constant of 3.5 or less. The dispersed resin particles contain the following general formula (1) only at one end of the polymer main chain containing at least one polymer component represented by the following general formula (IIa) or (■b). Weight average molecular weight I formed by bonding polymerizable double bond groups represented by XIO' to 2X
A comb-shaped copolymer consisting of at least a monofunctional macromonomer (M) of IO' and a monomer represented by the following general formula (II[) is prepared in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. A monofunctional monomer (A) that is soluble in an aqueous solvent but becomes insolubilized by polymerization, and at least two polar groups and/or polar linking groups represented by the following general formula (IV). This was achieved by a liquid developer for electrophotography, which is characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing at least one of each of the above-mentioned monomers (B). .

General formula N) CH=C ■- In formula (1), ■ is -COQ-, -0CO-, (CHl)
-OCO-1 (CH bar C00-1-〇-1-CONHCOO-2-
CONHCO-1-SOZ-1 History Here, Z represents a hydrogen atom or a hydrocarbon group, and 2 represents an integer from 1 to 3.

al and a2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
Coo-Zg or one coo-z via a hydrocarbon.

(22 represents a hydrogen atom or an optionally substituted hydrocarbon group).

General formula (■a) b, b.

+CH-(IJ- X, -Q.

General formula (Ilb) b+ bz +CH-(J- In formula (I[a) or (IIb), Xo represents the same content as V in formula (1).

Qo represents an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

Hydrogen atom, halogen atom, alkoxy group or C00Zs
(Zs represents an alkyl group, an aralkyl group, or an aryl group).

bl and bt may be the same or different from each other, and are expressed by the formula (1
81 in ) represents the same content as A2.

General formula (I[[)% formula% In formula (Ill), X represents the same content as xo in formula (IIa), and OI represents the same content as 00 in formula (I[a)] d+ and dt may be the same or different, and represent the same content as al and A2 in formula (1).

However, the macromonomer (M) represented by the general formula (l[)
In the monomer component represented by general formula (III), at least one of Qo and Ql represents an aliphatic group having 10 to 22 carbon atoms.

General formula (IV) In general formula (IV), E is -o--coo-2-OCO
-11"CToOCO-1-3O,--CONll-1-3OJ
H--CONl" or -3O,N-(R, is a hydrocarbon group or the general formula (T
Bonding group in V): +AT-BI)r- (represents the same content as -At-829-R).

R is a hydrogen atom or a halogen atom, -0R1-CN,
-Nil! , -COOH, -5O3H or ~POz
Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with Ht.

8, and Bg may be the same or different, and each is -0-1-S--CO-1-COz--0CO--5o
1 or -NICONH- (pg indicates the same content as R above).

A+ and A2 may be the same or different from each other, and CBS and B, which may be interposed in the bond of the main chain, may be the same or different from each other and have the same content as B+ and Bg above, and A4 represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, and R1 has the same content as R above] represents a hydrocarbon group having 1 to 18 carbon atoms.

C5 and eg may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -COO-124 or -Coo-Ra via a hydrocarbon (R4 is a hydrogen atom or an optionally substituted hydrocarbon group) ).

m, n and p may be the same or different, and each is 0 to 4
represents an integer of , provided that m, n, and p are never O at the same time.

The resin for dispersion stabilization of the comb-shaped copolymer provided in the present invention is as follows:
Its weight average molecular weight is 2 x 104 to 2 x 104,
-PO*tltM, (zo represents -Z+e group or -02, group, zl) at one end of the polymer main chain.

is a hydrocarbon group), a formyl group, and an amino group.

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

The carrier liquid having an electrical resistance of 10" Ω or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon; Halogen substitutes can be used, such as octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isopar E1
Isopar G1 Isopar H, Isopar t (Isopar; trade name of Exxon), Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Co.)
, Amsco OMS, Amsco 460 t9 agent (Amsco; trade name of Spirits Inc.), etc. are used alone or in combination.

Non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are dispersed in a non-aqueous solvent in the presence of the dispersion stabilizing resin, which is the comb-shaped copolymer described above. , produced by polymerization and granulation by copolymerizing a monofunctional monomer (A) and a monomer (B) containing a small number (two or more) of polar groups and/or polar linking groups. It is.

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, Isopar E1 Isopar G2 Isopar H, Isopart 1 Schiersolf 0. Cielzol 71, Amsco OMS, Amsco 4601 agent, 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 (For example, methylene dichloride, chloroform, carbon tetrachloride, 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 satisfies the condition of 109Ωc11 or more.

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

This book is used to make a stable resin dispersion of a solvent-insoluble copolymer produced by copolymerizing a -functional monomer (A) and a monomer (B) in a non-aqueous solvent. The dispersion stabilizing resin of the invention has a -functional macromonomer (M) and a general formula (III
) is a comb-shaped copolymer polymerized containing at least one kind of each of the monomers represented by the following formulas, and is characterized by being soluble in the non-aqueous solvent. More preferably, it is a comb-shaped copolymer in which the above-mentioned specific polar group is bonded to one end of the polymer main chain of the comb-shaped copolymer.

The weight average molecular weight of the comb copolymer is 2×104 to 2×
104, preferably 3X10' to lXl0', if the zero weight average molecular weight is less than 2x104 or more than 2x104, the average particle size of the resin particles obtained by polymerization granulation becomes coarse. Alternatively, the particle size distribution becomes wide, impairing monodispersity, or even forming an aggregate rather than a dispersion.

The proportion of the monofunctional macromonomer (M) as a copolymerization component of the comb-shaped copolymer is 1% to 70% by weight, preferably 5% to 50% by weight. If the proportion is less than 1% by weight, the number of comb parts will be significantly reduced, resulting in a chemical structure similar to that of conventional random copolymers, and the improvement in redispersibility, which is the effect of the present invention, will not be observed. On the other hand, if the proportion exceeds 70% by weight, copolymerizability with the monomer represented by general formula (III) becomes insufficient.

Further, the proportion of the monomer represented by the general formula (III), which is another copolymerization component, in the comb-shaped copolymer is 30
~99% by weight, preferably 50-95% by weight.

On the other hand, the macromonomer (M) of the present invention that forms the comb portion of the comb copolymer has a weight average molecular weight of lX10' to
2×104, preferably 2×104 to lXl0'
When the zero weight average molecular weight is less than lXl0'',
The redispersibility of the obtained dispersed resin particles will be reduced. If it exceeds 2 x 104, the copolymerizability with the monomer represented by the general formula (III) will decrease, and a comb-shaped copolymer will not be obtained.

Since the comb-shaped copolymer of the present invention as described above is soluble in the non-aqueous solvent, it contains a soluble repeating unit in either or both of the polymer main chain portion and the comb portion. For this reason, in the macromonomer (M) component represented by general formula (ff) and the monomer component represented by general formula (III),

and Ql, at least one has 10 carbon atoms
~22 aliphatic groups.

That is, as a repeating unit of the macromonomer (M) which is a comb portion, Oo in the general formula (I[a) has a carbon number of 10
When representing an aliphatic group or an aromatic group less than or equal to the general formula (
In the case of the repeating unit represented by Ub), in the monomer represented by the general formula (I[[) constituting the main chain portion of the polymer, 01 represents an aliphatic group having 10 to 22 carbon atoms, In addition, when Q in the general formula (I
Qo in [a) contains a repeating unit of an aliphatic group having 1θ to 22 carbon atoms.

The contents of the comb-shaped copolymer will be further explained below.

The monofunctional macromonomer (M) is a monomer represented by the -a formula (In) only at one end of the main chain of the polymer consisting of repeating units represented by the general formula (IIa) or (Ilb). The weight average molecular weight formed by bonding a polymerizable double bond group represented by general formula (1) that can be copolymerized with
×104 macromonomer.

In general formula (1) and (IIa), (Ilb), a+
x ass VSbt, b! , Xo, Q, and Q each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted.

In formula (1), 2° in the substituent represented by ■ is a hydrogen atom, and preferred hydrocarbon groups include 1 to 1 carbon atoms.
22 optionally substituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group) , 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (e.g., 2-methyl-1-propenyl group, 2-butenyl group,
2-pentenyl group, 3-methyl-2-pentenyl group, l
-Pentenyl L 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7-
12 optionally substituted aralkyl groups (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-cyclohexylethyl group, 2-cyclopentylethyl group, etc.)
, or an optionally substituted aromatic group having 6 to 12 carbon atoms (
For example, 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. group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
acetamidophenyl group, propioamidophenyl group,
dobcyroylamidophenyl group, etc.).

It may have a substituent. As a substituent, a halogen atom (
Examples include chlorine atom, bromine atom, etc.), alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.).

a and ag 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-zz or -CIIzCOOZz (Zl 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 z1 above.

In formulas (IIa) and (■b), xo has the same meaning as ■ in formula (1), bl and bt may be the same or different from each other, and 81 or a! in formula (1) above! is synonymous with

0° preferably represents an aliphatic group having 1 to 22 carbon atoms,
Specifically, it represents the same content as the alkyl group explained for Zl above.

When Y is an alkoxy group, the alkyl residue is:
Specifically, the same examples as those shown in Q0 above can be mentioned. Further, z3 represents an alkyl group, an aralkyl group, or an aryl group, specifically, the above-mentioned group. Examples similar to those shown in .

Preferred ranges of Xo, b, and bt are the above-mentioned V, a+, and a!, respectively. The content is similar to that explained in .

a and a2 of formula (1) or formula (I[a), (I[b
), it is more preferable that either one of bl and b2 is a hydrogen atom.

The repeating unit of the macromonomer (M) of the present invention is a combination of at least one unit represented by the general formula (IIa) or (Ilb), and specific examples are given below. However, the scope of the present invention is not limited thereto.

In the following, Ql: pHtp- (p: integer from 1 to 18) or b:H or CH Tsu L: An integer from 2 to 12 11a.

H or Crthr++ (r: an integer from 1 to B).

(A) →CL F COOQ” (A) −(C1l−CH−)− C0QQ” (A) =6Hz cl+)− COOΩ1 CN C00Q” Coo (CHztrX j−Of+, −OH2(Rゝnee Cr1l□1. 1),
C.I.

-Br.

or -CN COOQ"GOlillR" (A)-10b b The macromonomer (M) provided in the present invention contains at least one repeating unit represented by the general formula (IIa) or (nb) as described above. Formula 0, which has a chemical structure in which the polymerizable double bond group represented by general formula (1) is directly bonded to only one end of the polymer main chain, or is bonded by an arbitrary linking group. (1) Components and formula (II
The group connecting the components a) or (Ilb) is carbon-
Carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and atomic groups of hetero atom-hetero atom bonds. It can be composed of any combination.

Among the macromonomers (M) of the present invention, preferred are those represented by formula (V).

Formula (V) In the formula, al, a2, b2, b, and ■ each represent the formula (1)
, represents the same content as explained in formulas (Ha) and (Ilb).

T represents 1X@-'Q@ represented by the general formula (lla) or 10 represented by the general formula (Ilb), each represented by the formula (II
a) represents the same content as explained in formula (I[b).

, is a simple bond or -(C)-(L, Z, is water, hydrogen atom, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), lower alkyl group (e.g., methyl group,
propyl group, etc.), cyano group, hydroxyl O--3--C
--N--COO-1-50! -1-CON-2 represents a single linking group or a linking group composed of any combination selected from atomic groups such as hydrogen atom, hydrocarbon group having the same content as z1 above], etc.

The general formula (1), (Ha), (Ilb) or (V
), xo, Y, V, an, a2, b8, b
For each of 2, particularly preferred examples are shown below.

As Xo, -COO--0CO--0--CH*CO
O- or -cthoco-, Y has 18 carbon atoms
The following alkyl groups or alkenyl groups are all of the above (however, 2. is a hydrogen atom),
Examples of a3, ats l1ls b2 include a hydrogen atom or a methyl group.

Below, in the general formula (V), V-dore represented by CIl・C Specific examples of groups are shown below.

However, within the present invention The content is not limited to these.

In the following, an integer from 1 to 12, nl: an integer from 2 to 12, or C1h represents.

(B)-1 CH! =C C00(C1lz-)TrS (B) Cl1t=C Coo (CHxh-rOCO(CHth S-(B
) C) I! =C CONH(CHalTS- (B)-5 CIl□2C C00C1hC1lCHzOOC(CHr)rrSH (B) CHt,C C00(C1l□ NHCO(CI(z?; 了5-(B)
)-9 CH,,C coo(CHzhgoNHCOO(CB Z)TT 5(
B)-10 H1G Coo(CHz)m汀NHCONH(CHzhiS-(
B)-13 CH,=C C0NIICOO(CIl□h105 (B)-16 CHt=C L N (B)47 cuz=c CH3 COOCHzCIICtl□OCO(CH Tsuji1C0■ N N (B)-19 CL= C CONHCOO(CHt)rrS- (B)-20 CHt C1l-OCO(Cl□h怀S HI (B)-21 CII = CH Coo (CHz+-j-rs CH.

(B) CH2CHCOOCHzCHCHtOOC(CHt+-rrSCI
.

(B) -23 CH=CH CHt H N (B) C1lt=CII-CHzOCO(CHth-TsCI
(3 (B)-27 CIIz=CI-CHzCOO(CHz+-fTCN CHl COOCFIzGHz COOCOOCHt) The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, by ■ anionic polymerization or cationic polymerization. A method using an ionic polymerization method in which various reagents are reacted at the ends of the resulting living polymer to form a macromer; (2) a polymerization initiator containing a reactive group such as a carboxyl group, a hydroxyl group, or an amino group in the molecule; and/or Alternatively, using a chain transfer agent, a radical polymerization method in which various reagents are reacted with an oligomer with a terminal reactive group bond obtained by radical polymerization to form a macromer; ■ Obtained by polyaddition or polycondensation reaction Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer in the same manner as the above-mentioned radical polymerization method.

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

Encycle, l'olym, Sci, Eng,
+7+551 (1987), p.

F; Rempp l E, Franta;
Adv, Po1y-, Sci, +58°1
(1984), V. Percec+ Appl.
Po1ya, Set,, 2f3iL95 (19
84), R, Asami, M, ↑aka
Ri, Makvamol.

Chew, 5upp1. , JJ, 163 (19
85), P, Re5pp+ etal, Makva
mol, Chew, 5upp+, 8. 3
(1984), Yuji Yogami, Chemical Industry, Tsuchi, 56 (
19B? ), Yuya Yamashita.

Polymers, ], 988 (1982), Shibe Kobayashi, Polymers, Separate.

625 (1981), Toshinobu Higashimura 1 Journal of Japan Adhesive Association,
18.536 (1982), Hiroshi Ito-1 Polymer Processing, ■
, 262 (1986), Shibe Tosan, Takashi Tsuda 5 Functional Materials, 1987. It can be synthesized according to the methods described in reviews such as Nl1I0.5 and the literature and patents cited therein.

Next, the monomer represented by the general formula (1), which becomes a copolymerization component of the comb-shaped copolymer together with the above-mentioned macromonomer (M), will be explained.

In formula (I[l), X represents the same content as x in formula (IIa), preferably -coo--oco
-I can do it.

Ql represents the same content as Q in formula (IIa), preferably represents an aliphatic group having 1 to 22 carbon atoms, specifically, the same as the aliphatic group 21 of formula (1) above. represents the content of

dl and d may be the same or different, and specifically represent the same content as al, , ai in formula (1).

Preferably, either d6 or d represents a hydrogen atom.

In the comb-shaped copolymer, the general formula (
Along with the monomer shown in III), other monomers that can be copolymerized with this monomer may also be contained.

For example, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, chlorostyrene, bromostyrene, vinylnaphthalene, heterocyclic compounds containing polymerizable double bond groups (e.g. vinylpyridine,
vinylimidacillin, vinylthiophene, vinyldioxane, vinylpyrrolidone, etc.), unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc.), itaconic anhydride, maleic anhydride, etc. Can be mentioned.

Any monomer other than these general formula (m) may be used as long as it is a copolymerizable monomer, but preferably the proportion of these other monomers in the total polymerization component of the comb-shaped copolymer is is preferably 30% or less.

Furthermore, the comb-shaped copolymer of the present invention may have the following specific polar group bonded only to one end of the polymer main chain.

That is, -POJz group, -50311 group, -COOH group,
−〇! One group indicates a group, Z,. indicates a hydrocarbon group),
It is a polar group selected from formyl group and amino group.

Among the polar groups, in the -pz group, Zo is a -Z1° group or H OZl. Indicates the group zl. preferably represents a hydrocarbon group having 1 to 1 carbon atoms. zl. More 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,
pentyl group, hexyl group, butenyl group, pentenyl group,
hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, hensyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), or optionally substituted aromatic groups (e.g. phenyl group) , tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In the polar group of the present invention, the amino group -NH, independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, specifically, , represents the same content as the hydrocarbon group of Zl described above.

Even more preferably, Z. , zlI and Z1! 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 comb-shaped copolymer component and the polar group includes a carbon-carbon bond (-poly bond or double bond),
It is composed of any combination of atomic groups of carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and heteroatom-heteroatom bonds.

Among the comb-shaped copolymers of the present invention in which a specific polar group is bonded to one end of the polymer main chain, preferred are those shown by formula (Via) or formula (Vlb).

Formula (Vla) Formula (Vlb) ■ Wd to I+- to set (Va) and (vb), al, ats bus b
l, d, Sd, SX, , Ql, ■, -1, and T represent the same content as each symbol in formulas (1) to (I[I) and (■).

U represents the aforementioned polar group bonded to one end of the comb-shaped copolymer.

6 represents a simple bond or a group connecting the specific polar group U and the main chain portion of the polymer, and specifically represents the same content as explained for Hl.

As mentioned above, in the case of a comb-shaped copolymer in which a specific polar group is bonded to the end of the polymer main chain, phosphono groups, carboxyl groups, sulfo groups, hydroxyl groups, formyl groups are present in the polymer main chain. A valve type H containing a polar group such as a group, an amino group, a mercapto group, or a -P-ZO group is preferably one that does not contain a gold component.

In order to produce comb-shaped copolymers in which a specific polar group is bonded only to one end of the polymer main chain, various reagents are added to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. A method of reacting (method using ionic polymerization method), a method of radical polymerization using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (method using radical polymerization method), or It can be easily produced by a synthetic method such as a method in which a polymer containing a terminal reactive group obtained by an ionic 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, Q
uirk+Encyc1. Polysi, Sc
i, Eng,, 7. 551 (1987)
, Yoshiki Chujo, Yuya Yamashita, “Dye and Medicine J, 30.
232 (1985), Akira Ueda, Susumu Nagai, “Science and Industry”
, starvation.

57 (1986) and the literature cited therein.

As a polymerization initiator containing a specific polar group in the molecule described above, for example, 4.4゛-azobis(4-cyanovaleric acid)
, 4,4'-azobis(4-cyanovaleric acid chloride)
, 2.2″-azobis(2-cyatuburobanol), 2
．． 2'-azobis(2-cyanopentanol), 2,
2°-azobis(2-methyl-N-(2-hydroxyethyl)-propioamide), 2.2″-azobis(2
-Methyl-N-(1,1-bis(hydroxymethyl)ethyl]propioamide), 2.2°-Azobis(2-methyl-N-(1,1-bis(hydroxymethyl)ethyl)-2-
Hydroxyethyl]propioamide! 2.2'-azobis(2-(5-methyl2-imidacylin-2-yl)propane), 2'-azobis(2-(4,5,6,7
-tetrahydroIH-1,3-diazepin-2-yl)propane), 2,2'-azobis(2-(3,4゜5
．． 6-tetrahydropyrimidin-2-yl)propane)
, 2.2°-azobis(2-(5-hydroxy-3,4
, 5,6-tetrapyrimidin-2-yl)propane),
2.2°-Azobis(2(1-(2-hydroxyethyl)-2-imidacillin-2-yl)propane), 2.2
' -azobis(N-(2-hydroxyethyl)-2-
Examples include azobis-based compounds such as methyl-propionamidine) and 2,2°-azobis(N-(4-aminophenyl)-2-methylpropionamidine).

Further, as a chain transfer agent containing a specific polar group in the molecule, for example, a mercapto compound containing the polar group or a substituent that can be derived from the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2- Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N (2-mercaptopropionyl) glycine,
2-mercaptonicotinic acid, 3-(N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-(N-(
2-Mercaptoethyl)aminocopropionic acid, N-(
3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1mercapto-2-propatol , 3-mercapto-
2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 0.5 to 5 parts by weight.

In the comb-shaped copolymer of the present invention having a polar group bonded to one end of the polymer main chain, preferred is the general formula (Vla
) or (Vlb), in which u
Further specific examples of the portion represented by -6- are shown below. However, the scope of the present invention is not limited thereto.

In the following, k: an integer of l or 2, 2: an integer from 2 to 16, k: represents an integer of 1 or 3.

(C) 1100C(Ctl girls (C) HOOC-CH-5 1100cmCH! (C) 1(00C(CHz)ryoooc(C1l□hgo5(C)
) tloOc(CHz)yrNHco(CIlzhry5(
C)-7 HO(C41z)yrS (C)-8 HzN(CHz-h-YS- (C) HOCH-Cn2S- 0CHz HO-P-0(C1l Hough YS CH R-0-P-0(Ctlz) rzs OHR:C.

6 alkyl group 110.3 (CIri ts CHx (C) HOOCfC)11hC N CH.

(C) HO(C1h)ryC N CHx (C)-19 HO(CHz)rrOOC(CHzhC-N L (C) HooC(CHx)rrcOo(CIIa1]GN Ctl3 0■ N CH3 (C)-23 R-NHCO -C L HtOH R: HOofCtlz)y, 113C-C-C11,0
)I R'Z; (CHz)y.

(GHz) r - CH2CIICHa R゛; l1l -CIIzCHzOtl CI1゜ (R+; ■.

-NHt.

01l) CHt(C)-26 0IIC(CHthe M(C)-29 HOOC(CHz)tNH(CHt)yrs(C)-3
0 HOOC+GHz)rrcONH(C1h)yrS The monomers used in producing the non-aqueous dispersion resin include a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and A monomer (B
) can be distinguished.

The monomer (A) in the present invention may be any monofunctional monomer that is soluble in non-aqueous solvents but becomes insolubilized by polymerization.
) are mentioned.

General formula (■) α-β In general formula (■), α is -COO-1-OCO-1-CI
l! Represents 0CO-1.

Here, R2 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group). 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-methoxypropyl group, etc.).

β 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, 2゜2-dichloroethyl group, 2,2 .2-) Lifluoroethyl 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, 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-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

r+ and f! may be the same or different, and each represents the same content as al or R2 in the general formula (1).

Specific examples of the Ichinomiya functional monomer (A) include vinyl esters or allyls of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.). Esters; optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (as an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2hydroxyethyl group,
2-cyanoethyl group, 2nitroethyl 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, bromo Styrene, 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; Acrylonitrile; Methacrylunitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, the Society of Polymer Science and Technology, "Polymer Data Handbook - Group W Edition - J% p175-184, Baifukan ( (published in 1986), such as N-vinylpyridine, N
-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxaprine, vinylthiazole, N-vinylmorpholine, etc.)
etc.

- Two or more functional monomers (A) may be used in combination.

Next, the monomer (B) represented by the general formula (Tt/) used in the present invention will be further explained.

In general formula (IV), preferably E is 10-1-C
OO--0CO--CI(tOCO-1-CONII-
or -CON [preferably an optionally substituted alkyl group having a total of 1 to 16 carbon atoms, an optionally substituted alkenyl group having a total of 2 to 16 carbon atoms, an optionally substituted fatty acid having a total of 5 to 18 carbon atoms; Cyclic group or bonding group in general formula (IV): +^, -
B, ÷ represents the same content as ÷A, -B, →=ll.

R is preferably a hydrogen atom, a halogen atom (eg, a chloro atom, a bromo atom, etc.), -0HS-CN.

It represents an aliphatic group having a total of 1 to 16 carbon atoms (the aliphatic group is, for example, an alkyl group, an alkenyl group, or an aralkyl group) which may be substituted with COOH.

B and B2 may be the same or different, preferably -0-1-S--CO-1-coo--oc.

Rz Rz CON- or -NGO- (R1 each indicates the same content as R above).

A and 80 may be the same or different from each other, and preferably, they may be substituted, or CH- may be interposed in the bond of the main chain to form B "tAa Bah-R3, which has 1 to 12 carbon atoms. represents a hydrocarbon group (the hydrocarbon group is an alkylene group, alkenylene group, arylene group, or cycloalkylene group).

However, B1 and B4 may be the same or different, and the above B1,
The same contents as B2 are shown, A4 preferably represents an optionally substituted alkylene group, alkenylene group or arylene group having 1 to 12 carbon atoms, and R3 has the same contents as the above R.

C3 and C) may be the same or different from each other, and are preferably a hydrogen atom, a methyl group, -Coo-R4 or -C)1
□Coo-R4 (R4 is preferably a hydrogen atom, carbon number 1
-18 alkyl group, alkenyl group, aralkyl group or cycloalkyl group).

Furthermore, m, n and p may each be the same or different,
Preferably, it represents a number of 0.1.2.3. However, m,
n and p never become 0 at the same time.

Furthermore, more preferably in formula (TV), E is -COO-1
represents -CONH- or -CON-, and e and B2 may be the same or different and represent a hydrogen atom, a methyl group, -CO
O-R.

or -GHzCOO-Ra (Ra more preferably represents an alkyl group having 1 to 12 carbon atoms).

Furthermore, regarding AI and 8:, specific examples include a group, a halogen atom, etc.), -(CII=C)l)
-1 and p have the same meanings as the above symbols).

Further, in the bonding group in general formula (IV): E+A+ 8+→1-←Ax Bt-+-R, from E to R (i.e., E, At, B1, At, Bz
and R) is preferably composed of a total number of atoms of 8 or more, where -+ A r
-B + -)f-(-A z -B rh-R, the connecting main chain composed of R is also included in the connecting main chain. Furthermore, AI and At have -CH- as the main chain. Chain B, −←
＾B3+A in the case of a hydrocarbon group interposed in the bond of -84□R1
aBnh-Rs is also included in the linking backbone. As for the number of atoms in the connecting main chain, for example, E is -COO- or -
When CONH- is represented, an oxo group (=0 group) and a hydrogen atom are not included in the number of atoms, but carbon atoms, ether type oxygen atoms, and nitrogen atoms that constitute the connecting main chain are included in the number of atoms. Therefore, -000 and -CON)l- have 2 atoms.
It is counted as. Similarly, for example, when R represents -CJ+q, hydrogen atoms are not included in the number of atoms, but carbon atoms are included.

Therefore, in this case, the number of atoms is counted as 9.

Monomer (B) teeth, More specifically, The following compound Examples include things.

(■ CH.

CH Yi=! =C COOC00(Cut)zOcOc+v(N CHl ■ CH,=(: Coo (CHt) 10cOc+ +Ls (IV-3) CH.

CHt-C? Coo (CIlz)! OCO(CHt) 5OcO
clh(IV-4) CI.

CH1=C COO(CIlz) l1lOCOC&H13(IV-
5) CHt CIl□=C COCoo(CH+.C00CIHI?(IV-6) (rV-7) CH[÷C ■ C0NH(CHz) acOOcsH+ 7(IV-8
) C11゜CHt-c 嘗COO(CIlz)JHCO(CHz)scOOcII
s(■ ■ CH2 Coo (CHz) *0COCII=CI-COOC
6111s(■ CH3 ■ CI, =C C00CII□CHCHzOCOCsH+ 1OCOC
sH+ + (IV-11) CH3 cut=c COOCHtC) ICHzOCOCall+3OCOC
! H7 (■ CH8 C1,=C C0NCl1zCHzOCOCsH++CHz(JhO
COCstl+ I (IV-13) 1h (IV-14) CH3 CH=CH COO(CIlz) r. 0COC3H (IV-15) CII.

CH,=CCH.

■ C0NHCCHiOCOCaH* CHzOCOCJ* coz=c COO(CHi)ioco(C1h)3COOCHIC
H2CZCIl,=CH0CO(CI+□),. 0COCdb (IV-18) CH.

CIl=C C00CHzCHtCIIOCOCsl(++0COC
sH+ + (■-19) CH.

CH a=C C00CIhCHz(jl□Cll0COC6H+ 5
OCOC&+1+3 (IV-20) CHi coz=c C00CHiCHOCOCsll.

0COCHzCHzCOOCJ7 (IV-21) CH.

(IV-22) C.I.

CH,=C C00CIIzC1lCLOOCCIl□CHzCOO
Call*0COC3H? (rV-23) CH3 ct+t=c COOCHxCHzCHCHzOCOCaHwoooCC
H-OCOCJy CHg-OCOCztl? (■ CH3 OC0C6H+3 (IV-25) (IV-26) CHt-CHCH port OCO (CHt)zcOOcIhc
HcHgOcOcJq0COCJ* (IV-27) CH3 (IV-28) COOCToCHtNHCOOCnHv (■ The dispersion resin of the present invention consists of at least one type each of monomer (A) and monomer (B), and the important thing is that If the resin synthesized from these monomers is insoluble in the nonaqueous solvent,
A desired dispersed resin can be obtained. More specifically,
It is preferable to use the monomer (B) represented by the general formula (IV) in an amount of 0.1 to 10 percent, more preferably 0.2 to 8 percent, based on the monomer (A) to be insolubilized. %. Further, the molecular weight of the dispersion resin of the present invention is preferably 103 to 1.
0', more preferably 10' to 10''.

In order to produce the dispersion resin (latex particles) used in the present invention, generally, the above-mentioned dispersion stabilizing resin, monomer (A) and monomer (B) are mixed in a non-aqueous solvent and subjected to filtration. The polymerization may be carried out by heating in the presence of a polymerization initiator such as benzoyl oxide, azobisisobutyronitrile, or butyllithium.

Specifically, (1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, monomer (A), and monomer (B), (2)
A method in which monomer (A) and monomer (B) are dropped together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved; A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing a part of the mixture of monomers (B),
Furthermore, there are methods such as (1) optionally adding a mixed solution of a dispersion stabilizing resin and a monomer together with a polymerization initiator to a non-aqueous solvent, and any method can be used for production.

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

The amount of the soluble resin as a dispersion stabilizer is 1 to 100 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total monomers used above.

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 the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the nonaqueous solvent used in the reaction, or when the monomer (A) or monomer (B) to be polymerized and granulated is ) If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than its boiling point or distilling it off, or by distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, especially after repeated use over a long period of time in a developing device. It has good dispersibility and is easy to redisperse even when the development 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 has excellent dispersion stability, redispersibility, and fixing properties even when the development and fixation process is accelerated and the maintenance interval is extended for a long time.

In the liquid developer of the present invention, a colorant may be used if desired, but the colorant is not particularly limited.
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. As described above, there is a method of producing a copolymer containing a dye 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.

If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, capri will likely occur in non-image areas.

Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and the amount is 0.5 parts by weight per 1000 parts by weight of the carrier liquid.
Approximately 100 parts by weight can be added.

The charge control agent as described above is preferably used in an amount of 0.001 parts by weight to 160 parts by weight based on 1000 parts by weight of the carrier liquid. Furthermore, 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 Ωcm, 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 manufacturing the dispersion stabilizing resin, manufacturing examples of latex particles, and examples of the present invention are illustrated below, but the present invention is not limited thereto.

A mixed solution of 100 g of Maromomer's methyl methacrylate, 5 g of mercabutoprobionic acid, and 200 g of toluene was heated to a temperature of 75 "C while stirring under a nitrogen stream. 2.2" Azobisisobutyronitrile (abbreviation ^, lB, N,) 1.
0g was added and reacted for 4 hours, and then A, 1. B, N, 0.5
Then, 0.3 g of A, 1B, and N were added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to this reaction solution.
and 0.5 g of t-butylhydroquinone, and the temperature was 1.
The reaction solution was stirred at 00''C for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2I! to obtain 82 g of white powder. The weight average molecular weight of the 0 polymer was 6,500.

Macromonomer M-1: CH3 OHC00CHs Macromonomer 2 to 27: M-2 to M-27 In Production Example 1 of Macromonomer, only methacrylate was replaced with a compound corresponding to Table 1 below.
React in the same manner as macromonomers M-2 to M-27
was synthesized. The weight average molecular weight of each macromonomer obtained was in the range of 5,000 to 7,000.

Table-1 C11゜Table-1 (continued 1) Table 1 (continued 2) Macromonomer ゛1h28: A mixed solution of 90 g of M-28 dodecyl methacrylate, 10 g of methacrylic acid, 5 g of thioethanol, and 200 g of toluene was stirred under a nitrogen stream. At the same time, the temperature was increased to 70'C. A.1. B
, N, as 1. Og was added and the mixture was reacted for 4 hours.

Furthermore, 0.5g of ^, r, B, and N were added for 3 hours, and then A, 1. 0.3g of B and N were added and reacted for 3 hours. This reaction solution was cooled to room temperature, 18.2 g of 2-carboxyethyl methacrylate was added, and to this was added 24 g of dicyclohexylcarbodiimide (abbreviated as C, C).
A mixed solution of 150 g of methylene chloride was added dropwise over 1 hour.

Add 1.0 g of t-butylhydroquinone and leave as is for 4
Stir for hours.

The filtrate obtained by filtering off the precipitated crystals was reprecipitated into methanol 21. The precipitated oil was collected by decantation, dissolved in 150 d of methylene chloride, and re-precipitated in 11 d of methanol. The oil was collected and dried under reduced pressure to yield 54 g of a polymer having a weight average molecular weight of 5,800.

Macromonomer M-28: CH.

In the production example of macromonomer M = 28, the methacrylate monomer = (corresponding to dodecyl methacrylate) and the unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) were changed, and in the same manner as in the production example of M2S,
Each of the macromonomers shown in Table 2 below was produced. The weight average molecular weight of each macromonomer obtained is 5ooo to 700.
It was 0.

Table 2 (continued) Macromonomer 36:M-36n-dodecyl methacrylate 70g, t-butyl methacrylate 3
A mixed solution of 0 g, 4 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran was heated at a temperature of 70 g under a nitrogen stream.
Warmed to ℃. A.1. B, N, 1. Og was added and reacted for 4 hours, and then A, 1. 0.5g of B and N were added and reacted for 4 hours.Next, this reaction solution was cooled in a water bath to a temperature of 2.
The temperature was adjusted to 0'C, 6.5g of triethylamine was added, and 5.6g of acrylic acid chloride was added dropwise with stirring at a temperature of 25°C or lower.After 0 dropwise addition, the mixture was further stirred for 1 hour. Then, add 0.5g of t-butylhydroquinone and heat to 60°.
C. and stirred for 4 hours. After cooling, methanol 21
The reprecipitation operation was performed twice to obtain 63 g of a pale yellow viscous substance with a zero weight average molecular weight of 6.600.

Macromonomer M-3El COOC+gHts COOC4■, (t) Macromonomer 37: A mixed solution of 100g of M-37 octadecyl methacrylate, 150g of tetrahydrofuran and 50g of isopropyl alcohol was heated to 75°C under a nitrogen stream.

4.4'-7zohis (4-cyanovaleric acid) (abbreviation: A
, C, V, ) was added and reacted for 5 hours.
C, V, 1. Og was added and the mixture was reacted for 4 hours. After cooling, the reaction solution was reprecipitated into 1.5 mL of methanol, and the oil was collected by decantation and dried under reduced pressure. Yield was 85g.

50 g of the obtained oil (oligomer), 15 g of glycidyl methacrylate, 1.0 g of SN,N-dimethyldodecylamine, and 1.0 g of 2,2'-methylenebis(6-1-butyl-p-cresol). In addition, temperature 100
Stirred at °C for 15 hours. After cooling, this reaction solution was reprecipitated into 1 l of petroleum ether to obtain 42 g of a white powder with a zero weight average molecular weight of 7,500.

Macromonomer M-37: OHCN C00C+Jat macromonomer 38: M-38 In production example 37 of macromonomer, 50g of the intermediate oligomer obtained, 2-
Add O, C, C to a mixed solution of 2.8 g of hydroxyethyl methacrylate and 100 g of methylene chloride at room temperature while stirring.
,4. A mixed solution of Og, 0.5 g of 4-dimethylaminopyridine and 10 g of methylene chloride was added dropwise over 1 hour.

The mixture was stirred for an additional 4 hours. Separate the precipitated crystals by filtration,
The filtrate was reprecipitated twice in methanol,
The obtained powder was dried under reduced pressure. The yield was 43 g, and the weight average molecular weight was 7,300.

Macromonomer M-38: C11゜CN C00C+*Hit t:pt octadecyl methacrylate) 80g, Macromonomer M
A mixed solution of 20 g of -1 and 150 g of toluene was heated to 75°C while stirring under a nitrogen stream.

A, C, V, 1. Add Og and react for 4 hours.
, V, and added 0.3 g for 2 hours.
3g was added and reacted for 3 hours. After cooling, it was reprecipitated into methanol 21, and after collection by filtration, the obtained white powder was dried to obtain 76 g of powder having a weight average molecular weight of 4.8 XIO'.

Dispersion stabilizing resin P-1= CN　　　　C00C++1ht CH.

In Production Example 1 of P-1, each dispersion stabilizing resin was produced by reacting in the same manner as in Production Example 1, except that octadecyl methacrylate and macromonomer M-1 were replaced with the compounds shown in Table 3 below. Weight average molecular weight of each resin: 3.5
10'~5. It was OX 10'.

16:P-16 70g of octadecyl methacrylate, macromonomer M
30g of -10, 0.8g of thiomalic acid, 10g of toluene
A mixed solution of 0g and 50g of isopropyl alcohol,
It was heated to a temperature of 80°C under a nitrogen stream. 1.1'Azobis(cyclohexane-1-lupodianide) (abbreviation: ^,
Add 0.8g of B, C, C,) and react for 4 hours, and then add A,
Add 0.4g of B, C, and C for 3 hours, then add A, B, and C.
, C, was added and reacted for 4 hours. After cooling, it is reprecipitated in methanol 22, collected by filtration, and dried to give a white powder 78
I got g. The weight average molecular weight was 3.8 x 10'.

Dispersion stabilizing resin p-+6: CH3Cuff HOOC-CHg C00C+eHxt
*0■ ooc 811 engineering i's 17~25:P-17~P-25P-16
In Production Example 1, octadecyl methacrylate, macromonomer M-10, and mercapto compound (thiomalic acid) were each replaced with compounds corresponding to Table 4 below, and the reaction was carried out in the same manner as in Production Example 16 to produce each resin P-17 to P-25 was manufactured. The weight average molecular weight of each resin is 3. OX 10'
It was ~4X10'.

No. 26 to 31: P-26 to P-31 In Production Example 1, the procedure was repeated in the same manner as in Production Example 1, except that the azobis compounds shown in Table 5 below were used instead of the polymer initiators ^, C, and V. Each resin was manufactured using the following methods.

The weight average molecular weight of each resin obtained was 3. OX 10'~
It was 6 x 10'.

Table-5 R-N-N-RF azobis compound Table-5 (continued) n-dodecyl methacrylate 85g, macromonomer M
A mixed solution of 15 g of -28 and 150 g of toluene was heated to a temperature of 75°C under a nitrogen stream. ^, 1. B, N
, 1.Og was added for 4 hours, and then A, 1. B, N, 0.
5g was added and reacted for 3 hours. Furthermore, A.1. After adding 0.3g of B and N, the mixture was heated to 90°C and reacted for 2 hours. After cooling, the anti-6 product was reprecipitated into methanol 21,
The precipitated viscous material was collected by decantation and dried under reduced pressure.

The yield of a transparent viscous substance was 76 g, and the weight average molecular weight was 4.
It was 3 x 10'.

Dispersion stabilizing resin P-32: C00C+JtsC00C+tHts Cool (33~42:P-33~P-42P-32
In Production Example 32, each resin P-3 was reacted in the same manner as in Production Example 32, except that n-dodecyl methacrylate and macromonomer M-28 were replaced with a mixture corresponding to Table 6 below.
3 to P-42 were manufactured. The weight average molecular weight of each resin is 3
．． It was 5 x 10' to 4.5 x 10'.

-1 x ゛''-1:D-1 16g of dispersion stabilizing resin P-4, 100g of vinyl acetate,
A mixed solution of 1.5 g of compound example rV-19 of monomer (B) and 384 g of Isopar H was heated to a temperature of 70° C. with stirring under a nitrogen stream. 0.8 g of 2.2'-azobis(isovaleronitrile) (abbreviation: ^, lV, 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. Temperature 100″C
The mixture was raised to a high temperature and stirred for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth and was a latex with a polymerization rate of 86% and an average particle size of o, 2o.

--S 1~: In Production Example 1 of D~D latex particles, in place of dispersion stabilizing resin P-4 and monomer (B) compound example ■-19, the compounds listed in Table 7 below were used. Each latex particle was produced in the same manner as in Production Example 1, except that the dispersion stabilizing resin and monomer (B) were used.

The polymerization rate of each particle was 85 to 90%.

Table (continued) 8g of dispersion stabilizing resin P-25 (as solid content), 7g of poly[dodecyl methacrylate], vinyl acetate lon
A mixed solution of 1.5 g of Compound Example IV-15 (monomer (B)) and 380 g of n-decane was heated to 75° C. with stirring under a nitrogen stream. 2゜2'-azobis(isobutyronitrile) (abbreviations: A, 1.B, N,) in 1.
0g was added and reacted for 4 hours, and then A, 1. B, N, 0.
5g was added and reacted for 2 hours. Raise the temperature to 110°C2
The mixture was stirred for hours and the low boiling point solvent and residual vinyl acetate were distilled off. After cooling, it was passed through a 200 mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.204.

24: 14 g of D-24 dispersion stabilizing resin-25, 85 g of vinyl acetate, 2.0 g of compound example ■-23 of monomer (B), 1 N-vinylpyrrolidone
A mixed solution of 5 g and 400 g of isododecane was heated to 65° C. with stirring under a nitrogen stream. A, lB
, N, were added and reacted for 4 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 pm.

25: 14 g of D-25 dispersion stabilizing resin-32, 100 g of vinyl acetate, monomer (B
) 1.5 g of compound example ■-18, 5 g of 4-pentenoic acid
A mixed solution of 383 g of Isopar G and Isopar G was mixed under a nitrogen stream.
While stirring, bring the temperature to 60°C. A.1. V,
N, 1. Og was added and the mixture was reacted for 2 hours.

Furthermore ^, 1. 0.5g of V and N were added and reacted for 2 hours.

After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.25μ.

--S: D- A mixed solution of 20 g of dispersion stabilizing resin P-1, 2 g of compound example ■-16 of monomer (B), 1 g of n-dodecyl mercaptan, 100 g of methyl methacrylate, and 478 g of Isopar H was heated in a nitrogen stream. While stirring, the mixture was heated to 65°C.

A.1. 1.2g of V and N were added and reacted for 4 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 nm.

27: A mixed solution of 20 g of D-27 dispersion stabilizing resin-18, 100 g of styrene, 4 g of monomer (B) compound example ■-25, and 380 g of Isopar H was stirred under a nitrogen stream. It was heated to a temperature of 50°C. An amount of n-butyllithium hexane solution having a solid content of 1.0 g was added and reacted for 4 hours. After cooling 20
The white dispersion obtained through the 0 mesh nylon cloth was a latex with an average particle size of 0.25-.

A mixed solution of 20 g of M-X's 2A polyC octadecyl methacrylate (weight average molecular weight 35,000), 100 g of vinyl acetate, 1.5 g of monomer (B) compound example TV-19, and 380 g of Isopar H was added. A white dispersion of latex particles with a polymerization rate of 88% and an average particle size of 0.23- was obtained by processing in the same manner as in Production Example 1 of Latex Particles except for the use. (corresponding to the latex particles described in JP-A No. 62-151868) 29 B 14 g of dispersion stabilizing resin with the following structure, 100 vinyl acetate
g, processed in the same manner as in Production Example 1 of latex particles except for using a mixed solution of 1.5 g of monomer (B) compound IV-19 and 386 g of Isopar H, with a polymerization rate of 90%,
A white dispersion of latex particles with an average particle size of 0.25 was obtained. (Corresponding to the latex particles described in JP-A-63-66567) Dispersion stabilizing resin> C00C+5Hzt C00(CHx)+. C0
0CH=Ctb (weight composition ratio) Weight average molecular weight 43,000 Example 1 10 g of dodecyl methacrylate-acrylic acid copolymer (copolymerization ratio; 9515 weight ratio), 10 g of nigrosine, and 30 g of Isopar G were placed in a paint shaker with glass beads. (Tokyo YTM! 4TL) 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 dispersion, 0.07 g of octadecene-half-maleic acid octadecylamide copolymer, and higher alcohol F OC-1600 (manufactured by Nissan Chemical ■) 1
An electrostatic photographic liquid developer was prepared by diluting 5 g of Isopar G to 11.

'-A and B Two types of liquid developers A and B for comparison were prepared by replacing the resin dispersion with the following resin dispersion in the production of the liquid developer described above.

・゛　　A Ni Resin dispersion of latex particle production example 28.

6′ B Resin dispersion of latex particle production example 29.

These liquid developers were processed using a fully automatic plate making machine ELP404V (
The electrophotographic photosensitive material ELP Master ■ type (manufactured by Fuji Photo Film ■) was exposed and developed using it as a developer for Fuji Photo Film ■. The plate making speed was 7 plates/min. In addition, 3 types of ELP master ■
After processing 000 sheets, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image is 30%
This was done using the original manuscript. The results are shown in Table-8.

As is clear from the results shown in Table 8, when plates were made using each developer under severe forced plate-making conditions with extremely high plate-making speeds as described above, no staining of the developing device occurred, and 30%
The developer of the present invention was the only developer that produced a clear image on the 00th plate making plate.

On the other hand, offset printing master plates (ELP masters) obtained by plate making using each developer were printed using a conventional method, and the number of prints was compared until the printed image showed missing characters, fading in solid areas, etc. However, in the master plates obtained using the developers of the present invention, Comparative Example A, and Comparative Example B, no problem occurred even after 10,000 sheets or more were produced.

As shown in the above results, only the developer made using the resin particles of the present invention does not cause any staining of the developing device, and
The number of printed master plates was also good.

That is, in the case of Comparative Examples A and B, there was no problem with the number of prints, but the developing device was stained and could not withstand continuous use.

Although the staining of the developing device in Comparative Example B was dramatically improved compared to Comparative Example A, it still did not reach satisfactory performance when the developing conditions were severe.
The known dispersion stabilizing resin of Comparative Example B has a component containing a polymerizable double bond group that copolymerizes with the monomer (A) [vinyl acetate in this example] contained in the polymer.
It is characterized by being a random copolymer in which the polymerizable double bond group is present in a portion close to the polymer main chain, and for this reason, the redispersibility of latex particles is inferior to that of the dispersion stabilizing resin of the present invention. It seems that there is.

Example 2 White resin dispersion 1 obtained in latex particle production example 1
A mixture of 00 g and 1.5 g of Sumikalon Black was heated to 100°C and stirred for 4 hours.

After cooling to room temperature, the remaining dye was removed by passing it through a 200-mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.25 μm.

30g of the above black resin dispersion, 0 zirconium naphthenate
．． 05g, FOC-1600 (made by Nissan Chemical ■) 20g
A liquid developer was prepared by diluting Shersol 71 to 12.

When this was developed using the same device as in Example 1, the result was 300
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 A mixture of 100 g of the white resin dispersion obtained in Production Example 25 of latex particles and 3 g of Victoria Blue B was heated to a temperature of 70'C to 80C and stirred for 6 hours.

After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.25.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05 g of FOC-1400 (manufactured by Nissan Chemical Company, Ltd.) to 11 g of Isopar H.

When this was developed using the same device as in Example 1, the result was 300
Even after developing 0 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.

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 4 Poly(decyl methacrylate) 10g, Isopar 83
0 g 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 3 obtained in latex particle production example 1
0 g, 4.2 g of the above alkali blue dispersion, 15 g of higher alcohol F OC-1400 (manufactured by Nissan Chemical Co., Ltd.), and 0.06 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride were added to lIl of Isopar G. A liquid developer was prepared by diluting it.

When this was developed using the same device as in Example 1, the result was 300
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 5 to 21 In Example 4, latex particles shown in Table 9 were used instead of the white resin dispersion of Production Example 1 of latex particles, and the solid content was changed to 6. A liquid developer was prepared in the same manner as in Example 4 except that the amount of Og was used.

Table-9 Table-9 (Continued) When this was developed using the same device as in Example 1, 300
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.

(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 very high plate-making speeds, the developing device does not become dirty, and maintenance intervals can be extended for a long period of time. The image quality of the printed matter after printing was very clear.

Claims (2)

[Claims] (1) Electrical resistance 10^9Ωcm or more and dielectric constant 3.5
In the electrostatographic liquid developer comprising at least a resin dispersed in the following non-aqueous solvent, the dispersed resin particles contain at least one of the polymer components represented by the following general formula (IIa) or (IIb). A polymer with a weight average molecular weight of 1 x 10^3 to 2
A comb-shaped copolymer consisting of at least a 10^4 monofunctional macromonomer (M) and a monomer represented by the following general formula (III) is prepared in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. A monofunctional monomer (A) that is soluble in an aqueous solvent but becomes insolubilized by polymerization, and at least two polar groups and/or polar linking groups represented by the following general formula (IV). A liquid developer for electrophotography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing at least one of each of the above-mentioned monomers (B). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), V is -COO-, -OCO-, ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -O-, -CONHCOO-, -CONHC
Represents O-, -SO_2-, -CO-, ▲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.▼. Here, Z_1 represents a hydrogen atom or a hydrocarbon group, and l
represents an integer from 1 to 3. a_1 and a_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z_2, or -COO-Z via a hydrocarbon.
_2 (Z_2 represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IIa) or (IIb), X_0 is V in formula (I) represents the same content as . Q_0 is an aliphatic group having 1 to 22 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group. Q represents -CN or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, Y represents a hydrogen atom, a halogen atom, an alkoxy group, or -COOZ_3 (Z_3 represents an alkyl group, an aralkyl group, or an aryl group). b_1 and b_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_1 represents the same content as X_0 in formula (IIa), and Q_1 is the same as Q_0 in formula (IIa). represents the content of d_1 and d_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). However, in the macromonomer (M) component represented by general formula (II) and the monomer component represented by general formula (III),
At least one of Q_0 and Q_1 represents an aliphatic group having 10 to 22 carbon atoms. General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (IV), E is -O-, -COO-, -OCO
-, -CH_2OCO-, -SO_2-, -CONH-
, -SO_2NH-, -CON-, or -SO_2N-
(R_1 is a hydrocarbon group or a bonding group in general formula (IV):
▲Represents the same content as ▼ (including mathematical formulas, chemical formulas, tables, etc.). R is a hydrogen atom or a halogen atom, -OH, -CN,
-NH_2, -COOH, -SO_3H or -PO
_3 Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with H_2. B_1 and B_2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2-, -OC, respectively
Represents O-, -SO_2-, ▲Mathematical formulas, chemical formulas, tables, etc.▼ or -NHCONH- (R_2 indicates the same content as R above). A_1 and A_2 may be the same or different from each other,
Each may be substituted, or ▲a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [B_3, B_4 are
They may be the same or different from each other and have the same content as B_1 and B_2 above, A_4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R_3 has the same content as R above] Represents a hydrocarbon group having 1 to 18 carbon atoms. e_1 and e_2 may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -COO-R_4, or -COO-R_4 via a hydrocarbon (R_4 is a hydrogen atom or an optionally substituted hydrocarbon group) ). m, n and p may be the same or different, and each is 0 to 4
represents an integer. However, m, n, and p do not become 0 at the same time. (2) The dispersion stabilizing resin has -PO_3H_2 groups, -SO_3H groups, -COOH groups at one end of its polymer main chain,
-OH group, -SH group, -P-Z_0 group (here, Z_0
represents -Z_1_■ group or -OZ_1_■ group, Z_1
＿■ indicates a hydrocarbon group), a formyl group, and an amino group with a weight average molecular weight of 2×10
The liquid developer for electrophotography according to item (1), which is a comb-shaped copolymer of ^4 to 2 x 10^5.