JPH0313964A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain a developer having superior dispersion stability, redispersibility and fixability by dispersing nonaq. dispersible resin particles obtd. by copolymerizing a monomer with a specified macromonomer in the presence of a dispersion stabilizing resin in a specified nonaq. solvent. CONSTITUTION:A liq. carrier having >=10<9>OMEGAcm electric resistance and <=3.5 dielectric constant is mixed with a nonaq. solvent and a monomer A is copolymerized with a macromonomer M in the presence of a dispersion stabilizing resin not contg. a graft group polymerizing with the monomer A to disperse nonaq. dispersible resin particles. The monomer A is a monofunctional monomer which is soluble in the nonaq. solvent but is insolubilized by polymn. The macromonomer M is a macromonomer having <=10<4> number average mol. wt. obtd. by bonding a group having a polymerizable double bond, represented by formula II and copolymerizable with the monomer A to only one terminal of the principal chain of a polymer consisting of repeating units represented by formula I. A developer having superior dispersion stability, redispersibility and fixability can be obtd.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10 Ωcat or more and a dielectric constant of 3.5 or less. In particular, it relates to a liquid developer with excellent redispersibility, storage stability, stability, image reproducibility, and fixing properties.

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

In such developers, the resin is dispersed as insoluble latex particles with a diameter of several nanometers to several hundred nanometers, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and an insoluble latex are dispersed. Due to insufficient bonding with the particles, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. Therefore, the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, resulting in the particles settling, agglomerating, or depositing, and the polarity becoming unclear. In addition, since the particles that have aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. This has the disadvantage that redispersion stability is insufficient for practical use, such as solidification, making redispersion difficult, and furthermore causing equipment failure and smudging of copied images. In addition, in the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized. In general, particles with a wide particle size distribution containing a large amount of coarse particles, or polydisperse particles with two or more average particle sizes were formed.

Furthermore, it is difficult to obtain a desired average particle size with monodispersed 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 types of polar components are used. A method for improving the dispersity, redispersibility, and storage stability of particles by
It is disclosed in No. 62-151868 and the like.

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

JP-A-60-179751 and JP-A No. 62-15186
Dispersed resin particles produced according to the method disclosed in No. 8 have advantages in terms of particle dispersibility and redispersibility when development speed is increased, when fixing time is shortened or when large plate size ( For example, in the case of master plates of A-3 size or larger), their performance has not always been satisfactory in terms of printing durability.

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

The purpose of the present invention is to provide a liquid developer that speeds up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in electrophotographic engraving systems that use large-sized master plates. It is to be.

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 fat resistance and stiffness resistance 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) The above aspects of the present invention are an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 104 Ωcm or more and a dielectric constant of 3.5 or less. in the presence of a resin that is soluble in the non-aqueous solvent and does not contain a graft group that polymerizes with the monomer; The monofunctional monomer (A) to be insolubilized and the following -In formula (a polymerizable double bond group represented by the following general formula (II) only at one end of the polymer main chain consisting of a repeating unit represented by N) Copolymer resin particles obtained by polymerizing a solution containing at least one monofunctional macromonomer (M) having a number average molecular weight of 104 or less, each consisting of This was achieved using an electrostatographic liquid developer.

General formula (I) % formula % General formula (It) b+ bi CH=C 1- General formula (I) niite, V, is -0-1-S-1-C
OO-1-OCO--CIIsOCO- or -CHIC
Represents oO-.

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

X and Xt may be the same or different from each other and 1, Y
+ -O--CO-1-CO wealth--oco--so wealth--N
- represents a symbol).

1? , and R, may be the same or different from each other;
a, which may be substituted, or -CH- in the main chain X s (
R4-X a )y Y z bond may be interposed (
XX and X4 may be the same or different from each other, and
1, represents the same symbol as x8, R1 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and Y8 represents the same symbol as Y] A hydrocarbon group having 1 to 18 carbon atoms represent.

als at may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO
-R5 or -Coo-Rs via a hydrocarbon (Rs represents a hydrogen atom or a hydrocarbon group which may be substituted).

m, n and p may be the same or different, and are O~4
represents an integer. However, m+n is at least 1 or more.

In general formula (II), V is -o--coo--
OCO--CIl□0CO-1-CHtCOO-1-s
o, --CONH-1 or --CONICONH- (wherein, R6 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

b and b8 may be the same or different, and each has the same meaning as a or a in the above general formula (I).

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

The electrical resistance used in the present invention is 109 Ωcm or more, and the dielectric constant is 3.
Preferably, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, and halogen-substituted products thereof can be used as the carrier liquid. For example, octane, isooctane, Decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G5 Isopar H1 Isopar L (Isopar; trade name of Exxon), Shellzol 70, Shellzol 71 (Shellzol; trade name of Shell Oil Company),
Amsco OMS, Amsco 460 T8 agent (Amsco;
Spirits Co., Ltd.'s product name) etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are prepared by dispersing monomer (A) and It is produced by copolymerizing with a macromonomer (M) (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 carbons. Examples include hydrogen and halogen-substituted products thereof, such as hexane, octane, isooctane,
Decane, Isodecane, Decalin, Nonane, Dodecane, Isododecane, Isopar E1 Isopar G, Isopar H, Isopar, Scherzol 70, Scherzol 7
1. Amsco OMS, Amsco 460 solvent, etc. are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohol R (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 M (For example, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methylene 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 104 Ωcm or more.

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

The dispersion stabilizing resin necessary to make a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing monomer (A) and macromonomer (M) in a non-aqueous solvent is , graph) 5 which polymerizes with monomers, and conventionally known dispersion stabilizing resins can be used. That is, various synthetic resins or natural resins soluble in non-aqueous solvents are used alone or in combination of two or more types. For example, the total carbon number is 6.
~32 alkyl chains or alkenyl chains [These aliphatic groups may contain substituents such as halogen atoms, hydroxy groups, amino groups, alkoxy groups, or oxygen atoms,
Esters of acrylic acid, methacrylic acid, or crotonic acid, which have 6 or more carbon atoms (carbon-carbon bonds in the main chain may be mediated by a heteroatom such as a sulfur atom or a nitrogen atom)
Polymers of 22 higher fatty acid vinyls, alkyl vinyl ethers, or olefins such as butadiene, isoprene, diisobutylene, etc., or copolymers of two or more of them, as well as soluble in non-aqueous solvents such as those mentioned above. Copolymers obtained by polymerizing the monomers forming the polymer and one or more of the following various monomers at a ratio within a range where the resulting copolymer is soluble in a nonaqueous solvent are also used. be able to.

The monomers include, for example, vinyl acetate; allyl acetate; methyl, ethyl, or propyl esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, inic acid, and itaconic acid; styrene derivatives ( (e.g. styrene, vinyltoluene, α-methylstyrene, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or their acid anhydrides; hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate , N-vinylpyrrolidone, acrylamide, acrylonitrile, 2-chloroethyl methacrylate, 2,2.2
-) Hydroxy group, amino group, amide group, cyano group, sulfonic acid group, such as lifluoroethyl meccrylate,
Examples include monomers containing various polar groups such as carbonyl groups, halogen atoms, and heterocycles.

Or, in addition to the above synthetic resins, alkyd resins,
Natural resins such as alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can also be used.

The monomers used in producing the non-aqueous dispersion resin include a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a co-monomer (A) that is soluble in the non-aqueous solvent. A distinction can be made between monofunctional macromonomers (M) that undergo polymerization.

Examples of the monomer (A) include vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, etc.);
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
C1-3 alkyl esters or alkylamides of unsaturated carboxylic acids such as maleic acid; styrene derivatives such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene; acrylic acid, methacrylic acid, crotonic acid, maleic acid acids, unsaturated carboxylic acids such as itaconic acid, their anhydrides or amides; hydroxyethyl methacrylate, hydroxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, trimethoxysilylpropyl methacrylate, N - Hydroxy group, amino group, amido group, cyano group, such as vinylpyrrolidone, acrylonitrile, methacrylaterile, 2-cyanoethyl methacrylate, 2-chloroethyl methacrylate, N-vinylpyridine, N-vinylimidazole, 2-furfurylethyl methacrylate, etc. Examples include polymerizable monomers containing various polar groups such as a sulfonic acid group, a sulfonic acid group, a carbonyl group, a halogen atom, and a heterocyclic group.

Monofunctional macromonomer (M) Ha, -1Q formula (I)
- general formula (II) which can be copolymerized with monomer (A) only at one end of the polymer main chain consisting of repeating units represented by
It is a macromonomer having a number average molecular weight of 104 or less, which is formed by bonding a polymerizable double bond group represented by:

In general formulas (I) and (II), a7, ats Yl
The hydrocarbon groups contained in l, Yl, Y, b, b, and R each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted. It's okay.

The repeating unit represented by general formula (I) used in the present invention will be further explained.

V, is -0--3--COO--0CO--CI! 0
CO- or -C)1. Represents COO-.

Yo preferably represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms in total. Preferred aliphatic groups include an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group,
2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), 2 with 4 to 18 carbon atoms
an optionally substituted alkenyl group (R4, for example, 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, ■-pentenyl L
1-hexenyl group, 2-hexenyl group, 4-methyl-
2-hexenyl L, etc.>, optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
(naphthylmethyl 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 ( For example, cyclohexyl group, 2-cyclohexylethyl group,
2-cyclopentylethyl group, etc.).

×1 and XN may be the same or different, and O-
-CO-1-COO--0CO--5O*--N-I represents coo--oco- or -N-.

R6 and h may be the same or different from each other, and 119
or -CI+- may be replaced by Xff(R4-
X, )? rY! These are hydrocarbon groups having 1 to 18 carbon atoms (hydrocarbon groups include aliphatic groups such as alkyl groups, alkenyl groups, aralkyl groups, and alicyclic groups) that may be interposed in a bond. Preferred specific examples of the aliphatic group include the same content as the preferred aliphatic group of Y mentioned above. However, Xl and X4 may be the same or different, and the above X+
, Xt-& represents the same symbol, R4 represents an optionally substituted alkylene group, alkenylene group or aralkyl group having 1 to 18 carbon atoms, and Y! indicates the same symbol as Y above.

Furthermore, regarding R1 and R2, to give a specific example, R
1 1? .

), -fCII=CH)-1Q+C)
! )-(Xl, x4, Y8, R1, and p are composed of any combination of atomic groups such as the above-mentioned X, iRa-Xah "'lt" symbol, 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 I to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.),
-COO-RS or -CIItCOORs (Rs 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 Y,
represents the same content as that described above).

Furthermore, m, n and p may each be the same or different,
0, ■, 2.3.4, where m+n is at least 1 or more.

Further specific examples of the repeating unit represented by the general formula (I) as described above are given below. However, the content of the present invention is not limited to these. In the following, a represents 11 or C11, R represents an alkyl group of CI-+S, and R' represents a hydrogen atom or an alkyl group of CI-II. ,kl,
kt is an integer from 1 to 12, j! , , 12 represents an integer from 1 to 100.

(A) -(CH2-C)- Coo(C,)Izi0COR (A) -(-CHl-Cl- Coo(CutyaC00R (A) -(CHI C-)- Coo(C1l□Resent OCO(CHz Rock0COR(A) -(CHI Cl- COO(CHl+OCO(C1l) PigeonC00R(A
) (8) 1 (A)-12 -(CH2-C)- COOCIIICII! GOOR CIl□C00R (A) 3 (C112Cl- CHzCOO(CHtdanC00R (A) 4 1+CHI CH C00(CI+!YaOCO(CH山5OfR(A) 5 CH.

1←H-CH)- Coo (CHzY0COR (^) -(CIl□-〇)- C00(CHr)B70COC1l・Cl1-COoR
(8) -(CO.

C)-COOCHzC1lCHzOCOR C0R (^) -)C1-fJ- Coo (CI, 70CO(CI+□)2Nll-+1
(A) -(CHl2C)-Coo(C)IICH! 0韮−R゛(A) 0 −(C1h C′)−CH3COO(CHffiCHO加1(A)6CH.

1+CII-CII >-- COOCII□CHCH20COR C0R (8) 7 -(C1h-CH)- OCO(CHz■0COR (A) 8 ncIIZ-CIlh (Clldy, Coo(Cll□)-; COOR general formula (It) In, represents 00 OCO H2OC0 -CH2CO0 SO□ ONH or C0NHCON11-.

However, R5 is a hydrogen atom or represents a hydrocarbon group having 1 to 18 carbon atoms.

As the hydrocarbon group, an aliphatic group having 1 to 18 carbon atoms is preferable, and specific examples thereof include those described for v0 above.

b and b2 are They may be the same or different from each other, It has the same meaning as 81 or a8 in the above general formula (I). b.

and b! The preferred ranges of al and a are respectively the above-described ranges.
! The content is similar to that explained in .

a of general formula (I), and a! Either one of the general formula (II), and b! It is more preferable that either one of them is a hydrogen atom.

The macromonomer provided in the present invention has only one end of the polymer main chain containing at least a repeating unit represented by the general formula (I) as described above.
) has a chemical structure in which the polymerizable double bond groups shown in () are directly bonded or bonded by an arbitrary linking group. Examples of the group connecting the formula (I) component and the formula (If) component include a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (heteroatoms include, for example, an oxygen atom, a sulfur atom, , nitrogen atoms, silicon atoms, etc.),
It is composed of any combination of atomic groups of heteroatom-heteroatom bonds.

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

Formula ([[[) In formula (Ill), aIs ass b+, b2, Yo,
Vo, Vl, R+, Rt, X,,X,,m,,n
each represents the same content as explained in general formulas (I) and (II).

9 R3゜ Elementary atom, halogen atom (I, e.g., fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g., methyl group, ethyl group, -so, -1-
CON-2-3O,N-1-)JHCOO-1-NHC
ONH-1R.

Si-(Rz and Rtz each represent a hydrogen atom or the R
+! represents a single linking group or a linking group composed of any combination selected from the atomic groups such as [indicates a hydrocarbon group expressing the same content as Yo].

The upper limit of the number average molecular weight of the macromonomer (M) is lXl0
If it exceeds ', the rigidity resistance will decrease. On the other hand, if the molecular weight is too small, stains will occur (due to the amount of spraying, it is preferably 1×10 3 or more).

In the general formula (I), (It) or (lI[), vo, vo, ■3, al, a2, bl, b! Particularly preferred examples are shown for each of the following.

As vo, -COO--0CO--0--CIIC
OO- or -coz6co-, Yo is an alkyl group or alkenyl group having 18 or less carbon atoms, Vl is all of the above (however, R6 is a hydrogen atom), al, a2, bl, b , includes a hydrogen atom or a methyl group.

b, b.

C) v, -t in I-C shown in general formula (I) below
In the following, specific examples of i- are shown, but the content of the present invention is not limited thereto, and b is II.
or C11, is an integer from 2 to 12, and n is an integer from 1 to 12.
Represents an integer of 12.

(B)-1Cl1t・C COO(C15)v7 s- (B)-2Cl1l-C C00(CHx)v70CO(C11*)117S-(
B) 4 CH1=C CONH(CHg)r7S - ■ (B)-5cut・C C00CHxCHCHzOOC(CL)i〒S-H (B)-9CIh=C C00(C8! Around NHCOO(C1l龜rTs-(B)
−10cog=c COO(C8ff￥NHCONI((CIl z)Ii
〒5(B)-8 CIl□-〇Coo(CHz)-fiNHco(C)It)ITs-
(B)-13CH2=C C0NHCOO(CH!) IT S (B)-14CH1=CCHff COO(CH convex, 7cm N N In addition, in the macromonomer (M) provided for the present invention,
Along with the repeating unit represented by general formula (I), other repeating units may be contained as copolymerization components.

As the other copolymerization component, any repeating unit may be used as long as it is a repeating unit composed of another monomer that can be copolymerized with the monomer corresponding to the repeating unit of general formula (L). Examples of such other monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinylacetic acid, 4-
Unsaturated carboxylic acids such as pentenoic acid and esters or amides of these unsaturated carboxylic acids; C1-22 fatty acid vinyl esters or allyl esters; vinyl ethers; styrene and styrene mR forms; Examples include heterocyclic compounds.

Specifically, examples thereof include the compounds exemplified as monomer (A) described above, but are not limited thereto.

In the total sum of repeating units of the macromonomer (M),
The content of the repeating unit represented by the general formula (I) is preferably 40% by weight or more, more preferably 60 to 100% by weight.

If the content of the component represented by general formula (I) is less than 40% by weight of the total, the mechanical strength of the image area formed by dispersed resin particles will not be maintained sufficiently, and therefore the rigidity resistance when used as an offset original plate will be insufficient. The effect of improvement is no longer visible.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, ① Ionic polymerization method in which the ends of living polymers obtained by anionic polymerization or cationic polymerization are reacted with various reagents to form macromers; ② Carboxyl groups, hydroquine groups, amino groups, etc. in the molecule. A method using a radical polymerization method in which various reagents are reacted with an oligomer with a terminal reactive group bond obtained by radical polymerization using a polymerization initiator and/or a chain transfer agent containing a reactive group to produce a macromer. , a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer obtained by a zero-polyaddition or polycondensation reaction in the same manner as the above-mentioned radical polymerization method.

Specifically, P, Dreyfuss & R, P, Q
uirk+Encyc1. Po1y+m, Sci,
Eng., 1.551 (I987), P.

F. Rempp; E. Franta;
Adv, Polym, Sci, +58+1
(I984), V. Percec, 8p.
pl, Polym, Sci, + 2ndan.

95 (I984), R, ^sami, M, Ta
kaRi, Makvamol.

Chem, 5upp1. , 12. 163 (
I985), P. Rempp, etat.
Makvamol, Chew, 5upp1. +
s, 3 (I984), 11 soil materials, chemical industry,
38.56 (I987), Yuya Yamashita.

Polymer, 31.91118 (I982), Shibe Kobayashi, Polymer, Betsu 625 (I981), Toshinobu Higashimura 2 Journal of Japan Adhesive Association, 18°536 (I9B2), Hiroshi Io-1
Polymer Processing, 35.262 (I986), Tokishibu,
Takashi Tsuda 5 functional materials, U[.

It can be synthesized according to the method described in the review of Nα10.5 etc. and the literature/patents cited therein.

The dispersion resin of the present invention comprises a monomer (A) and a macromonomer (
A desired dispersion resin can be obtained if the resin synthesized from these monomers is insoluble in the non-aqueous solvent. More specifically, it is preferable to use the macromonomer (M) in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the monomer (A) to be insolubilized. More particularly preferred is 0.3 to 3% by weight. Further, the molecular weight of the dispersion resin of the present invention is 103 to 104, preferably 104 to 5×104.

In order to produce the dispersion resin used in the present invention as described above, -i, the above-mentioned dispersion stabilizing resin, monomer (A) and macromonomer (M) are peroxidized in a non-aqueous solvent. The polymerization may be carried out by heating in the presence of a polymerization initiator such as benzoyl, azobisisobutyronitrile, butyllithium, etc. Specifically, ① dispersion stabilizing resin, monomer (A), and macromonomer (M) A method of adding a polymerization initiator to a mixed solution of
■ A method in which the monomer (A) and the macromonomer (M) are dropped together with a polymerization initiator into a solution in which the dispersion stabilizing resin is dissolved, or ■ The total amount of the dispersion stabilizing resin and the monomer (A
) and a part of the macromonomer (M) mixture, the remaining monomer mixture is optionally added together with a polymerization initiator; There are also methods of optionally adding a mixed solution of the monomer (A) and the macromonomer (M) together with a polymerization initiator, and it can be produced using either method.

The total amount of the monomer (A) and the macromonomer (M) varies from 5 to 80 parts by weight per 100 parts by weight of the nonaqueous solvent,
Preferably it is 10 to 50 parts.

The amount of the soluble resin which is the +lk stabilizing resin is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the monomer and macromonomer used above.

The appropriate amount of the polymerization initiator is 1 to 5% by weight of O8 based on the total amount of Qi support and macromonomer.

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

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

The non-aqueous dispersion resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and at the same time exhibits extremely stable dispersibility, and can be used repeatedly for a long time, especially in a developing device. Even if the developing speed is increased, the dispersibility is good, and even if the developing speed is increased, redispersion is easy, and no stains are observed on various parts of the device.

Furthermore, when fixed by heating or the like, a strong film was formed and exhibited excellent fixing properties.

In particular, the non-aqueous dispersion resin described in JP-A No. 62-151868 has a monomer that polymerizes and becomes insolubilized, and a monomer that can be copolymerized with a small number of ester bonds (both contain two or more). This is a resin particle obtained by coexisting with a monomer that can be A plate making machine using a master plate (for example, Fuji Photo Film Co., Ltd., EPL-560, EPL-82)
0, etc.), or when the processing speed of the plate making machine was increased, there was still a problem with the dispersibility of the particles. However, when the resin particles provided by the present invention are used, no problem occurs even under such severe conditions.

As described above, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-size master plate is used.

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

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known Dn materials or dyes. ing. 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 the amount is less than 0.5 part by weight, the image density will be insufficient, and if it exceeds 50 overlapping parts, fogging may easily 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 o,oot to 1.0 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, the electrical resistance of the liquid developer with toner particles removed is lower than 109ΩC11l (If this happens, it will be difficult to obtain a high-quality continuous tone image, so the amount of each additive added should be controlled within this limit. is necessary.

Embodiments of the present invention are illustrated below, but the content of the present invention is not limited thereto.

A mixed solution of 96 g of M-2-(II-hexylcarbonyloxy)ethyl methacrylate, 4 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 70''C while stirring under a nitrogen stream. 2.1.0 g of 2'-azobis(isobutyronitrile) (abbreviated as A, 1.B, N,) was added and reacted for 8 hours.Next, 8 g of glycidyl methacrylate and N,N-dimethyldodecylamine were added to this reaction solution. 1.
0g and 0.5g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100°C for 12 hours. After cooling, this reaction solution was reprecipitated into methanol 21 to obtain 82 g of an oily substance.
The number average molecular weight of the polymer was 5.600.

Macromonomer M-1: Synthesized. The number average molecular weight of each macromonomer obtained was in the range of 5,000 to 7,000.

Table 1 In Production Example 1 of H3 macromonomer, the macromonomer was reacted in the same manner as in Production Example 1, except that only 2-(II-hexylcarbonyloxy)ethyl methacrylate was replaced with a compound corresponding to Table 1 below. Monomers in Table 1 (Continued Table ■ (Continued 2) 2.3-Diacetoxypropyl methacrylate 96 g
A mixed solution of 4 g of thioethanol and 200 g of toluene was heated to a temperature of 70'C while stirring under a nitrogen stream. A.1. B, N, 1. Og was added and the mixture was reacted for 4 hours. Furthermore, ^, 1. 0.5g of B and N were added for 3 hours, and then 0.3g of A, r, B, and N were added and reacted for 3 hours. This reaction solution was cooled to room temperature, 9.6 g of 2-carboxyethyl methacrylate was added, and to this was added 12.7 g of dicyclohexylcarbodiimide (abbreviated as C,C,'').
A mixed solution of g and 50 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred for 4 hours. The precipitated crystals were separated by filtration, and the resulting filtrate was reprecipitated into 2 J of methanol. The precipitated oil was collected by decantation, dissolved in 150 d of methylene chloride, and reprecipitated again in 1 liter of methanol. The oil was collected and dried under reduced pressure to obtain a polymer with a number average molecular weight of 3800 in a yield of 54 g.

Macromonomer M-22: C.I.

table C00CHtCHCHzOCOCHz 0COCR.

Macromomer 2 to 29: M-23 to M-9 In the production example of macromonomer M-22, 2゜3-diacetoxypropyl methacrylate and unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) were each replaced. The macromonomers shown in Table 2 below were each produced in the same manner as in the production example of M-22. The number average molecular weight of each macromonomer obtained was in the range of 3,000 to 6,000.

Table 2 (continued) Macromonomer 30: M-302-[3-methoxycarbonylpropyleneoxy]ethyl methacrylate 96 g, 2-mercabutoe(-ruamine 4
A mixed solution of 200 g of tetrahydrofuran and 200 g of tetrahydrofuran was heated to a temperature of 70''C under a nitrogen stream.

^, T, B, N, 1. Og was added and reacted for 4 hours, and then A
, 1. B.N.

0.5g of was added and reacted for 4 hours. The reaction solution was then cooled in a water bath to a temperature of 20°C and triethylamine 6
．． Then, 5.6 g of acrylic acid chloride was added dropwise with stirring at a temperature of 25° C. or lower. 'a left after up and down 1
Stirred for an additional hour. Thereafter, 0.5 g of L-butylhydroquinone was added and the mixture was heated to 60°C and stirred for 4 hours. After cooling, reprecipitation into methanol 22 was performed twice to obtain 54 g of a pale yellow viscous substance. Number average molecular weight is 430
It was 0.

Macromonomer M-30: Macromonomer 31:M-3 A mixed solution of 95g of 2,3-dipropyloxypropyl methacrylate, 150g of tetrahydrofuran, and 50g of isopropyl alcohol was heated to a temperature of 75°C under a nitrogen stream. 4
．． 4'-azobis(4-cyanovaleric acid) (abbreviation: A, C
, V,) was added and reacted for 5 hours, and then A, C, V
, 1. Og was added and the mixture was reacted for 4 hours.

After cooling, the reaction solution was mixed with 1.51 liters of water! The oil was collected by decantation and dried under reduced pressure. Yield is 8
It was 5g.

50 g of this oil (oligomer), 15 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 1.0 g of 2.2'-methylenebis(6-t-butyl-p-cresol) were added at a temperature of 100°C. Stirred for 15 hours. After cooling, this reaction solution was reprecipitated into petroleum ether 12 to obtain 36 g of a transparent viscous substance. The number average molecular weight was 3,600.

Macromonomer M-31: OHCN COOC)IiCHCHgOCOCNCooC)IiC
HCH macromonomer 32:M-2 In production example 31 of macromonomer, 50 g of the intermediate oligomer (oil ') obtained, 5.6 g of 2-hydroxyethyl methacrylate, and 100 g of methylene chloride.
To a mixed solution of g, D, C, C, 9,
A mixed solution of Og, 0.5 g of 4-dimethylaminopyridine, and 20 g of methylene chloride was added dropwise over 1 hour. The mixture was stirred for an additional 4 hours. The precipitated crystals were separated by filtration, and the filtrate was reprecipitated twice in petroleum ethanol 11, and the obtained oil was dried under reduced pressure.

The yield was 28 g and the number average molecular weight was 3,000.

Macromonomer M-32: CH.

Macromonomer M-33: C11° ococzos A gamma kneading solution of 95 g of 2-(II-nonylcarbonyloxy)ethyl crotonate and 200 g of tetrahydrofuran was heated to 75° C. under a nitrogen stream. 2°2°−
5 g of azobis (cyanoheptatool) was added and reacted for 8 hours.

After cooling, the reaction solution was brought to a temperature of 20°C in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour, and then stirred for 6 hours at a temperature of 60°C.

After cooling the obtained reaction product, the operation of reprecipitating it into methanol 22 was performed twice to obtain 62 g of a colorless and transparent viscous material.

Two macro-Natsuma-M had a number average molecular weight of 6,200.
In the production example of -1, methacrylate monomer (2-
(II-hexylcarbonyloxy)ethyl methacrylate], the mercapto compound (corresponding to thioglycolic acid), and the epoxy group-containing ester [corresponding to glycidyl methacrylate] were changed in the same manner as in the production example of M-1. Each of the macromonomers shown in Table 3 below was produced.

-1 class: D-1 18 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, the compound of macromonomer production example 1 (M-
A mixed solution of 1.0 g of 1) and 380 g of Isopar H was heated to 75° C. with stirring under a nitrogen stream. ^
, 1. Add 0.8g of B and N, react for 4 hours, and then add A
, 1. 0.4g of B 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 polymerization rate was 90%.
The latex had an average particle size of 0.25 tIm.

2: D-octadecyl methacrylate/2-hydroxyethyl methacrylate (copolymerization ratio: 92/8M ratio) copolymer 1
6g, vinyl acetate 100g, macromonomer production example 2
1.0 g of compound (M-2) and 38 g of Isopar H
5g of the mixed solution was heated to a temperature of 70°C while stirring under a nitrogen stream.
Warmed to ℃. 2. 1.0 g of 2'-azobis(isovaleronitrile) (abbreviated as A, 1.V, N) was added and reacted for 2 hours, and then A, 1. After adding 0.4 g of V and N and reacting for 2 hours, the temperature was raised to 100° C., and the mixture was stirred for 1 hour to distill off the remaining vinyl acetate. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.22.

--S ~: D-~D-3
In Production Example 2 of Latex Particles, each latex particle was produced under the same conditions as Production Example 2, except that the resin for dispersion stabilization and the macromonomer were replaced with the compounds shown in Table 4 below. The polymerization rate of each latex particle was 80-85%.

32:D-3 20 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, 5 g of crotonic acid, 1.0 g of the compound (M-6) of Macromonomer Production Example 6, and 4 g of Isopar E
68g of the mixed solution was heated to a temperature of 7 while stirring under a nitrogen stream.
Warmed to 0°C. A.1. After 1.3 g of V and N were added and reacted for 6 hours, the temperature was raised to 100°C and stirred for 1 hour to distill off the remaining vinyl acetate. 200 after cooling
The white dispersion obtained by passing through a mesh nylon cloth was a latex with a polymerization rate of 85% and an average particle size of 0.23.

M-X 3: D-3 20g poly(dodecyl methacrylate), 1 vinyl acetate
A mixed solution of 00g, 4-pentenoic acid, 6.0g, 1.5g of the compound (M-7) of Macromonomer Production Example 7, and 380g of Isopar G was heated to a temperature of 75°C while stirring under a nitrogen stream. Warmed. A.1. B, N, 0.
7g was added and reacted for 4 hours, and then A, 1. B, N, 0.
5g was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth and had an average particle size of 0.
It was 24-inch latex.

m-x: D-dodecyl methacrylate/2-hydroxyethyl methacrylate (copolymerization ratio; 8/2 molar ratio) copolymer 18g1
85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of the compound (M-1) of Macromonomer Production Example 1
A mixed solution of 380 g of n-decane was heated to 75° C. while stirring under a nitrogen stream. ^, 1. Add 1.7g of B and N, react for 4 hours, and then add ^, 1. 0.5g of B and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with an average particle size of 0.
．． It was 20-g latex.

20 g of D-poly(octadecyl methacrylate), 100 g of isopropyl methacrylate, 1.0 g of the compound (M-8) of Macromonomer Production Example 8, and 470 g of n-decane
The mixed solution of g was heated to 70℃ while stirring under a nitrogen stream.
It was heated to A.1. V, N, 1. Og was added and the mixture was reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.45.

M-X 36:D-36 poly(tridecyl meccrylate) 25g1. 100 g of styrene, the compound of macromonomer production example 25 (M-
A mixed solution of 0.6 g of 25) and 380 g of Isopar H was heated to a temperature of 60° C. while stirring under a nitrogen stream. Add 0.6g of A, r, V, N, and react for 4 hours,
Furthermore, A.1. 0.3g of V and N were added and reacted for 3 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.2 days.

A) Manufacturing Example 1 of Latex Particles except for the macromonomer (M'-1) was carried out in the same manner as in Example 1, and the resulting white dispersion had a polymerization rate of 85% and an average particle size of 0. It was 25-g latex.

38 B) 18 g of poly(octadecyl methacrylate-N, 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate and 3 g of Isopar H)
85 g of mixed solution was prepared, and the other operations were the same as in Production Example 1.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.2.
2I! It was latex of m. (Unexamined Japanese Patent Publication No. 60-179
Corresponding to the latex particles of No. 751) --S 9C)
A mixed solution of 18 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, and monomers having the following chemical structure (1 g of N and 385 g of Isopar H) was prepared, and the other operations were carried out in the same manner as in Production Example 1.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.2.
It was 4- latex. (Unexamined Japanese Patent Publication No. 62-15186
(equivalent to latex particles No. 8) Monomer (I) HI HI-C COO (CHx)zOcOcJ+v (II) Example 1 Dodecyl methacrylate/acrylic # (copolymerization ratio 195
15 weight ratio) copolymer Log, 10 g of Nigrosine, and 30 g of Shell Silua 1 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of Nigrosine.

3 resin dispersion (D-1) of latex particle production example 1
0g, 2.5g of the above nigrosine dispersion, FQC1400
(Manufactured by Nikki Kagaku ■: Tetradecyl alcohol) 15g, (
Octadecene-half-maleic acid octadecylamide copolymer) 0.08g was added to Shell Sila 1! .

A liquid developer for electrostatic photography was prepared by diluting it to .

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

″ 2A Resin dispersion formula of latex particle production example 37 ′
B Resin dispersion of Nilatex particle production example 38 C Resin dispersion of latex particle production example 39 These liquid developers were used as a developer in fully automatic plate making 1ELP404V (manufactured by Fuji Photo Film ■), and electrophotographic exposure was performed. The material ELP Master ■ type (manufactured by Fuji Photo Film ■) was exposed and developed. The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original.

The results are shown in Table-5.

Table 5 When each developer was plate-made under the above-mentioned plate-making conditions, the developer of the present invention was the only one that did not cause staining of the developing device and provided a clear image on the 2000th plate-making plate.

On the other hand, an offset printing master plate (ELP master) obtained by plate making using each developer was 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, the present invention and comparative example A
In the master plate obtained using the developer of Comparative Example C, the problem did not occur even after 10,000 sheets or more, and in the master plate using Comparative Example B, the problem occurred after 8,000 sheets.

As can be seen from the above results, only the developer made from the resin particles of the present invention did not cause any staining of the developing device and at the same time significantly increased the number of Yaster plates printed.

That is, in the case of Comparative Example A, although there was no problem with the number of prints, the developing device was extremely dirty and could not withstand continuous use.

In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 5.
When used at high plate-making speeds such as sheets/minute (conventionally, the plate-making speed was 2 to 3 sheets/minute), the developing device (especially on the back electrode plate) becomes dirty, and after 2,000 sheets, the plate becomes dirty. The number of prints on the master plate, which affected the quality of the copied image (decreased D+*ax, blurred thin lines, etc.), was not a problem in Comparative Example C, but decreased in Comparative Example B. did.

These results demonstrate that the resin particles of the present invention are clearly superior.

Example 2 White dispersion 10 obtained in Production Example 2 of Latex particles
A mixture of 0 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 s.

32 g of the above black resin dispersion, FOC-1600 (
20g of Nissan Chemical I grade, hexadecyl alcohol), 0.05g of zirconium naphthenate, and 1 part of Shell Silua 1
A liquid developer was prepared by diluting the solution to 1:1.

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

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

Example 3 White dispersion 10 obtained in latex particle production example 33
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 0.25.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 0.5 g of Isopar H to 11 g.

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

Example 4 32 g of white resin dispersion obtained in latex particle production example 3
, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-
1800 (manufactured by Nissan Chemical ■, octadecyl alcohol) 1
5 g and 0.02 g of a semi-docosanylamidated copolymer of diisobutylene and maleic anhydride were added to 1 of Isopar G.
A liquid developer was prepared by diluting the solution to 1:1.

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

Further, after leaving this developer for 3 months, the same treatment as above was performed, but there was no difference at all from before the aging.

Example 5 Poly (decyl methacrylate) Log, Isopar H
and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

30 g of the white resin dispersion obtained in Production Example 23 of Latex Particles, 4.2 g of the above alkali blue dispersion, and 0.06 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride were added to Isopar G if. A liquid developer was prepared by diluting it.

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

Examples 6 to 27 In Example 5, D- of latex particle production example 23
A liquid developer was prepared in the same manner as in Example 5, except that each latex shown in Table 6 below was used in place of Example 23.

Table 6 After this developer was left to stand for 3 months, the same treatment as above was performed, but there was no difference at all from before.

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device does not become contaminated, and both the image quality of the obtained offset printing master plate and the image quality of the printed matter after single-sheet printing are very clear. Ta.

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.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles In the presence of a resin that is soluble in an aqueous solvent and does not contain a graft group that polymerizes with the monomer, a monofunctional monomer (A ) and the following general formula (I)
A monofunctional product with a number average molecular weight of 10^4 or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (II) only to one end of a polymer main chain consisting of repeating units represented by A liquid developer for electrostatic photography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing at least one macromonomer (M). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) In general formula (I), V_0 is -O-, -S-, -
COO-, -OCO-, -CH_2OCO- or -CH
Represents _2COO-. Y_0 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. X_1 and X_2 may be the same or different from each other,
-O-, -CO-, -CO_2-, -OCO-, -SO
＿2, ▲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.▼ (Y_1 represents the same symbol as Y_0 above). R_1 and R_2 may be the same or different from each other,
They may be substituted, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ may be interposed in the bond of the main chain. , R_4 represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, and Y_2 represents a hydrocarbon group having 1 to 18 carbon atoms, and Y_2 has the same symbol as Y_0. a_1 and a_2 may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-R_5 or -COO-R_5(R
_5 represents a hydrogen atom or a hydrocarbon group that may be substituted. m, n and p may be the same or different, and are 0 to 4
represents an integer. However, m+n is at least 1 or more. In general formula (II), V_1 is -O-, -COO-
, -OCO-, -CH_2OCO-, -CH_2COO
-, -SO_2-, -CONH-, -SO_2NH-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
-CONHCOO- or -CONHCONH- (wherein R_6 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). b_1 and b_2 may be the same or different from each other,
Each has the same meaning as a_1 or a_2 in the above general formula (I).