JPH06295105A - Electrostatic liquid developer - Google Patents

Abstract

PURPOSE:To provide an electrostatic liq. developer with the dispersibility, redispersibility and printing durability improved even when the developing-fixing stage is quickened or a long-sized master plate is used. CONSTITUTION:This developer contains a polymer resin grain obtained by polymerizing a soln. contg. a star-shaped copolymer (2X10<4>-1X10<6> mol.wt.) as the dispersion stabilizing resin P formed by combining at least three A-B block polymer chains consisting of a block A having a monofunctional monomer A, an oligomer B contg. a polar group at the end of the principal chain and a polymer component having a specified polar group or a polymer component equivalent to the monomer A and a block B having a >=8C aliphatic group in an org. molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid developer for electrostatic photography, which is obtained by dispersing at least a resin in a carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, and particularly redispersion. The present invention relates to a liquid developer having excellent properties, storability, stability, image reproducibility, and fixability.

[0002]

2. Description of the Related Art A general liquid developer for electrophotography is 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, which are petroleum-based. It is dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and a polar control agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, vinylpyrrolidone is added. . In such a developer, the resin is dispersed as insoluble latex particles in the form of particles having a diameter of several nm to several hundreds of nm, but in the conventional liquid developer, the soluble dispersion stabilizing resin, the polarity control agent and the insoluble latex particles are used. The resin for stabilizing the soluble dispersion and the polarity control agent were easily diffused in the solution because of insufficient bonding with. For this reason, the soluble dispersion stabilizing resin is desorbed from the insoluble latex particles by long-term storage and repeated use,
Particles settle, agglomerate, accumulate, or have unclear polarity,
There was a drawback. Further, since particles once aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to the failure of the developing machine such as dirt on the image area and clogging of the liquid feeding pump.

In order to improve these drawbacks, means for chemically bonding the soluble dispersion stabilizing resin and the insoluble latex particles have been devised and are disclosed in US Pat. No. 3,990,980. However, although these liquid developers have improved the dispersion stability against the spontaneous sedimentation of particles to some extent, they are still insufficient, and when used in an actual developing device, the toner adhered to each part of the device is in the form of a coating film. It has a drawback that it is hard to re-disperse, and it is difficult to perform re-dispersion, and further, it causes failure of the apparatus, stains on copied images, and the like, and is insufficient in re-dispersion stability for practical use. Further, in the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle size distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the insolubilizing monomer, and generally, The particles have a wide particle size distribution and contain a large amount of coarse particles, or are polydisperse particles having two or more average particle sizes. Further, it was difficult to obtain a desired average particle diameter 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 manufactured through a complicated and long manufacturing process.

Further, in order to improve the above-mentioned drawbacks, the insolubility 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 of improving the dispersibility, redispersibility and storage stability of particles by using dispersed resin particles is disclosed in JP-A-60-17.
No. 9751, No. 62-151868 and the like. In addition, insoluble dispersed resin particles of a copolymer of a monomer that becomes insoluble and a monomer that contains a long-chain alkyl moiety in the presence of a polymer that uses a bifunctional monomer or a polymer that uses a polymer reaction The method of improving the dispersibility, redispersibility and storage stability of the particles by using
2-166362, 63-66567, etc. Further, as a dispersion stabilizing polymer, a conventional random copolymer is used as a block copolymer of a solvating polymer part and a non-solvating polymer part to improve redispersibility and storage stability. An improved method is disclosed in Japanese Patent Laid-Open No. 3-1266.
6, No. 3-77965, No. 3-225353, and No. 4-46354.

[0005]

On the other hand, in recent years, a method of printing a large number of 5000 or more sheets by using a master plate for offset printing by an electrophotographic system has been attempted. It has become possible to print more than 10,000 sheets in plate size. or,
The operation time of the electrophotographic plate making system has been shortened, and the development-fixing process has been accelerated. JP-A-60-179751, JP-A-62-151868, JP-A-62-166362, JP-A-63-66567, JP-A-3-12666, JP-A-3-77965, and JP-A-3-225.
No. 353 and No. 4-46354, the dispersed resin particles produced according to the means disclosed herein are those in the case where the developing speed is increased, the dispersibility and redispersibility of the particles are increased, and the fixing time is shortened. Or large size (for example, A-
In the case of master plates of 3 sizes or more), the printing durability was not always satisfactory.

The present invention solves the problems of the conventional liquid developers described above. The purpose of the present invention is to
It is an object of the present invention to provide a liquid developer which has a rapid development-fixing process and is excellent in dispersion stability, redispersibility and fixing property even in an electrophotographic plate making system using a large plate size master plate. Another object of the present invention is to provide a liquid developer capable of producing an original plate for offset printing having excellent oil sensitivity and printing durability of printing ink by an electrophotographic method. Another object of the present invention is to provide a liquid developer suitable for various electrostatic photography and various transfers in addition to the above-mentioned applications. Still another object of the present invention is to provide a liquid developer which can be used in any system in which the liquid developer can be used such as ink jet recording, cathode ray tube recording and recording of various changing steps such as pressure change or electrostatic change. That is.

[0007]

The above-mentioned various objects are achieved by a liquid developer for electrostatic photography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less. In the above, the dispersed resin particles are at least one monofunctional monomer (A) which is soluble in the non-aqueous solvent, but is insolubilized by polymerization, from the repeating unit represented by the following general formula (I). A carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and a -P (= O) (OH) G ¹ group [wherein G ¹ is a carbon atom] Of an oligomer (B) having a number average molecular weight of 1 × 10 ⁴ or less, which is formed by bonding at least one polar group selected from a hydrogen group or a —OG ² group (G ² represents a hydrocarbon group). At least one, and a phosphono group, cal Voxyl group, sulfo group, hydroxyl group, formyl group, amino group, -P (= O) (OH) R
¹ group [R ¹ represents a -R ² group or a -OR ² group, R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ NR ³ R ⁴
A group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from a cyclic acid anhydride-containing group, and / or Block A containing at least one polymer component corresponding to the monofunctional monomer (A) and block B containing at least one polymer component represented by the following general formula (II).
And at least three AB-type block polymer chains composed of and are bonded to an organic molecule, and each AB-type block polymer chain is bonded to block B of the polymer main chain of block A. It is bonded to the organic molecule at one end opposite to the end and has a weight average molecular weight of 2 × 10 ⁴ to 1 ×.
Electrostatically characterized by being polymer resin particles obtained by polymerizing a mixture containing at least one kind of dispersion-stabilizing resin [P] comprising a star-type copolymer of 10 ⁶ This is accomplished with a photographic liquid developer.

[0008]

[Chemical 5]

In the formula (I), V ⁰ is --COO-- or --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO -, - O
_{-, - SO 2 -, -} CONHCOO -, - CONHCO
^{NH -, - COND 11 -,} - SO 2 ND 11 -, or a phenylene group [hereinafter, a phenylene group in -Ph-, -P
h- includes a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group]. Here, D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents an integer of 1 to 4. a ¹ and a ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom,
Cyano group, (shown here D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group) hydrocarbon group, -COO-D ^12, or a hydrocarbon representative of the -COO-D ¹² through a group. D ⁰ is
It represents a hydrocarbon group having 1 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0010]

[Chemical 6]

In the formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO.
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^11). A ¹ and A ² are
They represent hydrocarbon groups having 1 to 18 carbon atoms, which may be the same as or different from each other, may be respectively substituted, or may have Chemical Formula 7 below interposed in the bond of the main chain.

[0012]

[Chemical 7]

In the chemical formula 7, B ³ and B ⁴ may be the same as or different from each other, and have the same contents as the above B ¹ and B ^2, and A ⁴
Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and D ²³ has the same content as D ²¹ above. m, n and p
May be the same as or different from each other and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time.

[0014]

[Chemical 8]

In the general formula (II), X ¹ is --COO-- or --O.
_{CO -, - (CH 2)} x COO -, - (CH 2) x OCO-
[Here, x represents an integer of 1 to 3] or -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. b ¹ and b 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, —COO—Z ¹ ,
Alternatively, it represents —COO—Z ¹ via a hydrocarbon group (wherein Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group).

The liquid developer of the present invention will be described in detail below. The electric resistance used in the present invention is 10 ⁹ Ωcm or more,
As the carrier liquid having a dielectric constant of 3.5 or less, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof can be preferably used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L
(Isopar; trade name of Exxon), Shersol 7
0, Shelsol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Co.) and the like are used alone or in combination.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which is the most important constituent component of the present invention, is a star type block copolymer of the present invention for dispersion stabilization in a non-aqueous solvent. By polymerizing at least one of the monofunctional monomer (A) in the presence of the resin [P] and the oligomer (B) having a polar group at one end of the polymer main chain (so-called polymerization granulation method) It is manufactured.

Here, as the non-aqueous solvent, basically,
Any one that is miscible with the carrier liquid of the liquid developer for electrostatic photography 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. Examples thereof include hydrogen and halogen substitution products thereof. Hexane, for example
Octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shelsol 70, Shelsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

Solvents that can be mixed with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.). Cyclohexanone, etc., carboxylic acid esters (eg, methyl acetate,
Ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate etc.), ethers (eg diethyl ether, dipropyl ether, tetrahydrofuran, dioxane etc.), halogenated hydrocarbons (eg methylene dichloride, chloroform, etc.) Carbon tetrachloride, dichloroethane, methyl chloroform, etc.) and the like. It is desirable that the non-aqueous solvent used as a mixture of these is distilled off under heating or under reduced pressure after polymerization granulation, but even if it is brought into a liquid developer as a latex particle dispersion, the solution of the developer is There is no problem as long as the resistance satisfies the condition of 10 ⁹ Ωcm or more. Normal,
It is preferable to use the same solvent as the carrier liquid in the step of producing the resin dispersion, and as described above, a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon. And so on.

The monofunctional monomer (A) in the present invention is
Any monofunctional monomer that is soluble in the non-aqueous solvent but is insolubilized by polymerization may be used. Specific examples thereof include monomers represented by the following general formula (IV).

[0021]

[Chemical 9]

In the general formula (IV), T ¹ is --COO-- or --O.
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-CONHCOO-, -CONHOCO-, -SO
^{_{2 -, - CON (W 1}} ) -, - SO 2 N (W 1) -, or a phenylene group [-Ph-]. W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example,
Methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group , 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3-methoxypropyl group and the like).

D ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group) , 2,2,2-trifluoroethyl group, 2
-Bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-
Dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-
Methanesulfonylethyl group, 2-ethoxyethyl group,
N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, trimethoxysilylpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2- Pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4
-Sulfobutyl group, 2-carboxamidoethyl group, 3
-Sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

D ¹ and d ² may be the same or different and each has the same content as b ¹ or b ² in the general formula (II).

As a specific monofunctional monomer (A),
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Alkyl esters or amides of an unsaturated carboxylic acid such as maleic acid having 1 to 4 carbon atoms which may be substituted (eg, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2- Bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2 −
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) ethyl group, 2-carboxyethyl group,
2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-
Furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-
Carboxamidoethyl group, etc.); Styrene derivative (for example, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; Acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook-Basic Edition", edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986). ), For example, N-vinyl pyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
Etc. The monomer (A) may be used in combination of two or more kinds.

Next, the oligomer (B) used in the present invention will be further described. The oligomer (B) has a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and-on only one end of the main chain of the polymer composed of the repeating unit represented by the following general formula (I). P (= O) (OH) G ¹ group [wherein G ¹ represents a hydrocarbon group or a -OG ² group (G ² represents a hydrocarbon group)] is bonded to at least one polar group. Is an oligomer having a number average molecular weight of 1 × 10 ⁴ or less.

[0027]

[Chemical 10]

In the formula (I), V ⁰ is --COO--, --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO -, - O
_{-, - SO 2 -, -} CONHCOO -, - CONHCO
^{NH -, - COND 11 -,} - SO 2 ND 11 -, or a phenylene group (-Ph-) (wherein D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, r is 1 Indicates an integer of 4). a ¹ and a ² may be the same or different, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—D ¹² , or —CO via a hydrocarbon group.
Represents O—D ¹² (wherein D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group). D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0029]

[Chemical 11]

In the formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO.
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^11). A ¹ and A ² are
They are the same or different from each other, and each represents a hydrocarbon group having 1 to 18 carbon atoms, which may be substituted or may have the following Chemical formula 12 interposed in the bond of the main chain.

[0031]

[Chemical 12]

In Chemical formula 12, B ³ and B ⁴ may be the same or different from each other, and have the same contents as B ¹ and B ² ,
⁴ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and D ²³ has the same meaning as D ²¹ above. m, n and p
May be the same as or different from each other and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time.

The hydrocarbon groups contained in a ¹ , a ² , V ⁰ and D ⁰ in the general formula (I) each have the indicated carbon number (as an unsubstituted hydrocarbon group). The group may be substituted.

In the general formula (I), D ¹¹ in the substituent represented by V ⁰ is a hydrogen atom, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, Methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl Group, 3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms and which may be substituted (eg, 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.), carbon Number 7 to 1
2 optionally substituted aralkyl groups (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.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexyl) Ethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

When V ⁰ represents a phenylene group (-Ph-), the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.),
Alkyl group (eg, methyl group, ethyl group, propyl group,
Butyl group, chloromethyl group, methoxymethyl group, etc.) and the like.

A ¹ and a ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon number of 1 to 3
Alkyl group (eg, methyl group, ethyl group, propyl group, etc.), —COO-D ¹³ or —CH ₂ COO-D ¹³ (D
¹³ represents 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, which may be substituted, and specifically, the above-mentioned D ¹¹ was explained. Represents the same content as).

When D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms, it has the same details as those described for D ¹¹ above.

The case where D ⁰ represents a substituent represented by the general formula (III) will be described in detail. A ¹ and A ² may be the same as or different from each other, may be respectively substituted, or may have the above Chemical Formula 12 interposed in the bond of the main chain and have a hydrocarbon group having 1 to 18 carbon atoms (hydrocarbon group). Examples of the group include an alkyl group, an alkenyl group, an aralkyl group, and an alicyclic group, and specific examples thereof include the same contents as the specific examples listed for D ¹¹ . More specific examples of A ¹ and A ² are: -C (D ³¹ ).
(D ³² )-[D ³¹ and D ³² represent a hydrogen atom, an alkyl group, a halogen atom or the like],-(CH = CH)-, a phenylene group (-Ph-), a cyclohexylene group [hereinafter referred to as a cyclohexylene group. the - expressed in, "-C ₆ H _10" "- C ₆ H ₁₀ -"
Includes a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group], and the above chemical formula 12 and the like, which are composed of any combination of atomic groups.

Further, in the linking group in the general formula (I): -V ^0- (A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹ , V ⁰ to D ²¹ (that is, V ⁰ , A ¹ , B ¹ , A ² ,
The total number of atoms in the linked main chain composed of B ² and D ²¹ ) is 8
The above-mentioned structure is preferable. Where A ¹ and A ¹
There in the case of the hydrocarbon group interposing the reduction 12 in the binding of the main ^{chain, -B 3 - (A 4 -B} 4) p -D 23 is also included in the connecting backbone. The number of atoms in the main chain is, for example, V
^{When 0} represents -COO- or -CONH-, an oxo group (= O group) and a hydrogen atom are not included as the number of atoms, and a carbon atom, an ether-type oxygen atom, and a nitrogen atom which form the connecting main chain are the atoms. Included as a number. Therefore, -COO-
And -CONH- are counted as 2 atoms. Similarly,
If D ²¹ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included. Therefore, in this case, it is counted as 9 atoms.

In the repeating unit represented by the general formula (I) as described above, when D ⁰ represents the substituent represented by the general formula (III), that is, at least two or more repeating units are contained in the molecule. When containing a specific polar group,
More specifically, the following repeating units can be mentioned as examples. In the following, a is -H or -CH
₃ ; R is a C ₁ -C ₁₈ alkyl group; R'is a hydrogen atom or a C ₁ -C ₁₈ alkyl group; and k ₁ and k ₂ are each 1 to 1.
2 is an integer; m ₁ is an integer of ₁ to 100.

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

Further, the oligomer (B) used in the present invention
In, in addition to the repeating unit represented by the general formula (I), other repeating units may be contained as a copolymerization component. The other copolymerization component may be any compound as long as it is a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (I). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4-pentenoic acid, etc., and esters or amides of these unsaturated carboxylic acids, having 1 to 1 carbon atoms.
22 fatty acid vinyl esters or allyl esters, vinyl ethers, styrene and styrene derivatives,
Examples thereof include unsaturated bond-containing heterocyclic compounds. Specific examples thereof include the compounds exemplified as the above-mentioned monomer (A), but are not limited thereto.

In the total sum of the repeating units of the oligomer (B), the content of the repeating unit component represented by the general formula (I) is preferably 40% by weight or more, and more preferably 60 to 100% by weight. is there. When the amount of the component represented by the general formula (I) is less than 40% by weight based on the total amount, the mechanical strength of the image portion formed by the dispersed resin particles is not sufficiently retained, and thus the printing durability when used as an offset master plate. The improvement effect cannot be seen. The oligomer (B) of the present invention has a number average molecular weight of 1 × 10 ⁴ or less, preferably 1 × 10 ³ to 1 × 10 ⁴ , and more preferably 2
× 10 ^{3 to} 9 × 10 ³ . When the upper limit of the number average molecular weight of the oligomer (B) exceeds 1 × 10 ⁴ , the printing durability is deteriorated. On the other hand, if the molecular weight is too small, stains tend to occur, and it is preferably 1 × 10 ³ or more.

In the polar group bonded to only one end of the polymer main chain of the oligomer (B) used in the present invention, -P (=
O) (OH) G ¹ group, G ¹ is a hydrocarbon group or —OG
² groups (G ² represents a hydrocarbon group) are represented. G ¹ or G ²
The hydrocarbon group represented by is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), Or, it represents an aromatic group which may be substituted (eg, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In the polar group of the present invention, the amino group is --N.
H _2, represents a -NHG ³ or -NG ³ G ^4. G ³ and G ⁴ each represent a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, the hydrocarbon group of G ¹ or G ² described above. Represents the same content as. Even more preferably, the hydrocarbon group of G ¹ , G ² , G ³ and G ⁴ may be an alkyl group having 1 to 4 carbon atoms which may be substituted, an optionally substituted benzyl group, or an optionally substituted one. A phenyl group is mentioned.

Here, the polar group has a chemical structure which is directly bonded to one end of the polymer main chain or bonded through an arbitrary linking group. The group connecting the polymer main chain component of the oligomer (B) and the polar group includes a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom). , Nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bond. Among the oligomers (B) of the present invention, preferred are those represented by the following general formula (Ia) or general formula (Ib).

[0050]

[Chemical 17]

In the general formulas (Ia) and (Ib), a ¹ ,
a ² , V ⁰ and D ⁰ have the same contents as those in the general formula (I), and G ⁰ represents the above-mentioned polar group bonded to one end in the formula (I). L represents a single bond or, -CG ⁵ G ⁶ -
[Here, G ⁵ and G ⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group). , Propyl group) and the like], −
(CH = CH) -, - C≡C -, - C 6 H 10 - ( cyclohexylene group), - Ph- (phenylene group), - O-,
-S -, - CO -, - NG 7 -, - COO -, - SO
^{_{2 -, - CONG 7 -,}} - SO 2 NG 7 -, - NHCOO
It represents a linking group composed of any combination of —, —NHCONH— and the like. However, G ⁷ is a hydrogen atom or a carbon number 1
~ 18 hydrocarbon groups, specifically D in formula (I)
The same contents as described in ¹¹ are mentioned. In the polymer main chain, phosphono group, carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, -P (=
Those which do not contain a copolymerization component containing a polar group of O) (OH) G ¹ group are preferable.

The oligomer (B) of the present invention in which a specific polar group is bonded only to one end of the main chain of the polymer has various reagents at the end of the living polymer obtained by conventionally known anionic polymerization or cationic polymerization. A method of reacting (method of ionic polymerization method), a method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific polar group in the molecule (method of radical polymerization method),
Alternatively, it can be easily produced by a synthetic method such as a method of converting a polymer having a reactive group at a terminal obtained by an ionic polymerization method or a radical polymerization method as described above into a specific polar group of the present invention by a polymer reaction. You can Specifically, P. Dreyfuss & R. P. Quir
k, Encycl. Polym. Sci. Eng. ，
7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals" 30 , 232 (1985), Akira Ueda, Susumu Nagai "Science and Industry" 60 , 57 (1986), etc. and references cited therein. It can be produced by the method described.

As the polymerization initiator containing a specific polar group in the above-mentioned molecule, for example, 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ) -2-Hydroxyethyl] propioamide}, 2,
2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2-
(4,5,6,7-Tetrahydro-1H-1,3-diazepin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidine-2
-Yl) propane], 2,2'-azobis [2- (5-
Hydroxy-3,4,5,6-tetrapyrimidine-2-
Il) propane], 2,2'-azobis {2- [1-
(2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [N- (2-hydroxyethyl) -2-methyl-propionamidine],
2,2'-azobis [N- (4-aminophenyl) -2
-Methylpropionamidine] and other azobis compounds.

Further, examples of the chain transfer agent containing a specific polar group in the molecule include mercapto compounds, disulfide compounds, iodine-substituted compounds and the like, with preference given to mercapto compounds. For example, thioglycolic acid, 2-mercaptopropionic acid, thiomalic acid,
Examples thereof include 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptoethylamine, thiosalicylic acid, α-thioglycerin, 2-phosphonoethylmercaptan, hydroxythiophenol, and derivatives of these mercapto compounds.

These polymerization initiators and / or chain transfer agents are contained in an amount of 0.5 to 20 parts by weight based on the total amount of the monomer corresponding to the repeating unit represented by the general formula (I) and other polymerizable monomers. %, Preferably 1 to 10% by weight.

Preferred oligomers (B) for use in the present invention are represented by formula (Ia) or (Ib). Specific examples of the moiety represented by G ⁰ -L- in these formulas are shown below. Shown in. However, the scope of the present invention is not limited to these. In the following,
k ₁ is an integer of 1 or 2, k ₂ is an integer of ₂ to 16, k ₃
Represents an integer of 1 or 3. R represents an alkyl group having 1 to 6 carbon atoms.

[0057]

[Chemical 18]

[0058]

[Chemical 19]

[0059]

[Chemical 20]

The dispersion resin of the present invention is obtained by polymerizing at least one kind of the monomer (A) in the presence of the dispersion stabilizing resin [P] and the oligomer (B). If the resin synthesized from the monomer is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, the oligomer (B) is preferably used in an amount of 0.1 to 10% by weight, and more preferably 0.3 to 5% by weight, based on the insoluble monomer (A). The molecular weight of the dispersion resin of the present invention is preferably 1 × 10 ³ to 1 ×.
10 ⁶ and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

It is used for polymerizing a mixture containing the above-mentioned monomer (A) and oligomer (B) in a non-aqueous solvent, and forming the solvent-insoluble polymer into a stable resin dispersion. Regarding the dispersion stabilizing resin [P] of the present invention,
It will be described next. The dispersion stabilizing resin [P] has a weight average molecular weight of 2 × 10 ⁴ to 1 × 1 which is formed by bonding at least three polymer chains of the AB block copolymer component in an organic molecule.
0 ⁶ is a star copolymer. One block (block A) bonded to the organic molecule includes a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a -P (= O) (OH) R ¹ group [R ¹ is- shows the R ² group or -OR ² group, R ² represents a hydrocarbon group], -CO
At least one selected from a NR ³ R ⁴ group, a —SO ₂ NR ³ R ⁴ group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], and a cyclic acid anhydride-containing group. Of the polar group and / or at least one polymer component corresponding to the monofunctional monomer (A). Another one block (block B)
Contains at least one polymer component comprising the repeating unit represented by the general formula (II). Here, the order of arrangement in the polymer chains of block A and block B is such that the polymer main chain of block A is bound to an organic molecule at one end opposite to the end bound to block B. Then, the resin [P] is schematically shown as the following Chemical Formula 21.

[0062]

[Chemical 21]

In the chemical formula 21, X represents an organic molecule,
(A) represents block A, (B) represents block B,
(A)-(B) represents a polymer chain. Also, such AB
The upper limit of the type block polymer chains contained in the organic molecule is at most 15, usually about 10.

The abundance ratio of the block A and the block B in the star-type copolymer is 1 to 50/99 to 50 (weight ratio), preferably 5 to 40/95 to 60 (weight ratio). The specific polar group-containing polymer component contained in the block A is preferably 1 to 30 parts by weight, and more preferably 1 to 15 parts by weight in 100 parts by weight of the dispersion stabilizing resin [P]. Further, when the specific polar group-containing polymer component does not exist in the block A, the polymer component corresponding to the monofunctional monomer (A) is preferably 5 to 100 parts by weight of the resin [P]. It is 50 parts by weight, more preferably 10 to 40 parts by weight. The polymer component represented by the general formula (II) contained in the block B is
50% by weight of the dispersion stabilizing resin [P] is preferable.
To 99 parts by weight, more preferably 60 to 95 parts by weight. In the dispersion stabilizing resin [P], the above-mentioned predetermined existence ratio (that is, the above-mentioned block A and block B)
Of the specific polar group-containing polymer component contained in the block A or the polymer component represented by the general formula (II) contained in the block B). The redispersion stability of the dispersed resin particles obtained by polymerizing the mixture of the monofunctional monomer (A) and the oligomer (B) will be reduced. On the other hand, when the content of the monofunctional monomer (A) and the oligomer (B) is higher than the predetermined ratio, the average particle size of the dispersed resin particles obtained by the polymerization reaction of the mixture of the monofunctional monomer (A) and the oligomer (B) becomes coarse, and the particle distribution of the particles becomes small. Dispersibility is reduced.

Dispersion stabilizing resin [P] used in the present invention
Is soluble in an organic solvent, and specifically, at least 5 parts by weight or more of the dispersion stabilizing resin is dissolved in 100 parts by weight of a toluene solvent at a temperature of 25 ° C. The weight average molecular weight (Mw) of the dispersion stabilizing resin [P] of the present invention is 2 × 10 ⁴ to 1 × 10 ⁶ , and preferably 2.5 × 10 ^{4 to} 5.5 × 10 ⁵ .

Next, block A of dispersion stabilizing resin [P]
The polymer component constituting the above will be described in detail. The block A is composed of a polymer component corresponding to the monofunctional monomer (A) and / or the polymer component containing the specific polar group described above. Examples of the polymer component corresponding to the monofunctional monomer (A) include those having the same contents as those described above for the insolubilizing monomer (A). Preferably, it is composed of the same monomer as the monofunctional monomer (A) to be the dispersed resin particles.

In a specific polar group, -P (= O) (OH) R ¹
In the group, R ¹ represents -R ² group or -OR ² group, and R ²
Represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group for R ² is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, Hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc., and optionally substituted aromatic group (eg, phenyl group, tolyl group). Group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In the specific polar group, in the —CONR ³ R ⁴ group and the —SO ₂ NR ³ R ⁴ group, R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group (having 1 to 4 carbon atoms). 10, preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted)
Represents Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include those having the same contents as the hydrocarbon group represented by R ² .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride to be contained include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2.
-Dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, 2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride, and the like, These aliphatic dicarboxylic acid anhydrides may be substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride, naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride, and the like. Examples include halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as an alkoxy group, For example, it may be substituted with a methoxy group, an ethoxy group or the like).

Further, among the specific polar groups, the amino group is -N
H _2, represents a -NHR ⁵ or -NR ⁵ R ^6. R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. More preferably, it represents a hydrocarbon group having 1 to 7 carbon atoms, and specific examples thereof include those having the same contents as the hydrocarbon group represented by R ² .

The hydrocarbon groups of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are even more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted, a benzyl group which may be substituted, Or a phenyl group which may be substituted may be mentioned.

The monomer corresponding to the polymer component containing the above specific polar group may be any monofunctional monomer containing at least one specific polar group.
For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science, Japan, and Fuifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-form)
Bromo form, α-fluoro form, α-tributylsilyl form, α
-Cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, Crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid vinyl group or allyl group And a compound containing the polar group in the substituent of the amide derivative and the ester derivative of these carboxylic acids or sulfonic acids.

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, e
Is _{-H, -CH 3, -Cl, -Br} , -CN, -CH 2 C
OOCH ₃ or —CH ₂ COOH, f is —H or —
CH ₃ is shown, n is an integer of 2 to 10, and m is 1 to 1.
0 represents an integer and p represents an integer of 1 to 4. X ₁ is -C
OOH, -O-P (= O ) (OH) 2, -SO 3 H, -O
H, -NR _a R _b, -CHO or -O-P (= O) ( OH)
R _a is shown. Here, R _a, R _b represents an alkyl group having 1 to 4 carbon atoms. X ₂ represents a -COOH or -OH.

[0074]

[Chemical formula 22]

[0075]

[Chemical formula 23]

[0076]

[Chemical formula 24]

Next, block B of dispersion stabilizing resin [P]
The repeating unit represented by the general formula (II) which constitutes is described in detail. In the general formula (II), X ¹ preferably represents -COO-, -OCO- or -O-. Y ¹
Preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which 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,
Examples thereof include a linolel group.

B ¹ and b ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom, etc.), a cyano group, a carbon number of 1 to 3
Alkyl group (eg, methyl group, ethyl group, propyl group, etc.), —COO-Z ¹ or —CH ₂ COO-Z ¹ [Z ¹
Represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (for example, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.).

Z ¹ is specifically a hydrogen atom, and as a preferable hydrocarbon group, an alkyl group having 1 to 22 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group). Group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2- Cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3
-Bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (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, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.),
Aralkyl groups which may be substituted and have 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.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, etc.) and optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group) , Octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxy Carbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

In addition, the block B of the dispersion stabilizing resin used in the present invention may contain another repeating unit as a copolymerization component in addition to the repeating unit represented by the general formula (II). The other copolymerization component may be any compound as long as it is composed of a monomer that is copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). However, it is preferable that no other component is contained, and it is used in a range not exceeding 20 parts by weight in the block B at most. If it exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles deteriorates. In the block B, the repeating unit represented by the general formula (II) may be used in combination of two or more kinds.

On the other hand, the organic molecule according to the present invention, which is formed by binding at least three polymer chains, is not particularly limited as long as the molecular weight of the molecule is 1000 or less. For example, the trivalent hydrocarbon residue shown in Chemical formula 25 below may be mentioned.

[0082]

[Chemical 25]

[Here, r ^{1 to} r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, at least one of r ¹ and r ² is linked to the polymer chain, and at least one of r ^{3 to} r ⁶ is linked to the polymer chain. ] These organic residues consist structure alone or any combination thereof, in the case of combination, -O -, - S -, - N (r 7) -, - COO -, - C
^{ON (r 7) -, -} SO 2 -, - SO 2 N (r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO
-, -NHCONH-, a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom (for example, a thiophene ring,
Pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine ring, etc.) and the like.

Other examples of the organic molecule which bonds the polymer chain include those composed of a combination of the following chemical formula 26 and the above-mentioned bonding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0085]

[Chemical formula 26]

The star type copolymer [P] of the present invention can be synthesized by utilizing a conventionally known method for synthesizing a star type polymer of a monomer containing a polar group and having a polymerizable double bond group. it can. For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morton,
TE Helminiak et al “J. Polym. Sci.” 57, 471 (19
62), B. Gordon III, M, Blumenthal, JE Loftus et
al “Polym. Bull.” 11,349 (1984), RB Bates, W.
A. Beavers et al “J. Org. Chem.” 44, 3800 (1979)
Can be synthesized according to the method described in. However, when this reaction is used, the "specific polar group" of the present invention is used as a protected functional group to polymerize, and then the protective group is removed. The protection of the specific polar group of the invention with a protecting group and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above cited document, and further, Yoshio Iwakura and Keisuke Kurita "Reactive Polymer", Kodansha Co., Ltd. (1977
), TW Greene “Protective Groups in Organic S
ynthesis ”(John Wiley & Sons, 1981), JFW Mc
Omic “Protective Groups in Organic Chemistry” (Pl
The method described in detail in a review article such as enum Press, 1973) can be appropriately selected and performed.

As another method, the monomer of the present invention, which is not protected with a specific polar group, is used, and a compound having a disiocarbament group and / or a compound having a zanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu “Polymer” 3
7 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu “Polym. Rep. Ja
p. " 37 , 3508 (1988), JP-A 64-111, JP-A 64-26619, Nobuyuki Higashi et al.," Polymer Preprints, J. "
apan ” 36 (6), 1511 (1987), M. Niwa, N. Higashi et
al “J. Macromol. Sci. Chem.” A24 (5), 567 (198
It can be synthesized according to the synthetic method described in 7) and the like.

In order to produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin [P], the monomer (A) and the oligomer (B) as described above are mixed in a non-aqueous solvent. The polymerization may be carried out by heating in the presence of a polymerization initiator such as benzoyl oxide, azobisisobutyronitrile or butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin [P], the monomer (A) and the oligomer (B), and a method in which the dispersion stabilizing resin [P] is dissolved A method of dropping the monomer (A) and the oligomer (B) together with a polymerization initiator, or a mixture containing the entire amount of the dispersion stabilizing resin [P] and a part of the monomer (A) and the oligomer (B). A method of optionally adding the remaining monomer (A) and oligomer (B) together with the polymerization initiator to the solution,
Furthermore, there is a method in which a mixed solution of the dispersion stabilizing resin [P], the monomer (A) and the oligomer (B) is optionally added together with the polymerization initiator in a non-aqueous solvent. It can also be manufactured by using.

The total amount of the monomer (A) and the oligomer (B) is about 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The amount of the oligomer (B) is 0.1 with respect to 100 parts by weight of the monomer (A).
10 to 10 parts by weight is sufficient, preferably 0.3 to 5
Parts by weight. The dispersion stabilizing resin [P] is used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the monomer (A) used above. The amount of the polymerization initiator is appropriately 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 120 ° C. The reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers and esters is used in combination in the non-aqueous solvent used in the reaction, or when the monomer (A) to be polymerized and granulated is not contained. When the reaction product remains, it is preferably removed by heating the solvent or the monomer to a boiling point or higher and distilling it off, or by distilling under reduced pressure.

The non-aqueous dispersion resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution and, at the same time, exhibit very stable dispersibility.
In particular, even if it is repeatedly used in the developing device for a long time, the dispersibility is good, and even if the developing speed is improved, the re-dispersion is easy, and no adhesion stains are found on various parts of the device. Further, when fixed by heating or the like, a strong coating film was formed, and excellent fixability was exhibited. Furthermore, the liquid developer of the present invention is excellent in dispersion stability, redispersibility and fixability even when the development-fixing process is accelerated and a master plate of a large plate size is used.

As described above, the high redispersibility of the latex particles of the present invention is to be used together with the insolubilizing monomer (A).
It depends on the oligomer (B) containing a polar group at one end and a star type copolymer composed of a specific block.
That is, the dispersion stabilizing resin [P] of the present invention comprises a block B composed of a polymer component containing a long-chain aliphatic group having a high affinity for the non-aqueous solvent and a low affinity for the non-aqueous solvent. , A in which a block A composed of a polymer component having an affinity for the insoluble monomer (A) is bound
It is characterized by being a star-type copolymer in which at least three or more B-type block polymer chains are bound in an organic molecule. As a result, the block A portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the block B portion having a large affinity for the non-aqueous dispersion medium is for the solvent. Sufficiently solvated and also has a three-dimensional repulsion effect (so-called tail-like adsorption)
Since at least 3 or more polymer chains are present, it is presumed that the effect of the present invention was achieved by sufficiently efficiently exhibiting the adsorption effect and the steric repulsion effect.

On the other hand, in the conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, the component serving as the adsorbing portion is composed of a solvating component. Adhesion to dispersed resin particles is not sufficient because they are randomly bonded in the molecular chain, and the steric repulsion effect is also excluded due to the adsorption pattern becoming a loop, and dispersion stability is sufficient. It wasn't. Furthermore, A composed of block A and block B
A -B type block copolymer was developed, and the effect of improving dispersion stability was recognized as compared with the above random copolymer. However, the effect of dispersion stability is still insufficient for recent developments such as speeding up of the development speed of a plate making machine.

Further, high printing durability without deterioration of the toner image portion when printed as an offset master original plate is obtained by insolubilizing the monomer (A) and the oligomer (B) containing a polar group at one end used together therewith. It is presumed that the dispersion polymers adsorbed thereto have good compatibility with each other and are sufficiently compatible even under mild fixing conditions to form a uniform and strong film.

A colorant may be optionally 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. When the dispersed resin itself is colored, for example, as one of coloring methods, there is a method of physically dispersing it in a dispersed resin by using a pigment or a dye, and many pigments or dyes to be used are known. There is. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa yellow, quinacridone red,
Examples include phthalocyanine blue. As another method of coloring, there is a method of dyeing a dispersed resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, JP-A-53-53
There is a method of chemically bonding a dispersion resin and a dye, as disclosed in Japanese Patent Publication No. 54029, or Japanese Patent Publication No.
As described in, for example, No. 4-22955, there is a method of preparing a dye-containing copolymer by using a monomer containing a dye in advance in the production by the 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. 16, Vol. No. 2, page 44 is used. For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin, poly (vinylpyrrolidone), a copolymer containing a half-maleic acid amide component, higher alcohols having 8 or more carbon atoms, Examples include compounds such as polyethers and silicone oil.

The amount of each main component of the liquid developer of the present invention will be described below. Toner particles containing a resin (and a coloring agent used as desired) as a main component are contained in an amount of 0.5 parts by weight to 1000 parts by weight of the carrier liquid.
50 parts by weight is preferred. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fog will easily occur in the non-image area. Further, the carrier liquid-soluble resin for stabilizing the dispersion is optionally used, 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 used as the carrier liquid 100.
0.001 to 1.0 part by weight is preferable with respect to 0 part by weight. If desired, various additives may be added, and the upper limit of the total amount of these additives is restricted by the electric resistance of the developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image.
It is necessary to control within this limit.

[0098]

EXAMPLES The following will describe the effects of the present invention in more detail by showing the production examples of the oligomer of the present invention, the production examples of the dispersion stabilizing resin, the production examples of latex particles and the examples. It is not limited.

Production Example of Oligomer (B) 1: Oligomer B-1 2,3-diacetoxypropyl methacrylate 100
g, 5-mercaptopropionic acid 5 g, toluene 150
A mixed solution of 50 g of methanol and 50 g of methanol was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N.
0.4 g was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 2 liters of a mixed solution of methanol / water [(4/1) volume ratio], the methanol solution was separated by decantation, and the viscous material was dried, followed by a colorless viscous material. Was obtained. The number average molecular weight of the polymer was 3,300.

[0100]

[Chemical 27]

Production Examples 2 to 31 of Oligomer (B): Oligomer B-2 to B-31 In Production Example 1 of Oligomer B-1, instead of 2,3-diacetoxypropyl methacrylate and 3-mercaptopropionic acid. , Except that a methacrylate monomer and a mercapto compound corresponding to Table-A below were used,
Operating in the same manner as in Production Example 1, each oligomer B-2 to B-3
1 was produced. The number average molecular weight of the obtained oligomer was 2,500 to 5,000.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

Production Example 32 of Oligomer (B): Oligomer B-32 2- (n-nonylcarbonyloxy) ethyl crotonate 100 g, toluene 150 g, and ethanol 50 g.
The mixed solution of 1 was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 4,4'-azobis (4-cyanovaleric acid)
(Abbreviation: ACV) 8g was added and reacted for 5 hours. C. V. 2 g was added and reacted for 4 hours. The obtained reaction solution was cooled and then reprecipitated in a mixed aqueous solution of methanol / water [(4/1) volume ratio], the aqueous methanol solution was separated by decantation, and the viscous material was dried. The yield was 70 g and the number average molecular weight of the polymer was 2,600.

[0107]

[Chemical 28]

Production Examples 33 to 41 of Oligomer (B): Oligomer B-33 to B-41 In Production Example 32, the polymerization initiator A. C. V. In the same manner as in Production Example 32 except that the azobis compound of the following Table-B was used in place of and the monomer corresponding to the following structure was used in place of 2- (n-nonylcarbonyloxy) ethyl crotonate. Each oligomer B-33 to B-41 was produced. The number average molecular weight of the obtained oligomer is 2,000 to
It was 4,000.

[0109]

[Table 5]

[0110]

[Table 6]

Synthesis Example of Dispersion Stabilizing Resin [P] 1: Resin [P-1] Methyl Methacrylate 50 g, Methyl Acrylate 50
g, a mixture of 7.8 g of an initiator [I-1] having the following structure and 100 g of tetrahydrofuran under a nitrogen stream at a temperature of 50 ° C.
Warmed to. 10c of this solution with 400W high pressure mercury lamp
Light was irradiated from a distance of m through a glass filter for 8 hours to perform photopolymerization. The polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Next, the polymer 3
A mixed solution of 0 g, 70 g of stearyl methacrylate and 100 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream. Next, in the same manner as above, after performing light irradiation for 16 hours, the obtained reaction product was treated with methanol 1.5
It is reprecipitated in liter, the precipitate is collected, dried and the weight average molecular weight [Mw: Mw is a value by polystyrene conversion GPC method (GPC: size exclusion chromatography)] is 6 × 10 ⁴ at a yield of 80 g. A polymer of

[0112]

[Chemical 29]

[0113]

[Chemical 30]

Synthesis Examples 2 to 14 of Dispersion Stabilizing Resin [P]: Resins [P-2] to [P-14] In Synthesis Example 1 of dispersion stabilizing resin, the initiator [I-1] is used.
A polymer was synthesized in the same manner as in Synthesis Example 1 except that 0.011 mol of the initiator shown in Table C below was used instead of.
The Mw of each polymer obtained was in the range of 4 × 10 ^{4 to} 6 × 10 ⁴ .

[0115]

[Table 7]

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

Synthesis Examples 15 to 28 of Dispersion Stabilizing Resin [P]: Resins [P-15] to [P-28] Each monomer corresponding to the polymer component of block A shown in Table D below. A mixture of 0.01 mol of the initiator [I-7] and 100 g of tetrahydrofuran with respect to all the monomers used was heated to 50 ° C under a nitrogen stream. In this solution,
In the same manner as in Synthesis Example 1, light irradiation was performed for 12 hours to carry out a polymerization reaction. Next, each of the obtained polymers was added in a predetermined amount (x: as a solid content) shown in Table-D and each monomer corresponding to the polymer component of block B shown in Table-D below.
Using a predetermined amount (y: as a solid content amount) shown in, tetrahydrofuran was added so that the concentration of all compounds was 60% by weight, and the mixture solution was heated again to a temperature of 55 ° C. under a nitrogen stream. Next, after performing light irradiation for 16 hours in the same manner as above, the obtained reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. Yield 60-80
In g, each polymer having Mw of 3 × 10 ^{4 to} 6 × 10 ⁴ was obtained.

[0120]

[Table 11]

[0121]

[Table 12]

[0122]

[Table 13]

[0123]

[Table 14]

Latex Particle Production Example 1: Latex Particle D-1 14 g of dispersion stabilizing resin [P-1] and 1 of Isopar H
While stirring 77 g of the mixed solution under a nitrogen stream, the temperature is 60 ° C.
Warmed to. 50 g of methyl methacrylate, 50 g of methyl acrylate, 2.4 g of oligomer B-17, 1.0 g of 2,2′-azobis (isovaleronitrile) (abbreviation AIVN) as a polymerization initiator and Isopar H 200 g of the mixed solution was added dropwise over 2 hours, then 2
Stir for hours. Furthermore, A. I. V. N. 0.5 g was added and stirred for 3 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 98% and an average particle size of 0.22 μm. Particle size is CAPA-
It was measured with 500 (manufactured by Horiba, Ltd.).

Production Examples 2 to 22 of Latex Particles: Latex Particles D-2 to D-22 In Production Example 1 of latex particles, instead of the dispersion stabilizing resin [P-1], dispersion stability shown in Table E below. The latex particles D-2 to D-11 of the present invention were produced in the same manner as in Production Example 1 except that the resin for use was used. The polymerization rate of each latex particle obtained was 95 to 99%, the average particle diameter was in the range of 0.18 to 0.25 μm, and the monodispersity was good.

[0126]

[Table 15]

[0127]

[Table 16]

Production Example 23 of Latex Particles: Production of Latex Particles D-23 12 g of dispersion stabilizing resin [P-17], 10 parts of vinyl acetate
A mixed solution of 0 g, 3.5 g of oligomer B-19 and 384 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. A. as a polymerization initiator. I. V. N.
1.2 g was added and reacted for 3 hours. Add the initiator 2
A cloudiness occurred after 0 minutes, and the reaction temperature rose to 88 ° C.
Further, 0.5 g of an initiator was added and after reacting for 2 hours, the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion had a polymerization rate of 88% and an average particle size of 0.22μ.
m latex.

Production Examples of Latex Particles 24 to 40: Latex Particles D-24 to D-40 Monomer (A) (that is, methyl methacrylate and methyl acrylate) and oligomer B-used in Production Example 1 of latex particles. Latex particles were produced in the same manner as in Production Example 1 above, except that the compounds shown in Table F below were used instead of 17 and the dispersion stabilizing resin [P-1]. The degree of polymerization of each latex particle obtained was 95 to 99%, and the average particle diameter was 0.17 to 0.25 μm.
And the monodispersity was also good.

[0130]

[Table 17]

[0131]

[Table 18]

Production Example 41 of Latex Particles: (Comparative Example A) In Production Example 1 of latex particles, instead of 14 g of the dispersion stabilizing resin [P-1], a resin having the following structure [RP-
1] In the same manner as in Production Example 1 of latex particles except that 30 g was used, the polymerization rate was 98% and the average particle size was 0.40 μm.
A white dispersion of latex particles was obtained.

[0133]

[Chemical 31]

Latex Particle Production Example 42: (Comparative Example B) In Latex Particle Production Example 1, instead of the dispersion stabilizing resin [P-1] 14 g, a resin having the following structure [RP-
2] In the same manner as in Production Example 1 of latex particles except that 20 g was used, the polymerization rate was 90% and the average particle size was 0.30 μm.
A white dispersion of latex particles was obtained. (JP-A-4
-Equivalent to No. 46354)

[0135]

[Chemical 32]

Production Example 43 of Latex Particles: (Comparative Example C) In Production Example 1 of latex particles, instead of 14 g of the dispersion stabilizing resin [P-1], a resin having the following structure [RP-
3] In exactly the same manner as in Production Example 1 of latex particles except that 20 g was used, the polymerization rate was 92% and the average particle size was 0.35 μm.
A white dispersion of latex particles was obtained. (JP-A-3
Equivalent to -77965)

[0137]

[Chemical 33]

Example 1 10 g of a dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 10 g of nigrosine and 30 g of Shellzol 71 were used together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.). And dispersed for 4 hours to obtain a fine dispersion of nigrosine. 6 g of resin particles of Production Example 23 of latex particles (as solid content), 2.5 g of the above nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Kagaku KK, tetradecyl alcohol), and octadecene-half-maleic acid octadecylamide. A liquid developer for electrostatic photography was prepared by diluting 0.08 g of the copolymer with 1 liter of Isopar G.

(Preparation of Comparative Developers A to C) Three types of comparative liquid developers A, B and C were prepared by replacing the resin particles with the following resin particles in the production of the above liquid developer. Comparative liquid developer A: Resin particles obtained in Production Example 41 of latex particles. Comparative liquid developer B: resin particles obtained in Production Example 42 of latex particles. Comparative liquid developer C: resin particles obtained in Production Example 43 of latex particles.

These liquid developers are fully automatic plate-making machine ELP.
ELP Master II type (manufactured by Fuji Photo Film Co., Ltd.) which is an electrophotographic photosensitive material was exposed and developed using a developer of 404V (manufactured by Fuji Photo Film Co., Ltd.).
The plate making speed was 4 plates / minute. Further, after processing 2500 sheets of ELP Master II type, the presence or absence of toner adhesion stain on the developing device was observed. The blackening rate (image area) of the copied image was 30% using an original. The results are shown in Table-G.

[0141]

[Table 19]

When the plate-making was carried out using each developer under the above-mentioned plate-making conditions, the developing device was not contaminated, and the developer having a clear image on the 2500th plate-making plate was the case of the present invention. . On the other hand, a master plate for offset printing (ELP master) obtained by plate-making from each developer is printed by a conventional method, and the number of printed sheets until the occurrence of missing characters, blurring of solid parts, etc. in the image of the printed matter is compared. As a result, the master plate obtained using the developer of the present invention is 100
It did not occur even when the number of sheets was 00 or more, and it occurred with the number of 3000 in the master plate using Comparative Example A. In Comparative Example B, 7,000 sheets were produced, and in Comparative Example C, 6000 sheets were produced. As described above, only the developer using the resin particles of the present invention did not cause the developing device to be contaminated at all, and the number of printed master plates was remarkably improved. In the case of Comparative Example B and Comparative Example C,
If the plate making conditions are used under severe conditions (conventionally, the blackening rate of the copied image is about 8 to 10% at a plate making speed of 2 to 3 sheets / min), the developing device (especially on the back electrode plate) becomes dirty. Occurs, and the quality of the copied image on the plate is affected after 2500 sheets (Dmax decrease, fine line blurring, etc.).
Came out. Further, the number of printed master plates was remarkably reduced in Comparative Example A. These results are
This shows that the resin particles of the present invention are clearly superior.

Example 2 White Dispersion 10 Obtained in Production Example 28 of Latex Particles
A mixture of 0 g and Sumicaron Black 1.5 g at a temperature of 1
The mixture was heated to 00 ° C. and heated and stirred for 4 hours. After cooling to room temperature 2
The remaining dye was removed through a 00 mesh nylon cloth to obtain a black resin dispersion having an average particle diameter of 0.24 μm. 32 g of the above black resin dispersion, 0.05 g of zirconium naphthenate, FOC-1600 (Nissan Chemical Co., Ltd.)
Manufactured by Hexadecyl Alcohol) 20 g
A liquid developer was prepared by diluting 1 to 1 liter. When this was developed by the same apparatus as in Example 1,
Even after development of 2500 sheets, toner adhesion stains on the apparatus did not occur at all. 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 White Dispersion 10 Obtained in Production Example 35 of Latex Particles
A mixture of 0 g and 3 g of Victoria Blue B at a temperature of 7
The mixture was heated to 0 ° C to 80 ° C and stirred for 6 hours. After cooling to room temperature,
The remaining dye was removed through a 200-mesh nylon cloth to obtain a blue resin dispersion having an average particle size of 0.23 μm. A liquid developer was prepared by diluting 32 g of the blue resin dispersion and 0.05 g of zirconium naphthenate to 1 liter of Isopar H. When this was developed using the same apparatus as in Example 1, no toner adhesion stain was found on the apparatus even after development of 2500 sheets. or,
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 1 of Latex Particles
g, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC
-1400 (manufactured by Nissan Chemical Industries, Ltd., tetradecyl alcohol) 20 g and 0.02 g of half-docosanilamide compound of a copolymer of diisobutylene and maleic anhydride were diluted to 1 liter of Isopar G to prepare a liquid developer. did. When this was developed using the same apparatus as in Example 1, no toner adhesion stain was found on the apparatus even after development of 2500 sheets. 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 this developer was left standing for 3 months, the same treatment as above was carried out, but there was no difference from that before the passage of time.

Example 5 10 g of poly (decyl methacrylate), 30 g of Isopar H and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue. 30 g of the white resin dispersion D-34 obtained in Production Example 34 of latex particles, 4.2 g of the above alkali blue dispersion, 15 g of isostearyl alcohol, and a half-docosanilamide compound of a copolymer of diisobutylene and maleic anhydride 0 A liquid developer was prepared by diluting 0.06 g to 1 liter of Isopar G. When this was developed using the same apparatus as in Example 1, no toner adhesion stain was found on the apparatus even after development of 2500 sheets. 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 very clear.

Examples 6 to 35 Liquid developers were prepared in the same manner as in Example 5, except that the latex particles D-34 were replaced with the latexes shown in Table H below.

[0148]

[Table 20]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1, and its performance was examined. Each liquid developer exhibits the same performance as in Example 1,
Both redispersibility and printing durability were good.

[0150]

According to the present invention, a liquid developer having excellent redispersibility, storability and stability, and excellent image reproducibility and fixing property can be obtained. Particularly, a liquid having excellent redispersibility and stability of particles even when the developing-fixing process for an electrophotographic plate making system is accelerated, and having excellent printing durability even when a large plate master plate is used. A developer is obtained.

Claims (2)

[Claims] 1. A liquid developer for electrostatic photography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are At least one monofunctional monomer (A) that is soluble in an aqueous solvent but becomes insoluble by polymerization, one of the main chains of the polymer composed of repeating units represented by the following general formula (I) Carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and -P (= O) (OH) G ¹ group only at the terminal [wherein G ¹ is a hydrocarbon group or -OG ² group (G ² represents a hydrocarbon group), and at least one oligomer (B) having a number average molecular weight of 1 × 10 ⁴ or less, which is formed by bonding at least one polar group selected from Group, sulfo group, hydro Sill group, a formyl group, an amino group, -P (= O) (OH) R
¹ group [R ¹ represents a -R ² group or a -OR ² group, R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ NR ³ R ⁴
A group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from a cyclic acid anhydride-containing group, and / or Block A containing at least one polymer component corresponding to the monofunctional monomer (A) and block B containing at least one polymer component represented by the following general formula (II).
And at least three AB-type block polymer chains composed of and are bonded to an organic molecule, and each AB-type block polymer chain is bonded to block B of the polymer main chain of block A. It is bonded to the organic molecule at one end opposite to the end and has a weight average molecular weight of 2 × 10 ⁴ to 1 ×.
Electrostatically characterized by being polymer resin particles obtained by polymerizing a mixture containing at least one kind of dispersion-stabilizing resin [P] composed of a star-type copolymer of 10 ⁶ Liquid developer for photography. [Chemical 1] In formula (I), V ⁰ is -COO-, -OCO-,-(C
_{H 2) r COO -, -} (CH 2) r OCO -, - O -, - SO
_2- , -CONHCOO-, -CONHCONH-,-
COND ¹¹ −, —SO ₂ ND ¹¹ —, or a phenylene group (wherein D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents an integer of 1 to 4). a ¹ and a ²
May be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ^12,
Alternatively, it represents -COO-D ¹² via a hydrocarbon group (wherein D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group). D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (III). [Chemical 2] In formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO ₂ —, —OC.
_{O -, - SO 2 -,} - N (D 22) -, - CON (D 22)
- or an -N (D ²²⁾ CO- (wherein D ²² represents the same content as the D ^11). A ¹ and A ² may be the same as or different from each other, and each may be substituted, or the following chemical formula 3 may be interposed in the bond of the main chain, having 1 to 18 carbon atoms.
Represents a hydrocarbon group of. [Chemical 3] In the chemical formula 3, B ³ and B ⁴ may be the same as or different from each other, and have the same contents as the above B ¹ and B ^2, and A ⁴ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. D ²³ shows the same contents as D ²¹ above. m, n and p may be the same or different and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time. [Chemical 4] In the general formula (II), X ¹ is -COO-, -OCO-,-.
_{(CH 2) x COO -,} - (CH 2) [here x represents an integer of 1 to 3] _x OCO-, or an -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. b ¹ and b ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—Z ¹ , or —COO—Z ¹ via a hydrocarbon group (wherein Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 2. In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 50.
The liquid developer for electrostatic photography according to claim 1, wherein the liquid developer is / 99 to 50 (weight ratio).