JP2640170B2 - Liquid developer for electrostatic photography - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a liquid developer for electrostatography comprising at least a resin dispersed in a carrier liquid having an electric resistance of 109 Ωcm or more and a dielectric constant of 3.5 or less, and in particular, The present invention relates to a liquid developer having excellent redispersibility, storage stability, stability, image reproducibility, and fixability.

(Prior Art) A general liquid developer for electrophotography is a petroleum-based resin such as an organic or inorganic pigment or dye such as carbon black, nigrosine or phthalocyanine blue and a natural or synthetic resin such as alkyd resin, acrylic resin, rosin or synthetic rubber. Dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and added with a polarity controlling agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, and vinylpyrrolidone. .

In such a developer, the resin is dispersed in the form of particles having a diameter of several nm to several hundred nm as insoluble latex particles,
In the conventional liquid developer, the soluble dispersion stabilizing resin and the polarity controlling agent were easily diffused into the solution due to insufficient bonding between the soluble dispersion stabilizing resin and the polarity controlling agent and the insoluble latex particles. For this reason, there has been a drawback that the soluble dispersion stabilizing resin is detached from the insoluble latex particles due to long-term storage or repeated use, and the particles settle, aggregate, accumulate, and the polarity becomes unclear. Also, once aggregated,
The deposited particles are difficult to re-disperse, so that the particles remain attached to the developing device everywhere, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding 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.
However, the dispersion stability of these liquid developers against spontaneous sedimentation of particles has been improved to some extent, but it is still insufficient, and when used in an actual developing device, the toner adhered to each part of the device becomes a coating film. In addition, it is difficult to re-disperse, and furthermore, it is not sufficient for re-dispersion stability which can be used practically, for example, it causes a failure of the apparatus, stains of a copied image, and the like. Further, in the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle size distribution, there is a remarkable restriction on the combination of a dispersion stabilizer to be used and a monomer to be insolubilized. The resulting particles were large in particle size distribution containing a large amount of coarse particles, or polydispersed particles having two or more average particle diameters. In addition, it was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 μm or more or very fine particles of 0.1 μm or less were formed. Further, there is a problem that the dispersion stabilizer to be used must be produced through a complicated and time-consuming production process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components. A method for improving the dispersibility, redispersibility, and storage stability of particles is disclosed in JP-A-60-179951 and JP-A-62-17975.
No. 151868 and the like. Further, in the presence of a polymer utilizing a bifunctional monomer or a polymer utilizing a polymer reaction, an insoluble dispersion resin of a copolymer of a monomer insolubilized and a monomer containing two or more polar components Methods for improving the dispersibility, redispersibility and storage stability of particles by making them into particles are disclosed in JP-A-62-166362 and JP-A-63-66567.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing a large number of 5,000 or more sheets using a master plate for offset printing by an electrophotographic method has been attempted. It has become possible to print 10,000 sheets or more in plate size. Further, the operation time of the electrophotographic plate making system has been shortened, and improvement in speeding up the development-fixing process has been performed.

JP-A-60-179951, JP-A-62-151868 and JP-A-62-16
No. 6362 and No. 63-66567, the dispersed resin particles are produced in the case where the developing speed is increased, the dispersibility of the particles, the redispersibility, and the fixing time is reduced. Alternatively, in the case of a master plate of a large plate size (for example, A-3 size or more), the performance was not always satisfactory in terms of printing durability.

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

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid developer which has a fast development-fixing process and has excellent dispersion stability, re-dispersibility and fixability even in an electrophotographic plate making system using a large-size master plate. That is.

Another object of the present invention is to provide a liquid developer capable of producing an offset printing master having excellent printing ink oil sensitivity and printing durability by electrophotography.

Another object of the present invention is to provide a liquid developer suitable for various kinds of electrophotography and various kinds of transfer 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 ink jet recording, cathode ray tube recording, and recording of various change processes such as pressure change or electrostatic change. That is.

(Means for solving the problem) The above-mentioned objects are to achieve an electric resistance of at least 10 ⁹ Ωcm and a dielectric constant of 3.5
In a liquid developer for electrophotography comprising at least resin particles dispersed in the following non-aqueous solvent, the dispersed resin particles may be a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, a carboxamide group, Sulfoamide group, amino group, (R ₁₁ represents a —R ₁₂ group or —OR ₁₂ group, and R ₁₂ represents a hydrocarbon group), a polymer component containing at least one polar group selected from cyclic acid anhydride-containing groups, and / or Alternatively, an AB block composed of an A block containing a polymer component corresponding to the monofunctional monomer (A) and a B block containing at least a polymer component represented by the following general formula (I): A polymer is formed, and a polymerizable double bond group is bonded to the terminal of the polymer main chain of the B block.
A graft-type copolymer containing at least one monofunctional macromonomer (MM) of ^{3 to} 2 × 10 ⁴ and a monomer (B) represented by the following general formula (II); A monofunctional monomer (A) which is soluble in the non-aqueous solvent but insolubilized by polymerization in the presence of a dispersion stabilizing resin of the following general formula (II):
The polymer comprising a repeating unit represented by I) has a number average molecular weight of 1 × 10 ⁴ or less which is formed by bonding a polymerizable double bond group represented by the following general formula (IV) to only one end of the main chain. Achieved by a liquid developer for electrophotography, wherein the copolymer resin particles are obtained by polymerizing a solution containing at least one monofunctional macromonomer (M _A ). .

General formula (I) In the formula (I), V ₀ is -COO-, -OCO-, (L ₁ and l ₂ represent an integer of 1 to 3), -O-, -SO
_2- , -CO-, -CONHCOO-, -CONHCONH-, or Wherein R ₁₃ represents a hydrogen atom or a hydrocarbon group.

R ₀ represents a hydrocarbon group.

a ₁ and a ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z ₁ or a hydrocarbon group having 1 to 8 carbon atoms. Through which —COO—Z ₁ (where Z ₁ is a hydrogen atom or a group having 1 to 22 carbon atoms)
Represents a hydrocarbon group).

General formula (II) In the formula (II), V ₁ represents —COO—, —OCO—, (L _3, l ₄ is an integer of 1 to 3), or represent -O-.

R ₁ represents an aliphatic group having 8 or more carbon atoms.

b ₁ and b ₂ may be the same or different and each represent a hydrogen atom,
Represents a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

General formula (III) Wherein (III), T ₁ is _{-COO -, - OCO-, CH 2} l COO
_{-, CH 2 l OCO -,} - O -, - SO 2 -, - CONHCOO-,
−CONHCONH−, Represents (D ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. 1 represents an integer of 1 to 3.) G ₀ represents a hydrocarbon group having 1 to 22 carbon atoms. Where G ₀
, - - -O is in the carbon chain of the _{CO -, - CO 2 -,} - OCO -, -
SO ₂ −, May be contained. Here, D ₂ represents the same content as D _1.

d ₁ and d ₂ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ₃
Or —COO—D ₃ via carbon hydrogen (D ₃ represents a hydrogen atom or a hydrocarbon group which may be substituted).

General formula (IV) Wherein (IV), T ₂ represents T ₁ same content as the formula (III). e ₁ and e ₂ may be the same or different from each other;
It represents a d _1, d ₂ identical contents and I).

Furthermore, it is preferable that the monofunctional macromonomer (M _A ) to be copolymerized together with the monomer (A) used in the present invention contains at least a repeating unit represented by the following general formula (IIIa).

General formula (IIIa) Wherein _{(III a), d 1,} d 2, T 1 represents the same symbols as in formula (III).

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

J ₁ and J ₂ may be the same or different from each other;
-, - CO -, - CO 2 -, - OCO -, - SO 2 -, The representative (D ₄ represents the same content as D ₁ of the formula (III)).

W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain. Here, J ₃ and J ₄ may be the same or different from each other, have the same contents as J ₁ and J ₂ above, and W ₃ is
It represents a C1-C18 hydrocarbon group which may be substituted.

m, n and p each independently represent an integer of 0-3. However, none of them is 0 at the same time.

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

The electric resistance used in the present invention is 10 ⁹ Ωcm or more, and the dielectric constant is 3.5.
As the following carrier liquid, a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen-substituted product thereof can be preferably used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E,
Isopar G, Isopar H, Isopar L (Isoper; trade name of Exxon), Cielsol 70, Cielsol 71 (Cielsol; trade name of Ciel Oil), Amsco OMS, Amsco 460 solvent (Amsco; American
mineral. (Trade name of Spirits) or the like is used alone or in combination.

Non-aqueous dispersion resin particles, which are the most important components in the present invention (hereinafter sometimes referred to as latex particles)
Is a monofunctional monomer (A) in a non-aqueous solvent in the presence of a dispersion stabilizing resin which is a graft copolymer of the present invention.
And a monofunctional macromonomer (M _A ) by copolymerization (so-called polymerization granulation method).

Here, as the non-aqueous solvent, basically, any solvent that is miscible with the carrier liquid of the liquid developer for electrostatography can be used.

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. Hydrogen and halogen-substituted products thereof are exemplified. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isopaffin petroleum solvents such as Isopar E, Isopar G, Isopar H, Isopar L, Cielsol 70, Cielsol 71, Amsco OM
S, Amsco 460 solvent or the like is used alone or as a mixture.

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

The non-aqueous solvent used by mixing these, after polymerization granulation,
It is desirable to evaporate under heating or under reduced pressure.However, as a latex particle dispersion, even if brought into the liquid developer, there is a problem if the liquid resistance of the developer can satisfy the condition of 10 ⁹ Ωcm or more. No.

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

Monomers used in producing the non-aqueous dispersion resin,
A monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and a monofunctional macromonomer (M _A ) which is copolymerized with the monomer ( _A ). can do.

The monomer (A) in the present invention may be any monofunctional monomer which is soluble in a non-aqueous solvent but insolubilized by polymerization. Specifically, for example,
Examples include a monomer represented by the following general formula (V).

General formula (V) In the formula (V), U ₁ represents —COO—, —OCO—, —CH ₂ OCO—,
_{CH 2 COO -, - O -} , - CONHCOO -, - CONHOCO -, - SO 2
−, Represents Here, E ₂ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl A 3-methoxypropyl group).

E ₁ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2,2-dichloroethyl group, 2,2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
-Cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group , 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-sulfamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

f ₁ and f ₂ may be the same or different from each other, and each represents the same content as a ₁ or a ₂ in the general formula (I).

Specific monomers (A) include, for example, those having 1 to 1 carbon atoms.
6 vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid Alkyl esters or amides of a carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group as the alkyl group) Group, trifluoroethyl group, 2-hydroxyethyl group, 2
-Cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2- (N, N-dimethylamino)
Ethyl group, 2- (N, N-diethylamino) ethyl group, 2
-Carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
Chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc .; styrene derivatives (eg, styrene, vinyltoluene, α-methyl) Styrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid;
Maleic acid, itaconic acid cyclic acid anhydride; acrylonitrile; methacrylonitrile; polymerizable double bond group-containing heterocyclic compound (specifically, for example, "Polymer Data Handbook-Basic Edition-" edited by The Society of Polymer Science, Japan , P175-184, compounds described in Baifukan (1986), for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran,
Vinyloxazoline, vinylthiazole, N-vinylmorpholine and the like).

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

Next, the monofunctional macromonomer (M _A ) used in the present invention will be further described.

The monofunctional macromonomer (M _A ) can be copolymerized with the monomer (A) only at one terminal of the main chain of the polymer composed of the repeating unit represented by the general formula (III), It is a macromonomer having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by IV).

In the general formulas (III) and (IV), d ₁ , d ₂ , T ₁ , G ₀ , e
_1, the hydrocarbon group contained in e ₂ and T ₂ have each indicated number of carbon atoms (as unsubstituted hydrocarbon group), these hydrocarbon groups may be substituted.

In the formula (III), D ₁ in the substituent represented by T ₁ is a hydrogen atom.
To 22 optionally substituted alkyl groups (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl) Group,
Octadecyl, eicosanyl, docosanyl, 2-
Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms
Optionally substituted alkenyl group (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
Linolel group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group) , Methylbenzyl group, ethylbenzyl group, methoxybenzyl group,
A dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.), or a carbon number 6-12 optionally substituted aromatic groups (for example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl) , Butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamide Phenyl , De de white ylamide phenyl group, and the like).

T ₁ In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group, and the like).

G ₀ preferably represents a hydrocarbon group having 1 to 22 carbon atoms,
Specifically, representing the same contents as those described for D ₁ described above. However, in the carbon chain of the G ₀ -O -, - CO
_{-, - CO 2 -, -} OCO -, - SO 2, May be contained. Here, D ₂ represents the same content as D _1.

d ₁ and d ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -CO
O-D ₃ or -CH ₂ COOD ₃ (D ₃ is a hydrogen atom or a carbon atoms 1 to 1
8 alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, a specifically represent the same contents as those described above D ₁₎ Express.

Further, in the macromonomer (M _A ) provided in the present invention, G ₀ in the general formula (III) as a constituent repeating unit has at least one specific polar group, and a repeating unit component in a molecule. Having at least two or more specific polar groups in the general formula (III)
The component of a) is preferably contained.

General formula (IIIa) In the formula (IIIa), d ₁ , d ₂ and T ₁ are as described above.

J ₁ and J ₂ may be the same or different from each other;
-, - CO -, - CO 2 -, - OCO -, - SO 2 -, The representative (D ₄ represents the same content as D ₁ of the formula (III)).

W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms (as the hydrocarbon group, an alkyl group, an alkenyl group, an aralkyl group or an alicyclic group) which may be interposed in the bond of the main chain. Specific examples of preferable these aliphatic groups may include the same content as the preferred aliphatic groups D ₁ of the formula (III).

However, J ₃ and J _4, which may be the same or different, said J ₁
And J ₂ represent the same content and, W ₃ is the same content as W ₁ or W _2, represents a substituted also good C1-18 hydrocarbon group.

Further, for W ₁ and W ₂ , specific examples include: (D ₅ and D ₆ represent a hydrogen atom, an alkyl group, a halogen atom, etc.), CHCHCH, (J ₃ , J ₄ , W ₃ , G ₁ and p represent the same symbols as described above).

m, n and p may each be the same or different;
Represents the numbers 1, 2, and 3. However, none of them is 0 at the same time.

G ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. Preferably, it represents a aliphatic which may be substituted having 1 to 22 carbon atoms, specifically, represent the same contents as D ₁ of the formula (III).

Further, in the formula (IIIa), T ₁ , W ₁ , J ₁ , W ₂ , J ₂
And the total number of atoms of each atomic group of G ₁ is preferably 8 or more.

Specific examples of the repeating unit represented by the general formula (IIIa) as described above are further described below. However, the content of the present invention is not limited to these.

In the following, a is -H or -CH _3; an alkyl group R 'is a hydrogen atom or a C _1-18;; R an alkyl group of C _1-18 is k _1,
k ₂ each 1-12 of integer; l ₁ represents an integer of 1 to 100.

The macromonomer (M _A ) used in the present invention is represented by the general formula (IV) only at one end of the main chain of the polymer comprising the repeating unit represented by the general formula (III) as described above. The polymerizable double bond group has a chemical structure in which it is directly bonded or bonded through an arbitrary connecting group.

In the formula (IV), T ₂ has the same meaning as T ₁ in the formula (III), e ₁ and e ₂ may be the same or different from each other, and d ₁ or d _{2 in the} above formula (III) Is synonymous with T ₂ , e ₁ and e ₂
Are preferably the same as those described above for T ₁ , d ₁ and d ₂ .

More preferably, _one of d ₁ and d _{2 in} the formula (III) or e ₁ and e _{2 in} the formula (IV) is a hydrogen atom.

Examples of the group linking the components of formula (III) and formula (IV) include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen Atoms, silicon atoms, etc.), and any combination of heteroatom-heteroatom bond atomic groups.

Etc. Among macromonomers of the present invention (M _A) are those such formula (VI) and (VI a).

In the formulas (VI) and (VIa), except for A, the formula (III),
It represents the same symbol as each symbol in formula (IIIa) and formula (VI).

A is a single bond or [D ₇ and D ₈ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group) Etc.), CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, (D ₉ and D ₁₀ each independently represent a hydrogen atom, a hydrocarbon group having the same content as D ₁ , etc.) or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

In the general formula (IV), (IV) or (VIa),
Particularly preferred examples of each of d ₁ , d ₂ , e ₁ , e ₂ , T ₁ , and T ₂ are shown below.

The _{T 1, -COO -, - OCO} -, - O -, - CH 2 COO
— Or —CH ₂ OCO—, as T ₂ , all of the above (where D ₁ is a hydrogen atom), but d ₁ , d ₂ , e ₁ and e ₂ are each a hydrogen atom or a methyl group Is mentioned.

Hereinafter, the compounds represented by the general formulas (VI) and (VIa) A specific example will be described. However, the content of the present invention is not limited to these.

In the following, b is -H or -CH _3; m ₁ is an integer of 1 to 12; n ₁ is an integer of 2 to 12.

Further, the macromonomer (M _A ) used in the present invention may contain other repeating units as copolymer components together with the repeating units represented by the general formula (III) or (IIIa). As the other copolymer component, any compound may be used as long as it is a monomer copolymerized with a monomer corresponding to the repeating unit of the general formula (III). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, and 4-pentenoic acid, and esters or amides of these unsaturated carboxylic acids, and fatty acids having 1 to 22 carbon atoms Examples include vinyl esters or allyl esters, vinyl ethers, styrene and styrene derivatives, and heterocyclic compounds containing an unsaturated bond group. Specifically, for example, the compounds exemplified for the above-mentioned monomer (A) and the like can be mentioned, but it should not be construed that the invention is limited thereto.

In the sum of the repeating units of the macromonomer (M _A ),
The repeating unit component represented by the general formula (III) or (IIIa) is preferably contained in an amount of 40% by weight or more, more preferably 60 to 100% by weight.

When the content of the component represented by the general formula (III) is less than 40% by weight, the mechanical strength of the image area formed by the dispersed resin particles is not sufficiently maintained, and therefore, the printing durability when used as an offset master. The effect of improvement cannot be seen.

The above-mentioned macromonomer (M _A ) of the present invention preferably has a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ and preferably 2 × 10 ^{3 to} 9
× 10 ³ is more preferred.

The upper limit of the number average molecular weight of macromonomer (M _A ) is 1 × 10
^If it exceeds ⁴ , printing durability will decrease. On the other hand, if the molecular weight is too small, soiling tends to occur, so it is preferably 1 × 10 ³ or more.

The macromonomer (M _A ) of the present invention can be produced by a conventionally known synthesis method. For example, a method using an ionic polymerization method in which various reagents are reacted with the terminal of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer, a reactive group such as a carboxyl group, a hydroxy group, or an amino group in a molecule. By reacting an oligomer having a terminal reactive group bond obtained by radical polymerization with various reagents using a polymerization initiator and / or a chain transfer agent containing A method by a polyaddition condensation method in which a polymerizable double bond group is introduced into the oligomer obtained by the polycondensation reaction in the same manner as in the above-mentioned radical polymerization method.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp & E.Franta, A
dv, Polym.Sci., 58 , 1 (1984), V.Percec, Appl.Polym.Sc
i., 285, 95 (1984), R. Asami & M. TakaRi, Makvamol. Ch
em.Suppl., 12 , 163 (1985), P. Remppet al, Makvamol.Ch
em. Suppl., 8 , 3 (1984), Yusuke Kawakami "Chemical Industry" 38 , 56
(1987), Yuya Yamashita "Polymer" 31 , 988 (1982), Shiro Kobayashi "Polymer" 30 , 625 (1981), Toshinobu Higashimura "Journal of the Adhesion Society of Japan" 18 , 536 (1982), Koichi Ito "High molecular processing "35, 262
(1986), Takashiro Higashi, Takashi Tsuda "Functional Materials" 1987 , No.10,5
And can be synthesized according to the methods described in the literatures and patents cited therein.

The dispersion resin of the present invention comprises at least one of each of a monomer (A) and a macromonomer (M _A ). What is important is that a resin synthesized from these monomers is insoluble in the non-aqueous solvent. If so, a desired dispersion resin can be obtained.

More specifically, for the monomer (A) to be insolubilized,
It is preferred to use macromonomer (M _A) 0.05 to 10 wt%, more preferably from 0.1 to 5 wt%. Still more preferably, it is 0.3 to 3% by weight.

The molecular weight of the dispersion resin of the present invention is from 1 × 10 ³ to 1 × 10 ⁶ , preferably from 1 × 10 ^{4 to} 5 × 10 ⁵ .

The dispersion stabilizing resin used in the present invention comprises a monofunctional macromonomer (MM) composed of an AB type block copolymer component and a monomer (B) represented by the general formula (II). A graft copolymer obtained by polymerizing at least one kind of each, and characterized by being soluble in the non-aqueous solvent.

Particularly, in the graft portion of the graft copolymer, a block portion separated from the graft copolymer main chain (ie,
A block) is a specific polar group (-COOH group,-
PO ₃ H ₂ group, -SO ₃ H group, -OH group, The same as the polymer component containing at least one polar group selected from carboxyamide group, sulfoamide group, formyl group, amino group, and cyclic acid anhydride-containing group) and / or the monomer (A) to be insolubilized Characterized by comprising a polymer component corresponding to the above-mentioned monomer.

The weight average molecular weight of the graft copolymer is 1.5 × 10 ⁴ to
It is 3 × 10 ⁵ , preferably 2 × 10 ⁴ to 1 × 10 ⁵ .

When the weight average molecular weight is less than 1.5 × 10 ⁴ or more than 3 × 10 ⁵ , the average particle size of the resin particles obtained by polymerization granulation becomes coarse or the particle size distribution becomes wide, and the monodispersion occurs. The properties are impaired, and further, they are not dispersed but aggregated.

The proportion of the monofunctional macromonomer (MM) as a copolymer component of the graft copolymer is from 1% by weight to 60% by weight, preferably from 5% by weight to 40% by weight. If the ratio is less than 1% by weight, the number of grafted portions is significantly reduced, and the chemical structure becomes similar to that of the conventional random copolymer. I will not be able to. On the other hand, when the proportion exceeds 60% by weight, the copolymerizability with the monomer (B) represented by the general formula (II) becomes insufficient.

The proportion of the monomer (B) represented by the general formula (II), which is another copolymer component, in the graft copolymer is 40 to 99% by weight, preferably 60 to 95% by weight. %.

On the other hand, the weight average molecular weight of the monofunctional macromonomer (MM) of the present invention which becomes the graft portion of the graft copolymer is 1 × 10 ³ to 2 × 10 ⁴ , preferably 2 × 10 ³ to
It is 1 × 10 ⁴ . When the weight average molecular weight is less than 1 × 10 ³ , the redispersibility of the obtained dispersed resin particles is reduced. ^{On the other hand} , when it exceeds 2 × 10 ⁴ , the copolymerizability with the monomer (B) represented by the general formula (II) is lowered, so that a graft copolymer cannot be obtained.

Since the graft copolymer of the present invention as described above is soluble in the non-aqueous solvent, the polymer containing a repeating unit represented by the general formula (I) in the main chain portion or the graft portion of the polymer may be used.
One or both of the blocks contain a repeating unit that becomes soluble.

Hereinafter, the content of the graft copolymer will be described in more detail.

In the monofunctional macromonomer (MM) provided for the graft copolymer, as a polymer component constituting the A block, a component containing a specific polar group and / or an insolubilized monofunctional monomer ( Components corresponding to A) can be mentioned.

Specific polar groups include a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, a carboxamide group, a sulfamide group, an amino group, And cyclic acid anhydride-containing groups.

In the formula, R ₁₁ represents a —R ₁₂ group or an —OR ₁₂ group, and R ₁₂ represents a hydrocarbon group. The hydrocarbon group is preferably an aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxy group). Propyl, allyl, 1-propenyl, butenyl, cyclohexyl, benzyl, phenethyl, 3-phenylpropyl, methylbenzyl, chlorobenzyl, fluorobenzyl, methoxybenzyl, etc.) or substituted Aryl group (eg, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl,
Chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Examples of the monomer capable of deriving the “polymer component containing a specific polar group” as described above include, for example, a polymer component constituting the other block component of the AB block copolymer of the present invention [that is, a general polymer component] Any of the vinyl compounds which can be copolymerized with the vinyl compound corresponding to the repeating unit represented by the formula (I)] and have a polar group can be used. For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy, α-acetoxymethyl, α- (2-amino) methyl, α-chloro, α-bromo) , Α-fluoro body, α-tributylsilyl body, α-cyano body, β-chloro body, β-bromo body, α
-Chloro-β-methoxy, α, β-dichloro, etc.),
Methacrylic acid, itaconic acid, itaconic acid half esters,
Itaconic acid semiamides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-
Hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid,
Maleic acid half-esters, maleic acid half-amides, vinylbenzene carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and carboxylic acids or sulfonic acids thereof And a compound containing the polar group in the substituent of the ester derivative or the amide derivative.

The following are specific examples of these compounds. However, in each of the following examples, e is -H, -CH
_3, -Cl, -Br, -CN, indicates -CH ₂ COOCH ₃ or -CH ₂ COOH, f represents -H or -CH _3, n ₁ represents an integer of 2 to 18, m ₁ is 1 Represents an integer of ₁ to 12, and l ₁ represents an integer of ₁ to 4.

The polymer component constituting the A block may be a polymer component corresponding to the monomer (A) which is insolubilized by polymerization in addition to the specific polar group-containing polymer component as described above.
Specific examples thereof include a polymer component corresponding to the above-described monofunctional monomer (A).

The B block is at least composed of a polymer component comprising a repeating unit represented by the general formula (I).

In the general formula (I), V ₀ represents —COO—, —OCO—, (L ₁ and l ₂ represent an integer of 1 to 3), -O-, -SO
_2- , -CO-, −CONHCOO−, −CONHCONH−, or Represents

Here, in addition to a hydrogen atom, R ₁₃ is preferably a hydrocarbon group which may be an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group). 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.), 18 optionally substituted alkenyl groups (e.g., 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.) An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-
A naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms ( For example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group, etc.), or C6-C6
12 optionally substituted aromatic groups (for example, phenyl group,
Naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

V ₀ In the case where is represented, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy groups,
And a propoxy group and a butoxy group).

R ₀ represents a hydrocarbon group, and a preferable hydrocarbon group is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group) Octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, 3-bromopropyl group and the like, an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-
Butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-
Hexenyl group, 4-methyl-2-hexenyl group and the like, and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example,
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.) Good alicyclic groups (for example, cyclohexyl group, 2-
A cyclohexylethyl group, a 2-cyclopentylethyl group, etc., an aromatic group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
A bromophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, and a dodecyloylamidophenyl group.

a ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
A bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), - COO-Z ₁ or -COO-Z ₁ via a hydrocarbon ( Z
₁ is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, these may be substituted, specifically, the R ₁₃ Represents the same contents as those described for ().

Examples of the hydrocarbon in the —COO—Z ₁ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group.

More preferably, for general formula (I), V ₀ is -COO
-, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CON
H -, - SO ₂ NH- or And a ₁ and a ₂ may be the same or different from each other, and each represents a hydrogen atom, a methyl group, —COOZ ₁ or —CH ₂ COOZ ₁ . Here, Z ₁ more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, either a ₁ or a ₂ represents a hydrogen atom.

Furthermore, acrylonitrile, methacrylonitrile, and heteropolymer as monomers corresponding to other repeating units copolymerizable with the polymer component represented by the formula (I) as the polymer component contained in the B block. Cyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylprazole, vinyldioxane, vinyloxazine, etc.); These other monomers are contained in 2 parts by weight of 100 parts by weight of the total polymer
Used within a range not exceeding 0 parts by weight. Further, it is preferable that the B block does not contain a polymer component containing a polar group, which is a component of the A block.

In the monofunctional macromonomer (MM) used for the graft copolymer of the present invention, the proportion of the blocks A and B in the AB block copolymer is 1 to 50/99.
It is preferably from 50 to 50 (weight ratio).

The specific polar group-containing polymer component contained in the A block is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the dispersion stabilizing resin.

Next, in the macromonomer (MM) of the present invention, the A block composed of the above-mentioned component containing a polar group and the B block composed of the polymer component represented by the general formula (I) are represented by A-
The polymerizable double bond group linked to the B block and linked to the other end of the B block linked to the A block will be described.

Specific examples include a polymerizable double bond group represented by the following general formula (VII).

General formula (VII) In the formula (VII), V ₂ has the same content as V ₀ in the formula (I).

g ₁ and g ₂ may be different from each other, and in the formula (I)
Represents the same contents as a ₁ and a ₂ .

That is, as the polymerizable double bond group represented by the general formula (VII), more specifically, CH ₂ = CH-O-, CH ₂ = CH-CO-, And the like.

The macromonomer (MM) used in the present invention is obtained by directly bonding a polymerizable double bond group represented by the general formula (VII) to one end of the B block as described above, or
It has a chemical structure linked by an arbitrary linking group.

As the linking group, a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom It is composed of a combination of bonding atomic groups.

That is, specifically, a simple bond or [R ₁₄ and R ₁₅ may be the same or different and include a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, Propyl group, etc.), CH
= CH, -O-, -S-, -COO-, −SO ₂ −, -NHCOO-, -NHCONH-, [R ₁₆ and R ₁₇ may be the same or different and each represent a hydrogen atom or a hydrocarbon group having the same content as R ₀ in the above formula (1)] It represents a linking group or a linking group composed of any combination.

The macromonomer (MM) of the present invention can be produced by a conventionally known synthesis method. For example, in the monomer corresponding to the polymer component containing the specific polar group,
A polar group is set as a functional group protected in advance, and an ionic polymerization reaction using an organometallic compound (eg, alkyllithiums, lithium diisopropylamide, alkylmagnesium halides, etc.) or a hydrogen iodide / iodine system, and a porphyrin metal complex as a catalyst. After synthesizing an AB block copolymer by a known so-called living polymerization reaction such as a photopolymerization reaction or a group transfer polymerization reaction, various ends of the living polymer are reacted with various reagents to form a polymerizable double bond group. Is introduced. Thereafter, a method of forming a polar group by performing a deprotection reaction by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction, or the like on the functional group in which the polar group is protected, is mentioned. One example is shown in the following reaction scheme (1).

For example, P. Lutz, P. Masson et al, "Polym. Bull." 12 , 7,
9 (1984), BCAnderson, GDAndrews et al, “Macrom
olecules " 14 , 1601 (1981), K. Hatada, K.ute et al," P.
olym.J. "17, 977 (1985) , the same 18, 1037 (1986), the right hand Koichi, Koichi Hatada" Polymer Processing "36, 366 (1987), Higashimura Satoshinobe, Mitsuo Sawamoto" polymer Collected Papers "46 , 189 (1989), M. Kuro
ki, T. Aida, “J. Am. Chem. Soc.” 109 , 4737 (1987), Takuzo Aida, Shohei Inoue “Synthetic Organic Chemistry” 43 , 300 (1985), DY
Sogah, WRHertler et al, "Macromolecules " 20, 1473
(1987) and the like, and a living polymer can be easily synthesized. Further, as a method of introducing a polymerizable double bond group at the terminal of the living polymer,
The macromonomer of the present invention can be easily obtained according to a synthesis method of a conventionally known macromonomer method.

Specifically, see P. Dreyfuss & RPQuirk, “Encycl.Pol
ym.Sci.Eng. "7, 551 (1987 ), PFRempp, E.Franta," A
dv.Polym.Sci. " 58 , 1 (1984), V. Percec," Appl.Polym.
Sci. " 285, 95 (1984), R. Asami, M. TakaRi," Makvamol.
Chem. Suppl. " 12 , 163 (1985); P. Rempp et al," Makvam
ol. Chem. Suppl. " 8 , 3 (1984), Yusuke Kawakami" Chemical Industry " 3
8 , 56 (1987), Yuya Yamashita "Polymer" 31 , 988 (1982), Shiro Kobayashi "Polymer" 30 , 625 (1981), Toshinobu Higashimura "Journal of the Adhesion Society of Japan" 18 , 536 (1982), Ito Koichi "Polymer Processing" 35 , 2
62 (1986), Kishiro Higashi, Takashi Tsuda "Functional Materials" 1987 No.1
It can be synthesized according to the methods described in the reviews such as 0, 5 and references and patents cited therein.

Further, the protective group for protecting the specific polar group of the present invention and the elimination of the protective group (deprotection reaction) can be easily carried out using conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977)
TWGreene, “Protective Groups in Organic Sy
ntheses "John Wiley & Sons (1981), JFW McOmi
e, “Protective Groups in Chemistry” Plenum Press (1
973) can be carried out by appropriately selecting a method described in detail in a review article.

As another method for synthesizing an AB type block copolymer, a photoiniferter polymerization method using a dithiocarbamate compound as an initiator can be used. For example, Takayuki Otsu "polymer" 37, 248 (1988), Hinokimori Shunichi, Ryuichi Otsu "Polym.Rep.Jap." 37, 3508 ( 1988), JP-A-64-111
And the synthesis method described in JP-A-64-26619. The macromonomer of the present invention can be obtained by utilizing the above-mentioned macromonomer synthesis method.

Specific examples of the macromonomer (MM) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

In the following, a ₁ , a ₂ , a ₃ represent —H, —CH ₃ or —CH ₂ COOCH ₃ ; R represents —C _n H
_{2n + 1} (n: _{1~18 integer), CH 2 2 C 6 H} 5 (m: 1~3 integer), (X is _{-H, -Cl, -Br, -CH 3} , -OCH 3, or -COCH _3), or (P is an integer of 0 to 3) a; l is an integer of 2 to 12; a ₄ is -H or -CH _3; Y is -OH, -COOH, -SO ₃ H, Y 'is -COOH, -SO ₃ H, R 'is _{-C m H 2m + 1 (m} : 1~8 integer), or CH _{2 m} C ₆ H ₅
And k represents an integer of 2 to 6.

 -B- represents a block bond.

The dispersion stabilizing resin of the present invention is a graft copolymer containing at least one kind of the monomer (B) represented by the general formula (II) together with the monofunctional macromonomer (MM). .

In the general formula (II), V ₁ is preferably -COO-, -O
Represents CO- or -O-.

R ₁ represents an aliphatic group having 8 or more carbon atoms, preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms,
These may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc. .

b ₁ and b ₂ may be different or the same, and each preferably represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Specifically, hydrogen atom, chlorine atom,
Examples thereof include a bromine atom, a methyl group, an ethyl group, and a propyl group.

Further, as a component of the graft copolymer of the present invention, a macromonomer (MM) and a monomer (B) represented by the formula (II)
In addition, other monomers copolymerizable with these may be contained, but the content thereof is 20% by weight or less, preferably 15% by weight or less.

In order to produce the dispersion resin used in the present invention, generally, the dispersion-stabilizing resin of the graft copolymer of the present invention as described above, the monofunctional monomer (A) and the monofunctional macromonomer (M _A ) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (A) and a macromonomer (M _A ), A method of dropping the isomer (A) and the macromonomer (M _A ) together with the polymerization initiator,
Alternatively, a method of optionally adding the remaining monomer mixture together with a polymerization initiator to a mixed solution containing a total amount of the dispersion stabilizing resin and a mixture of the monomer (A) and the macromonomer (M _A ), Further, there is a method of optionally adding a mixed solution of a dispersion stabilizing resin and a monomer (A) and a macromonomer (M _A ) together with a polymerization initiator in a non-aqueous solvent,
It can be manufactured using any method.

The total amount of the monomer (A) and the macromonomer (M _A ) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent.

The amount of the soluble resin serving as the dispersion stabilizing resin is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of the polymerization initiator is suitably from 0.1 to 5% by weight based on the total amount of the monomers.

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

In the non-aqueous solvent used for the reaction, the alcohols described above,
When polar solvents such as ketones, ethers and esters are used in combination, or when the unreacted product of the monomer (A) to be polymerized and granulated remains, the boiling point of the solvent or monomer is increased. It is preferable to remove by heating or distilling off under reduced pressure.

As described above, the non-aqueous dispersion resin produced according to the present invention exhibits very stable dispersibility at the same time as being present as fine particles having uniform particle size distribution, and can be used repeatedly for a long time especially in a developing device. However, even if the dispersibility is good and the developing speed is improved, re-dispersion is easy, and it is not recognized at all that any contamination occurs on each part of the apparatus.

Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited.

Further, the liquid developer of the present invention has a rapid development-fixing process and is excellent in dispersion stability, re-dispersibility and fixability even when a large-size master plate is used.

In particular, JP-A-62-166362 or JP-A-63-66567
In the non-aqueous dispersion resin having the content described in the above item, together with a monomer containing at least two or more ester bonds or the like in the molecule, which can be copolymerized with a monomer that is polymerized and insolubilized, from the polymer main chain Resin polymerized and granulated using a random copolymer soluble in the non-aqueous solvent containing a copolymerizable component having a polymerizable double bond group at a site separated by at least 8 atoms, as a dispersion stabilizing resin. Particles (latex particles) whose dispersibility and printing durability have been greatly improved compared to conventional particles, but a plate making machine using a large-size offset printing master plate. (For example, ELP-560, ELP-820, etc., manufactured by Fuji Photo Film Co., Ltd.),
Alternatively, if the processing speed of the plate making machine is increased, there is still a problem in the dispersibility of the particles, and the plate making machine becomes dirty (especially, the developing device becomes dirty), the particles aggregate and settle, or the master plate is removed. At the time of printing, the strength of the image area was not yet sufficient, and the printing durability was reduced. When the resin particles used in the present invention are used, no problem occurs even under such severe conditions.

As described above, the high redispersibility of the latex particles of the present invention is due to the insolubilizable monomer (A) and macromonomer (M _A )
It depends on the soluble graft copolymer used together.

That is, the dispersion stabilizing resin of the present invention has a polymer main chain portion composed of a polymer component containing a long-chain aliphatic group having a high affinity for the non-aqueous solvent, and a small affinity for the non-aqueous solvent, It is a graft copolymer in which a graft block end block composed of a polymer component having an affinity for the monomer (A) to be insolubilized is bonded.

Thereby, the block B portion of the graft portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the polymer main chain portion having a high affinity for the non-aqueous dispersion medium is formed. It is presumed that sufficient solvation of the solvent and steric repulsion effect can be sufficiently exerted (so-called tail-like adsorption), and the effect of the present invention has been achieved.

On the other hand, in a conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, in the polymer chain in which the component serving as the adsorbed portion is composed of a solvating component. Randomly bonded to the resin particles, the adsorption to the dispersed resin particles was not sufficient, and further, the adsorption pattern became loop-shaped, so that the steric repulsion effect was also alienated, and the dispersion stability was not sufficient. .

Moreover, it high printing durability, good compatibility with the monomer copolymerized with the macromonomer (M _A) to be insolubilized is also under mild fixing conditions, which sufficiently compatibilized to form a uniform film It is estimated that this is achieved.

If desired, a colorant may be used in the liquid developer of the present invention. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used.

In the case of coloring the dispersion resin itself, for example, as one of the coloring methods, there is a method of physically dispersing the dispersion resin in a dispersion resin using a pigment or a dye. I have. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red, phthalocyanine blue and the like can be mentioned.

As another method of coloring, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, there is a method in which a dispersing resin and a dye are chemically bonded as disclosed in JP-A-53-54029.
As described in JP-A-44-22955 and the like, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol.
And those specifically described on page 44 are used.

For example, di-2-ethylhexylsulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin,
Examples include poly (vinylpyrrolidone) and a copolymer containing a semi-maleic acid amide component.

The amounts of the main components of the liquid developer of the present invention will be described below.

The toner particles mainly composed of a resin (and a coloring agent optionally used) are used in an amount of 0.1 parts by weight per 1000 parts by weight of the carrier liquid.
5 parts by weight to 50 parts by weight are preferred. When the amount is less than 0.5 part by weight, the image density is insufficient, and when the amount is more than 50 parts by weight, fogging to a non-image portion is liable to occur. Further, the carrier liquid soluble resin for stabilizing the dispersion is also used as desired, and about 0.5 to 100 parts by weight can be added to 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, the electric resistance of the liquid developer from which the toner particles have been removed is 10 ⁹ Ωc
If it is lower than m, it becomes difficult to obtain a good quality continuous tone image, so it is necessary to control the amount of each additive within this limit.

(Examples) Hereinafter, a synthesis example of the dispersion stabilizing resin according to the present invention, a production example of latex particles and an example will be described, but the content of the present invention is not limited thereto.

Synthesis Example 1 of Macromonomer (MM) 1: MM-1 30 g of triphenylmethyl methacrylate and toluene 1
00 g of the mixed solution was sufficiently degassed under a nitrogen stream and cooled to -20 ° C.

2 g of 1,1-diphenylbutyllithium was added and reacted for 10 hours.

Further, to this mixed solution, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was sufficiently degassed under a nitrogen gas stream, and then added, followed by further reacting for 10 hours. After the mixture was cooled to 0 ° C., carbon dioxide gas was bubbled at a flow rate of 60 ml / min for 30 minutes to terminate the polymerization reaction.

The obtained reaction solution was brought to a temperature of 25 ° C. with stirring, 6 g of 2-hydroxyethyl methacrylate was added, and a mixed solution of 5 g of dicyclohexylcarbodiimide, 0.2 g of 4-N, N-dimethylaminopyridine and 10 g of methylene chloride was further added. The mixture was added dropwise over 30 minutes and stirred for 3 hours.

After filtering out the precipitated insoluble matter, 10 ml of a 30% ethanol solution of hydrogen chloride was added to the mixed solution, and the mixture was stirred for 1 hour. Next, the solvent was distilled off under reduced pressure until the total amount of the reaction mixture became half, and the reaction mixture was reprecipitated in petroleum ether 1.

The precipitate was collected, dried under reduced pressure, and the polymer obtained had a weight average molecular weight of 6.5 × 10 ³ and a yield of 56 g.

Synthesis Example 2 of Macromonomer (MM): MM-2 5 g of benzyl methacrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and methylene chloride 60
g of the mixed solution was adjusted to a temperature of 30 ° C. under a nitrogen stream. 300 for this
W-xenon lamp light 25cm through glass filter
And irradiated for 12 hours. 45 g of butyl methacrylate was further added to the mixture, and the mixture was irradiated with light for 8 hours in the same manner. Then, 4-bromomethylstyrene was added to the reaction mixture.
4 g was added, and the mixture was stirred for 30 minutes to stop the reaction.

Next, Pd-C was added to the reaction mixture, and a catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, the precipitate was reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The obtained polymer has a yield of 33.
In g, the weight average molecular weight was 7 × 10 ³ .

Synthesis Example 3 of Macromonomer (MM) MM-3 A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed under a nitrogen stream, and cooled to 0 ° C. 2 g of lithium 1,1-diphenyl-3-methylpentyl was added, and the mixture was stirred for 6 hours. Further, to this mixture, a mixed solution of 80 g of dodecyl methacrylate and 100 g of toluene was sufficiently degassed under a nitrogen stream and then added, followed by a reaction for 8 hours. After ethylene oxide was bubbled through the reaction mixture at a flow rate of 30 ml / min for 30 minutes while sufficiently stirring, the mixture was cooled to a temperature of 15 ° C., 10 g of methacrylic acid chloride was added dropwise for 30 minutes, and the mixture was further stirred for 3 hours.

The reaction mixture is then added to a 10% 30% hydrogen chloride ethanol solution.
g and stirred at 25 ° C. for 1 hour.
Re-precipitate in and collect the collected precipitate in diethyl ether (300 ml).
And dried twice.

The obtained polymer had a weight average molecular weight of 7.8 × 10 with a yield of 55 g.
^{Was 3} .

Synthesis Example 4 of Macromonomer (MM): MM-4 40 g of triphenylmethyl acrylate and 100 of toluene
g of the mixed solution was sufficiently degassed under a nitrogen stream and cooled to -20 ° C. 0.2 g of sec-butyllithium was added and reacted for 10 hours.

Next, 60 g of octadecyl vinyl ether was added to this mixed solution.
After sufficiently degassing a mixed solution of 100 g of toluene and 100 g of nitrogen in a nitrogen stream, the mixture was added and reacted for 12 hours. After the mixture was cooled to 0 ° C., 4 g of benzyl bromide was added and reacted for 1 hour.
The reaction was further performed at a temperature of 25 ° C. for 2 hours.

The reaction mixture was added to 10% ethanol solution containing 30% hydrogen chloride.
Was added and stirred for 2 hours. After filtering off the insoluble matter, the precipitate was reprecipitated in n-hexane 1, and the precipitate was collected and dried under reduced pressure. The yield of the liquid polymer was 58 g, and the weight average molecular weight was 4.5 × 10 ^3.
Met.

Synthesis Example 5 of Macromonomer (MM): A mixture of 70 g of MM-5 octadecyl ethacrylate and 4.8 g of benzyl-N-hydroxyethyl-N-ethyldithiocarbamate was sealed in a container under a nitrogen stream, and the temperature was raised to 60 ° C. Heated.

This was irradiated with light for 10 hours through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp, and photopolymerized.

After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen and light irradiation was performed again for 10 hours.

6 g of 2-isocyanatoethyl methacrylate was added dropwise to the obtained reaction mixture at a temperature of 30 ° C. for 1 hour, and the mixture was further stirred for 2 hours.

The obtained reaction product was reprecipitated in hexane 1.5, collected and dried. The resulting polymer is 68 g and has a weight average molecular weight of 6.0 ×
It was 10 ³ .

Synthesis Example 1: Dispersion stabilizing resin 1: P-1 Octadecyl methacrylate 80 g, macromonomer MM
A mixed solution of 20 g of -1 and 150 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream.

2,2'-azobis (isobutyronitrile) (abbreviation: AI
BN) 6g and react for 4 hours, then AIBN every 3 hours
Was added and reacted for 6 hours.

The weight average molecular weight of the obtained copolymer was 5 × 10 ⁴ .

Synthesis Examples 2 to 12 of Dispersion Stabilizing Resins: P-2 to P-12 Polymers shown in Table 1 below were synthesized by the same polymerization method as in Synthesis Example 1 of dispersion stabilizing resins. The weight average molecular weight of each of the obtained polymers was 3 × 10 ^{4 to} 6 × 10 ⁴ .

Synthetic Examples P-13 to 35 of Dispersion Stabilizing Resin In Synthetic Example 1 of the resin, except that another macromonomer (MM) was used in place of the macromonomer MM-1, the following polymerization conditions were used. -2 copolymer was synthesized. The weight average molecular weight of each polymer obtained is 3 × 10 ⁴ -7.
× 10 ⁴

Preparation of Macromonomer M _A 1: M _A -1 methyl methacrylate 100 g, a 3-mercapto mixed solution of propionic acid 5g and toluene 200 g, while stirring under a nitrogen gas stream, was heated to a temperature of 75 ° C.. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviated AIBN) was added and reacted for 4 hours, and 0.5 g of AIBN was added for 3 hours.
Was added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate and N, N-dimethyldodecylamine were added to the reaction solution.
1.0 g and t-butyl hydroquinone 0.5 g were added, and the temperature was 10
The mixture was stirred at 0 ° C for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 82 g of a white powder. The number average molecular weight of the polymer was 6,500.

Preparation of Macromonomer M _A two to thirty-nine: Production Example 1 of M _A -2~M _A -39 macromonomer M _A, except that instead of the compound corresponding only methyl methacrylate in the following Table 3 are prepared Examples Macromonomer M _A-2
It was synthesized M _A -39. The number average molecular weight of each obtained macromonomer was in the range of 5,000 to 7,000.

Preparation of Macromonomer M _A 40: M _A -40 2,3- dipropylcarbamoylmethyl propyl methacrylate 96 g, while the mixed solution of thioethanol 4g and toluene 200g stirred under a nitrogen gas stream was heated to a temperature of 70 ° C.. 1.0 g of AIBN
The reaction was performed for 4 hours. Add 0.5g of AIBN and 3 hours,
Thereafter, 0.3 g of AIBN was further added and reacted for 3 hours. The reaction solution was cooled to room temperature, 16.2 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 60 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 filtrate obtained by filtering out the precipitated crystals was separated into methanol 2
Re-sinked inside.

The precipitated oil was collected by decantation, dissolved in 150 ml of methylene chloride and reprecipitated in methanol 1. The oil was collected and dried under reduced pressure to yield 54 g.
Thus, a polymer having a number average molecular weight of 6.30 × 10 ³ was obtained.

Preparation of Macromonomer M _A 41 to 47: Production Example of M _A ~41~M _A -47 macromonomer M _A -40, (equivalent to 2,3 dipropionate propyl methacrylate) methacrylate monomer and an unsaturated carboxylic acid (2-carboxyethyl corresponding ethyl methacrylate) instead respectively, in the same manner as production example M _a -40, we were prepared respectively macromonomer table -4. The number average molecular weight of each of the obtained macromonomers was in the range of 5 × 10 ³ to 8 × 10 ³ .

Preparation of Macromonomer M _A 48: M _A -48 dodecyl methacrylate 90 g, methacrylic acid 10 g, a mixed solution of thioethanol 5g and toluene 200 g, was heated to 70 ° C. with stirring under a nitrogen gas stream. 1.0 g of AIBN was added and reacted for 4 hours. Furthermore, 0.5g of AIBN is added and 3 hours,
Thereafter, 0.3 g of AIBN was further added and reacted for 3 hours. The reaction solution was cooled to room temperature, 20.2 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 10.2 g of DCC and 60 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 obtained filtrate was reprecipitated in methanol 2. The precipitated oil was collected by decantation, and dissolved in 150 ml of methylene chloride.
It re-sedimented again. Collect the oil, dry under reduced pressure,
A polymer having a number average molecular weight of 5,800 was obtained in a yield of 54 g.

Preparation of Macromonomer M _A 49: M _A -49 n- dodecyl methacrylate 70 g, t-butyl methacrylate 30g, a mixed solution of 2-mercaptoethylamine 4g and tetrahydrofuran 200g was heated to a nitrogen stream under temperature of 70 ° C.. Add 1.0g of AIBN and react for 4 hours.
0.5 g of BN was added and reacted for 4 hours. Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C., 7.9 g of triethylamine was added, and 6.3 g of acrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C., and stirred for 4 hours. After cooling, reprecipitation in methanol 2 was performed twice to obtain 63 g of a pale yellow viscous substance. The number average molecular weight was 6,600.

Preparation of Macromonomer M _A 50: M _A -50 octadecyl methacrylate 100 g, a mixed solution of tetrahydrofuran 150g and isopropyl alcohol 50g under a stream of nitrogen, was heated to a temperature of 75 ° C.. 4.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) was added and 5
After reacting for 1.0 hour, 1.0 g of ACV was further added and reacted for 4 hours.
After cooling, the reaction solution was reprecipitated in 1.5 of methanol, and the oil was collected by decantation and dried under reduced pressure. The yield is
85 g.

50 g of this oil, 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,
The mixture was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in petroleum ether 1 to obtain a white powder. The number average molecular weight was 7,500.

Production Example 1 of Latex Particles: D-1 _A mixed solution of 10 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 2.0 g of macromonomer MA-30 and 380 g of Isopar H was stirred under a nitrogen stream while stirring. Heated to a temperature of 75 ° C. 2,2'-azobis (valeronitrile) (abbreviation: ABV
N.) was added and reacted for 4 hours. Further, 0.4 g of ABVN was added and reacted for 2 hours. Twenty minutes after the initiator addition, cloudiness occurred,
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. 200 after cooling
Through a mesh nylon cloth, the resulting white dispersion is
It was a latex having a polymerization rate of 86% and an average particle size of 0.20 μm.

Production Example 2 of Latex Particles: D-2 _A mixture solution of 10 g of dispersion stabilizing resin P-2, 100 g of vinyl acetate, 1.0 g of macromonomer M _A- 1 and 380 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. Heated. 2,
2'-azobis (isovaleronitrile) (abbreviation AIV
N.) was added and reacted for 2 hours, and 0.6 g of AIVN was further added and reacted for 2 hours. Twenty minutes after the addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. The temperature was increased to 100 ° C., and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 88% and an average particle size of 0.21 μm.

Latex Particle Production Examples 3 to 19: D-3 to D-19 Same as Production Example 1 except that the dispersion stabilizing resin P-1 was replaced with each resin shown in Table 5 below in Production Example 1 of latex particles. Thus, each latex particle D-3 to D-19 was produced.

Preparation of latex particles 20~43: D-20~D-43 in Preparation Example 1 of latex grains D-1, a dispersion stabilizing resin P-1 and macromonomer M _A -30 in the compounds of Table -6 Except for the substitution, each latex particle was produced under the same conditions as in Production Example 1. The polymerization rate of each latex particle is 85
~ 90%.

The average particle size of the obtained particles was in the range of 0.18 to 0.25 μm, and the particle size distribution was sharp and the monodispersity was good.

Production Example 44 of Latex Particles: D-44 _A mixed solution of 90 g of vinyl acetate, 10 g of N-vinylpyrrolidone, 1.0 g of macromonomer MA-40, 18 g of dispersion stabilizing resin P-31 and 380 g of n-decane, was treated with nitrogen. The mixture was heated to a temperature of 75 ° C. while stirring under a stream of air. 1.7 g of AIBN was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 2 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.26 μm.

Production Example 45 of Latex Particles: D-45 A mixed solution of 25 g of dispersion stabilizing resin P-13 and 680 g of n-dodecane was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this solution, methyl methacrylate 100 g, the macromonomer M _A -28 1.0g, n-dodecyl mercaptan 1.0g
And a mixed solution of 0.8 g of ABVN was added dropwise over 2 hours.
After reacting for 2 hours, 0.3 g of ABVN was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had an average particle size of 0.25 μm.
m latex.

Preparation of latex particle 46: D-46 dispersion stabilizing resin P-21 to 18 g, vinyl acetate 95 g, crotonic acid 5g, macromonomer M _A -33 to 1.5g of Isopar E
468 g of the mixed solution was stirred at a temperature of 70 while stirring under a nitrogen stream.
Warmed to ° C. After adding 0.8 g of ABVN and reacting for 6 hours,
The temperature was raised to 100 ° C., and the mixture was stirred for 1 hour, and the remaining vinyl acetate was distilled off. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was 85% polymerized and had an average particle size of 0.1.
It was a 25 μm latex.

Production Example 47 of Latex Particles: D-47 _A mixed solution of 18 g of dispersion stabilizing resin P-25, 94 g of vinyl acetate, 6.0 g of 4-pentenoic acid, 1.5 g of macromonomer MA-26 and 380 g of Isopar G, While stirring under a nitrogen stream,
Heated to a temperature of 75 ° C. 0.7 g of ABVN was added and reacted for 4 hours, and further 0.5 g of ABVN was added and reacted for 2 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 48 of Latex Particles: D-48 While stirring a mixed solution of 20 g of a dispersion stabilizing resin P-33 having the following structure and 680 g of n-dodecane under a nitrogen stream, the temperature was lowered.
Heated to 60 ° C. In this solution, the macromonomer M _A- 27
, 1.2 g of methyl methacrylate, 1.0 g of n-dodecyl mercaptan and 0.8 g of ABVN were added dropwise over 2 hours. After reacting for 2 hours, 0.3 g of ABVN was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 49 of Latex Particles: D-49 _A mixed solution of 20 g of dispersion stabilizing resin P-27, 100 g of styrene, 1.0 g of macromonomer MA-43 and 380 g of Isopar H was added to a temperature of 45 ° C. while stirring under a nitrogen stream. Warmed. A hexane solution of n-butyllithium was added in an amount of 1.0 g as a solid content of n-butyllithium, and reacted for 4 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having an average particle size of 0.26 μm.

Production Example 50 of Latex Particles: (Comparative Example A) In Production Example 1 of latex particles D-1, 20 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 1.0 g of monomer (I) having the following structure and Isopar H were used. The same operation as in Production Example 1 was carried out except that 385 g of the mixed solution was used.

The resulting white dispersion had a conversion of 85% and an average particle size of 0.20 μm.
Latex. (Latex particles described in JP-A-60-179951) Production Example 51 of Latex Particles: (Comparative Example B) In Production Example 1 of latex particles D-1, 10 g of dispersion stabilizing resin R-1 having the following structure, The same operation as in Production Example 1 was carried out except that a mixed solution of 100 g of vinyl, 1 g of monomer (I) having the following chemical structure and 385 g of Isopar H was used.

The resulting white dispersion had a conversion of 86% and an average particle size of 0.24 μm.
Latex. (Latex particles described in JP-A-63-66567) Example 1 Dodecyl methacrylate / acrylic acid (copolymerization ratio: 95 /
(5 weight ratio) 10 g of the copolymer, 10 g of nigrosine and 30 g of Shellsol 71 were placed in a paint shaker (Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

The resin dispersion D-1 of Production Example 1 of latex particles was added to 30
g, 2.5 g of the above-mentioned nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol), [octadecene-half-maleic acid octadecylamide copolymer] 0.08
g was diluted with 1 of Shellsol 71 to prepare a liquid developer for electrostatography.

(Comparative Developers A and B) Two kinds of liquid developers A and B for comparison were prepared by replacing the resin dispersion in the above structural example with the following resin particles.

Comparative Liquid Developer A: Latex Particle Production Example 50 Resin Dispersion Comparative Liquid Developer B: Latex Particle Production Example 51 Resin Dispersion These liquid developers were fully automated plate making machine ELP-560 (Fuji Photo Using ELP Master II type (manufactured by Fuji Photo Film Co., Ltd.), which is an electrophotographic photosensitive material, was used as a developer of Film Co., Ltd. and exposed and developed. The plate making speed was 5 plates / min. Further, after the 2,000 sheets of ELP Master II type were processed, it was observed whether or not the toner adhered to the developing device. The blackening rate (image area) of the copied image was determined using a 30% original.

 The results are shown in Table-7.

When plate making was performed using each developer under the above-described plate making conditions, the developer which did not cause staining of the developing device and had a clear image on the 2000th plate making plate was only in the case of the present invention.

On the other hand, a master plate for offset printing (ELP master) obtained by making a plate on the tenth plate from each developer is printed by a conventional method until characters on the printed image are missing, and solid portions are blurred. When the number of printed sheets was compared, no master plate was obtained using any of the developers of the present invention and Comparative Examples A and B, even at 10,000 sheets or more.

As described above, only the developer using the resin particles of the present invention as a developer did not cause any stain on the developing device, and also significantly improved the number of printed master plates.

On the other hand, Comparative Examples A and B are used under severe plate making conditions (conventionally, the blackening rate of a copied image is about 8 to 10% at a plate making speed of 2 to 3 sheets / min). And the developing device (especially on the back electrode plate) becomes stained,
After 2,000 sheets, the quality of the copied image on the plate was affected (Dmax was reduced, fine lines were blurred, etc.). Therefore, with these master plates, when printed, the image quality of the printed matter is degraded from the start of printing and is no longer practical.

Example 2 100 g of the white dispersion obtained in Production Example 2 of latex particles
And 1.5 g of Sumicaron Black were heated to a temperature of 100 ° C., and heated and stirred for 4 hours. By cooling to room temperature and passing through a 200 mesh nylon cloth to remove the remaining dye,
A black resin dispersion having an average particle size of 0.24 μm was obtained.

32 g of the above black resin dispersion, zirconium naphthenate 0.5
g, FOC-1600 (manufactured by Nissan Chemical Co., Ltd., hexadecyl alcohol) was diluted with 1 of Shellsol 71 to prepare a liquid developer.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains occurred on the apparatus.

Further, 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 3 100 g of the white dispersion obtained in Production Example 2 of latex particles
And a mixture of 3 g of Victoria Blue B at a temperature of 70 ° C. to 80 ° C.
And stirred for 6 hours. After cooling to room temperature, it was passed through a 200-mesh nylon cloth to remove the remaining dye, and the average particle size was 0.2.
A 25 μm blue resin dispersion was obtained.

32 g of the above blue resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g to 1 of Isopar H.

This was developed with the same apparatus as in Example 1, and
Even after the development of 00 sheets, no toner adhesion stains were observed on the apparatus. Further, 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 4 White resin dispersion 32 obtained in Production Example 6 of latex particles
g, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-1400
A liquid developer was prepared by diluting 20 g of a tetradecyl alcohol (manufactured by Nissan Chemical Industries, Ltd.) and 0.02 g of a semi-docosanil amidated copolymer of diisobutylene and maleic anhydride into 1 of Isopar G.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains were observed on the apparatus. Further, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were clear.

After the developer was allowed to stand for three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

Example 5 10 g of poly (decyl methacrylate) and 3 parts of Isopar H
0 g and 8 g of alkali blue were put into 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 D-5 obtained in Production Example 5 of latex particles, 4.2 g of the above-mentioned alkali blue dispersion, 15 g of isostearyl alcohol and 0.06 g of a semi-docosanyl amidated copolymer of diisobutylene and maleic anhydride Was diluted to 1 of Isopar G to prepare a liquid developer.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains were observed on the apparatus. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after 10,000 sheets were printed were very clear.

Examples 6 to 29 Liquid developers were prepared in the same manner as in Example 5, except that the latex particles D-5 were replaced with the respective latexes shown in Table 8 below.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains occurred on the apparatus.

Further, 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.

After the developer was allowed to stand for three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

(Effect of the Invention) According to the present invention, a developer having excellent dispersion stability, redispersibility, and fixability was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speed, the developing device did not become stained, and the image quality of the obtained master plate for offset printing and the image quality of the printed matter after 10,000 sheets were printed were very clear. Was.

Claims (2)

(57) [Claims] 1. An electrophotographic liquid developer comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5, wherein the dispersed resin particles have a phosphono group, Carboxyl group, sulfo group, hydroxyl group, formyl group, carboxamide group, sulfoamide group, amino group, (R ₁₁ represents a —R ₁₂ group or —OR ₁₂ group, and R ₁₂ represents a hydrocarbon group), a polymer component containing at least one polar group selected from cyclic acid anhydride-containing groups, and / or Alternatively, an AB block composed of an A block containing a polymer component corresponding to the monofunctional monomer (A) and a B block containing at least a polymer component represented by the following general formula (I): A polymer is formed, and a polymerizable double bond group is bonded to the terminal of the polymer main chain of the B block.
A graft-type copolymer containing at least one monofunctional macromonomer (MM) of ^{3 to} 2 × 10 ⁴ and a monomer (B) represented by the following general formula (II); A monofunctional monomer (A) which is soluble in the non-aqueous solvent but insolubilized by polymerization in the presence of a dispersion stabilizing resin of the following general formula (III):
Having a number average molecular weight of 1 × 10 ⁴ or less, wherein a polymerizable double bond group represented by the following general formula (IV) is bonded to only one end of the main chain of a polymer comprising a repeating unit represented by _A liquid developer for electrophotography, comprising copolymer resin particles obtained by polymerizing a solution containing at least one functional macromonomer (M _A ). General formula (I) In the formula (I), Vo is -COO-, -OCO-, (L ₁ and l ₂ represent an integer of 1 to 3), -O-, -SO
_2- , -CO-, -CONHCOO-, -CONHCONH-, or Wherein R ₁₃ represents a hydrogen atom or a hydrocarbon group. R ₀ represents a hydrocarbon group. a ₁ and a ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z ₁ or a hydrocarbon group having 1 to 8 carbon atoms. -COO-Z ₁ (wherein Z ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms) via represent. General formula (II) In the formula (II), V ₁ represents —COO—, —OCO—, (L _3, l ₄ is an integer of 1 to 3), or represent -O-. R ₁ represents an aliphatic group having 8 or more carbon atoms. b ₁ and b ₂ may be the same or different and each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms. General formula (III) Wherein (III), T ₁ is _{-COO -, - OCO-, CH 2} l COO-,
_{CH 2 l OCO -, - O} -, - SO 2 -, - CONHCOO -, - CON
HCONH-, Represents (D ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. 1 represents an integer of 1 to 3.) G ₀ represents a hydrocarbon group having 1 to 22 carbon atoms. However, in the carbon chain of _{G 0, -O -, - CO} -, - CO 2 -, - OCO -, -
SO ₂ −, May be contained. Here, d ₂ represents the same content as d _1. d ₁ and d ₂ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ₃
Or it represents a -COO-D ₃ via a hydrocarbon (D ₃ represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (IV) Wherein (IV), T ₂ represents T ₁ same content as the formula (III). e ₁ and e ₂ may be the same or different from each other;
It represents a d _1, d ₂ identical contents and I). 2. The static material according to claim 1, wherein said monofunctional macromonomer (M _A ) contains at least a repeating unit represented by the following general formula (IIIa) as a repeating unit thereof. Liquid developer for electrophotography. General formula (IIIa) Wherein _{(III a), d 1,} d 2, T 1 represents the same symbols as in formula (III). G ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. J ₁ and J ₂ may be the same or different from each other, -O-,
_{-CO -, - CO 2 -,} - OCO -, - SO 2 -, The representative (D ₄ represents the same content as D ₁ of the formula (III)). W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain. Here, J ₃ and J ₄ may be the same or different from each other, have the same contents as J ₁ and J ₂ above, and W ₃ is
It represents a C1-C18 hydrocarbon group which may be substituted. m, n and p each independently represent an integer of 0-3.
However, none of them is 0 at the same time.