JPH0627747A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve the dispersiveness, re-dispersiveness, and printing endurance and improve the resist property of a toner image part and the printing endurance of a pate for offset master as a developer for the electrophotographic plate making system. CONSTITUTION:A graft type copolymeride is prepared by polymerization of a unifunctional monomer (A), an origomer (B) of Mw 1X10<4> or below in which a specific polar radical is coupled only at the termination of a polymeride main chain consisting of unit according to Formula I, a multi-functional monomer (D) capable of copolymerizing with the monomer (A), unifunctional macro- monomer (M) (Mw 1X10<3> thru 2X10<4>) where a double bond radical is coupled at the Block B termination of an A-B block copolymeride consisting of Block A of polymeride component having a specific polar radical and Block B having polymeride component according to Formula II and a polymerizative monomer according to Formula III having an aliphatic radical of a carbon number eight or more, wherein further copolymeride resin particles are included which are prepared through polymerizative reactions of a solution provided by dissolving a soluble resin [P] for dispersion stabilizing in a non-aqueous solvent.

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. And a liquid developer excellent in resist property.

[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. However, these particles should be as uniform in particle size as possible over time. It is important that particles do not agglomerate / precipitate, and if these are not satisfied, the reproducibility of the image area will become poor, the non-image area will become dirty, or the developer delivery pump of the developing device will become clogged. Will end up.

As an improvement of these, a non-aqueous dispersion polymerization method for obtaining insoluble latex particles having a fine particle size and good monodispersity has been proposed and various studies have been made.
For example, U.S. Pat. Nos. 3,990,980 and 4,61
No. 8,557, JP-A Nos. 1-257969 and 2-74.
956, 1-282566, 2-173667
No. 3,140,970, No. 3-225353, No. 4-15661, and the like, a method of improving with a soluble dispersion stabilizing resin is also disclosed in U.S. Pat. No. 1,237,668,
2-168276, 3-213165, 4-
No. 46354 describes a method of modifying the surface of latex particles by allowing an insolubilizing monomer and another compound having a physicochemical interaction to coexist.
It is disclosed that the particle size, redispersibility and storage stability can be improved.

[0005]

On the other hand, in recent years, the direct lithographic printing system to which the electrophotographic technique is applied has been actively put into practical use or developed. These systems
A toner image portion is formed on the surface of an electrophotographic photosensitive material by an electrophotographic method, and then processed to convert a non-image portion into a hydrophilic material to obtain a lithographic printing original plate. As a method of making the non-image portion hydrophilic, a method of eluting the portion with a treatment liquid and utilizing the hydrophilicity of the surface of the support of the electrophotographic photosensitive layer, or a method of making the surface portion of the non-image portion of the photosensitive layer The main method is to change from lipophilicity to hydrophilicity.

In recent years, as the latter method, an improvement of the conventionally known method for desensitizing the photoconductive zinc oxide in the photosensitive layer has been disclosed in JP-A-62-21669 and JP-A-1-19.
No. 1157, No. 2-15277, etc., the binder resin used in the photosensitive layer is converted to hydrophilic by treatment.
It is disclosed that the improvement of hydrophilicity is achieved.
In these systems, it is important to maintain the image portion of the toner image portion without any change with respect to the treatment liquid in the hydrophilic treatment (hereinafter referred to as the resist property to the treatment liquid).

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, the resist property of the toner is not sufficient when the non-image area is made sufficiently hydrophilic. In some cases, the image part was missing. In particular, this problem becomes noticeable in areas where the area of the toner image portion such as fine lines / characters or halftone dots is small, and deterioration of the printed matter was observed. Further, insoluble latex particles having high durability to the treatment liquid (for example, styrene-based latex) have sufficient resist properties, but have poor charge stability and redispersibility as toner particles,
Further, since the fixing property of the toner particles is poor and sufficient fixing requires a high heat and a long fixing time, the complexity of the apparatus becomes a problem.

The present invention solves the problems of the conventional liquid developer described above. The purpose of the present invention is to
It is an object of the present invention to provide a liquid developer excellent in dispersion stability, redispersibility, fixability and hydrophilic treatment liquid resist property in an electrophotographic plate making system. Another object of the present invention is to provide a liquid developer capable of producing an offset printing original plate excellent in reproducibility of a copied image with respect to an original image by an electrophotographic method. 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. Still another object of the present invention is to provide a liquid developer which enables production of an offset printing original plate using an inkjet recording, a cathode ray tube recording and a recording system of various changing steps such as pressure change or electrostatic change. Is.

[0009]

The above objects of the present invention are as follows.
In a liquid developer for electrostatic photography, wherein at least resin particles are 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, the dispersed resin particles are compatible with the non-aqueous solvent. At least one monofunctional monomer (A) which is soluble but is insolubilized by polymerization, a carboxyl group only at one end of the main chain of the polymer comprising a repeating unit represented by the following general formula (I) , Sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and —P (═O) (OH) G ¹ group [wherein G ¹ is a hydrocarbon group or —OG ² group (G ² is a hydrocarbon group. At least one 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 At least 2 possible polymerizable functional groups It is a polymer resin particle obtained by polymerizing a solution containing at least one of the above-mentioned polyfunctional monomer (D) and at least one of the dispersion stabilizing resin [P] having the following content. Achieved by a featured electrostatographic liquid developer. As the dispersion stabilizing resin [P]: (i) Phosphono group, carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, -P (= O) (O
H) R ¹ group [R ¹ represents an -R ² group or an -OR ² group,
R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -S
O ₂ NR ³ R ⁴ group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a polymer containing at least one polar group selected from cyclic acid anhydride-containing groups A composed of a block A containing a component and / or a polymer component corresponding to the monofunctional monomer (A) and a block B containing at least a polymer component represented by the following general formula (II). A weight average molecular weight of 1 ×, which forms a block copolymer B and has a polymerizable double bond group bonded to one end of the polymer main chain of block B opposite to the end adjacent to block A. Obtained by polymerizing a solution containing at least one of 10 ^{3 to} 2 × 10 ⁴ monofunctional macromonomers (M) and (ii) a monomer (B) represented by the following general formula (III). Is a graft-type copolymer, which is a dispersion-stabilizing resin soluble in the non-aqueous solvent. It

[0010]

[Chemical 6]

In the formula (I), V ⁰ is --COO-- or --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - 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, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—D ¹² , or —CO via a hydrocarbon group.
Represent O-D ¹² (wherein D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group). D ⁰ has 1 to 22 carbon atoms
Or a substituent selected from the substituents represented by the following general formula (IV).

[0012]

[Chemical 7]

In the formula (IV), 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) -,
-CON (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's may be the same as or different from each other, each may be substituted, or may represent a hydrocarbon group having 1 to 18 carbon atoms, which may be represented by the following chemical formula 8 in the bond of the main chain.

[0014]

[Chemical 8]

In the chemical formula 8, B ³ and B ⁴ may be the same or different from each other and have the same contents as the above B ¹ and B ² .
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 or different and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time.

[0016]

[Chemical 9]

In the formula (II), X ¹ is --COO-- or --OCO.
_{-, - (CH 2) x} OCO -, - (CH 2) x COO-
[Where x represents an integer of 1 to 3], -O-, -SO ₂
-, - CO -, - CON (R 11) -, - SO 2 N
(R ¹¹ )-[wherein R ¹¹ represents a hydrogen atom or a hydrocarbon group], -CONHCOO-, -CONHCONH-, or a phenylene group [hereinafter, a phenylene group is -Ph.
Is represented by-, -Ph- is a 1,2-phenylene group, 1,3
-Including a phenylene group and a 1,4-phenylene group.
The same applies below. Y ¹ represents a hydrocarbon group. b ¹ and b
² may be the same or different from each other, each is a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group having 1 to 8 carbon atoms,
-COO-Z ¹ or -COO-Z ¹ (wherein Z ¹ via a hydrocarbon group having 1 to 8 carbon atoms is 1 to hydrogen or carbon atoms
22 represents a hydrocarbon group of 22).

[0018]

[Chemical 10]

In the general formula (III), X ² is --COO-- or --O.
_{CO -, - (CH 2)} y OCO -, - (CH 2) y CO
O- [where y represents an integer of 1 to 3] or -O- is represented. Y ² represents an aliphatic group having 8 or more carbon atoms. d ¹
And d ² may be the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.

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, are the graft type copolymers of the present invention in the non-aqueous solvent. In the presence of the dispersion-stabilizing resin [P] soluble in, at least one of the monofunctional monomer (A), at least one of the oligomer (B), and at least one of the polyfunctional monomer (D). It is polymerized and granulated by polymerization.

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 used in combination with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluoroalcohol, 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 the polymerization and granulation. However, even if it is brought into a liquid developer as a latex particle dispersion, it is developed. There is no problem as long as the liquid resistance of the liquid is in a range that can satisfy the condition of 10 ⁹ Ωcm or more. Usually, 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 Examples include hydrocarbons.

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 include monomers represented by the following general formula (V).

[0026]

[Chemical 11]

In the formula (V), T ¹ is --COO-- or --OCO.
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, -
CONHCOO -, - CONHOCO -, - SO 2 -,
^{-CON (W 1) -, -} SO 2 N (W 1) -, or -P
represents h- (phenylene group). Here, W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, 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, etc.).

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.).

E ¹ and e ² may be the same or different and each is a ¹ or a ² in the general formula (I).
Represents the same content as.

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) is a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and- At least one polar group selected from the group P (= O) (OH) G ¹ [wherein G ¹ represents a hydrocarbon group or an -OG ² group (G ² represents a hydrocarbon group)] Is an oligomer having a number average molecular weight of 1 × 10 ⁴ or less.

[0032]

[Chemical 12]

In the formula (I), V ⁰ is --COO--, --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - COND 11 -,} - SO 2 ND 11 -,
Or represents a phenylene group (—Ph—) (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 as or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹² or —COO-D ¹² via a hydrocarbon group ( Here, 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 (IV).

[0034]

[Chemical 13]

In the formula (IV), 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) -,
-CON (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's may be the same as 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 14 interposed in the bond of the main chain.

[0036]

[Chemical 14]

In the chemical formula 14, 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, and A ⁴ is a carbon atom having 1 to 18 carbon atoms which may be substituted. A hydrogen group, and D ²³ has the same meaning as D ²¹ above. m, n
And p may be the same or different from each other, and each is 0 to 4
Represents the integer. 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 (for example, chlorine atom, bromine atom, etc.), an alkyl group (for example, 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 specifically has the same meaning as described above for D ¹¹ .

The case where D ⁰ represents a substituent represented by the general formula (IV) will be described in detail. A ¹ and A ² are
They may be the same as or different from each other, each may be substituted, or the Chemical formula 14 may be interposed in the bond of the main chain,
A hydrocarbon group having 1 to 18 carbon atoms (the hydrocarbon group includes an alkyl group, an alkenyl group, an aralkyl group, and an alicyclic group; specific examples thereof include the same contents as the specific examples listed in D ^11; Is represented). 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 is composed of any combination of atomic groups such as the chemical formula 14 above. is there.

[0044] Also, the general formula (I) bonded groups ^{in: -V 0 - (A 1 -B} 1) m - in _{^{(A 2 -B 2) n -D}} 21, from V ⁰ D ²¹ (ie, V ⁰ , A ¹ , B ¹ , A
It is preferable that the connecting main chain composed of ² , B ² , D ²¹ ) has a total number of atoms of 8 or more. here,
When A ^1, A ¹ is a hydrocarbon group of interposing the reduction 14 in the binding of the main ^{chain, -B 3 - (A 4 -B} 4) p -D
^{23 is} also included in the linking backbone. As the number of atoms of the connecting main chain, for example, when V ⁰ represents —COO— or —CONH—, an oxo group (═O group) and a hydrogen atom are not included as the number of atoms, and the number of carbon atoms constituting the connecting main chain is increased. Atoms, ether type oxygen atoms, and nitrogen atoms are included as the number of atoms. Therefore, -COO- and -CONH- are counted as having 2 atoms. Similarly, if the 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 a substituent represented by the general formula (IV), 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; k ₁ and k ₂ are each 1 to
12 is an integer; m ₁ is an integer of ₁ to 100.

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

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 of the repeating units of the oligomer (B), the repeating unit component represented by the general formula (I) is preferably contained in an amount of 40% by weight or more, 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-
It represents an OG ² group (G ² represents a hydrocarbon group). G ¹
Alternatively, the hydrocarbon group represented by G ² has 1 carbon atom
To 18 hydrocarbon groups are preferable, and more preferably aliphatic groups having 1 to 8 carbon atoms which may be substituted (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, or the like, or an aromatic group which may be substituted (for example, 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, represent -NHG ³ or -NG ³ G ^4. G ³ and G ⁴ each represent a hydrocarbon group having 1 to 18 carbon atoms,
It preferably represents a hydrocarbon group having 1 to 8 carbon atoms, specifically, the same content as the hydrocarbon group of G ¹ or G ² described above. Even more preferably, G ¹ , G ² , G ³
Examples of the hydrocarbon group of G ⁴ and G ⁴ include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, and an optionally substituted phenyl group.

Here, the polar group has a chemical structure 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).

[0055]

[Chemical 19]

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 is a single bond or -CG ⁵ G
^6- [wherein 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, ethyl group, a propyl group)], - (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 -, - N
It represents a linking group composed of any combination of HCOO-, -NHCONH- and the like. However, G ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and specific examples thereof include those described for D ¹¹ in the formula (I). Further, the main chain of the polymer contains a copolymer component containing a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, and a polar group such as -P (= O) (OH) G ¹ group. Those that do not are preferred.

The oligomer (B) of the present invention in which a specific polar group is bonded to only one end of the main chain of the polymer has various reagents at the end of a 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. %, And preferably 1 to 10% by weight.

Preferred oligomers (B) for use in the present invention are represented by the general formula (Ia) or (Ib). Specific examples of the moiety represented by G-L- in these formulas are shown below. Show. 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.

[0062]

[Chemical 20]

[0063]

[Chemical 21]

[0064]

[Chemical formula 22]

Next, a monomer (D) having two or more polymerizable functional groups, which is used together with the monofunctional monomer (A) and the oligomer (B), is copolymerizable with the monomer (A). (Less than,
The polyfunctional monomer (D) will be described below.
The polymerizable functional group contained in the polyfunctional monomer (D) may be any as long as it can be copolymerized with the monomer (A). Specifically, it is represented by the following general formula (VI). The functional groups shown may be mentioned.

[0066]

[Chemical formula 23]

[0067] In the formula ^{(VI), e 1, e} 2 and T ¹ have the same meanings as e ^1, e ² and T ¹ in the general formula (V).

The polyfunctional monomer (D) may be a monomer having two or more of these polymerizable functional groups which are the same or different, and the monomer (A) And a polymer which is insoluble in a non-aqueous solvent by polymerizing with the oligomer (B).

Specific examples of the monomer (D) having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene as the monomers having the same polymerizable functional group; Polyhydric alcohol (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 40
0, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (for example, hydroquinone, resorcin, catechol and them. Derivatives of methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers; dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, Itaconic acid etc.) vinyl esters, allyl esters, vinyl amides or allyl amides; polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine etc.) and vinyl Carboxylic acids having (e.g.,
Methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.) and the like.

As the monomer having different polymerizable functional groups, for example, a carboxylic acid having a vinyl group [for example,
Reactants of methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydrides and alcohols or amines (e.g., allyloxycarbonylpropionic acid, allyl). Oxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.] or a vinyl group-containing ester derivative or amide derivative (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconic acid, allyl methacrylate) , Allyl acrylate, allyl itaconic acid, methacryloyl vinyl acetate, methacryloyl vinyl propionate,
Allyl methacryloylpropionate, vinyloxycarbonylmethylmethacrylate methacrylic acid, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N-ally itaconic acid amide, methacryloylpropionic acid allylamide, etc.); or , Amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group-containing carboxylic acid condensates.

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A), the oligomer (B) and the monomer (D), and importantly, is synthesized from these monomers and oligomers. If the obtained resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. Specifically, the oligomer (B) is added in an amount of 0.1 to 0.1 with respect to the insolubilizing monomer (A).
It is preferable to use 10% by weight, and more preferably 0.3 to 5% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention is 2 of all the monomers.
It is used in an amount of 0 mol% or less, preferably 10 mol% or less, and polymerizes to form a resin. 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 .

The solvent-insoluble polymer produced by polymerizing the monomer (A), the oligomer (B) and the monomer (D) in a non-aqueous solvent is used to form a stable resin dispersion. The dispersion-stabilizing resin [P] of the present invention is a monofunctional macromonomer (M) composed of an AB type block copolymer component.
And a monomer (B) represented by the general formula (III), each of which is a graft-type copolymer obtained by polymerizing at least one kind, and is soluble in the non-aqueous solvent. In particular, in the graft portion of the graft copolymer, the block portion (that is, block A) separated from the main chain of the graft copolymer has a specific polar group described above (ie, phosphono group, carboxyl group, sulfo group, hydroxyl group). Group, formyl group, amino group, -P (= O) (OH) R ¹ group, -CON
R ³ R ⁴ group, —SO ₂ NR ³ R ⁴ group, cyclic acid anhydride-containing group} and / or a polymer component containing at least one polar group selected from the group (A) which is insolubilized. It is characterized in that it is composed of a polymer component corresponding to the same monomer.

The weight average molecular weight of the graft copolymer is 1.5 × 10 ^{4 to} 3 × 10 ⁵ , preferably 2 × 1.
It is 0 ⁴ to 1 × 10 ⁵ . Weight average molecular weight is 1.5 × 1
When it is less than 0 ⁴ or more than 3 × 10 ⁵ , in either case, the average particle size of the resin particles obtained by polymerization granulation becomes coarse or the distribution of the particle size becomes wide, and the monodispersity is impaired.
Furthermore, it does not become a dispersion but becomes an aggregate. The proportion of the monofunctional macromonomer (M) as a copolymerization component of the graft copolymer is 1% by weight to 60% by weight, preferably 5% by weight to 40% by weight. If the proportion is less than 1% by weight, the number of grafted portions will be significantly reduced, and the chemical structure will be similar to that of conventional random copolymers, and the improvement of redispersibility, which is the effect of the present invention, can be seen. I will not be able to. On the other hand, the proportion is 60% by weight
If it exceeds, the copolymerizability with the monomer (B) represented by the general formula (III) becomes insufficient.

The proportion of the other copolymerizable component (B) represented by the general formula (III) in the graft copolymer is 40 to 99% by weight, preferably 6% by weight.
It is 0 to 95% by weight.

On the other hand, the weight average molecular weight of the monofunctional macromonomer (M) of the present invention, which is the graft portion of the graft copolymer, is 1 × 10 ³ to 2 × 10 ⁴ , preferably 2 ×. It is 10 ³ to 1 × 10 ⁴ . When the weight average molecular weight is less than 1 × 10 ³ , the redispersibility of the obtained dispersed resin particles is deteriorated. If it exceeds 2 × 10 ⁴ ,
The copolymerizability with the monomer (B) represented by the general formula (III) is reduced, and a graft copolymer cannot be obtained.
Since the graft copolymer of the present invention as described above is soluble in the non-aqueous solvent, either the polymer main chain part or the B block containing the repeating unit represented by the general formula (II) of the graft part is either Or, both contain a repeating unit that becomes soluble.

The contents of the graft copolymer will be described in more detail below. In the monofunctional macromonomer (M) used for the graft copolymer, the block A
Examples of the polymer component constituting the component include a component containing a specific polar group and / or a component corresponding to the insoluble monofunctional monomer (A). Specific polar groups include phosphono groups, carboxyl groups, sulfo groups, hydroxyl groups, formyl groups, amino groups, -P (= O) (OH) R ¹ groups,-
Examples thereof include CONR ³ R ⁴ group, —SO ₂ NR ³ R ⁴ group, and cyclic acid anhydride-containing group.

In the -P (= O) (OH) R ¹ group, R
¹ represents a -R ² group or a -OR ² group, and R ² represents a hydrocarbon group. The hydrocarbon group preferably has 1 to 8 carbon atoms and may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Octyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 2-cyanoethyl group, allyl group, 1-propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopentyl group, cyclohexyl group, benzyl group , Phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, or the like, or an aryl group which may be substituted (eg, phenyl group, tolyl group, xylyl group, mesityl group) , Ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc. ) Etc. It is.

--CONR ³ R ⁴ group and --SO ₂ NR ³ R
^{In the 4} groups, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted). Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include the same as those of the hydrocarbon group represented by R ¹ and R ² .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an 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).

In the polar group of the present invention, the amino group is -N
H _2, represents a -NHR ⁵ or -NR ⁵ R ^6. R ⁵ , R ⁶
Represents a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and specifically, the above R
Examples thereof include those having the same content as the hydrocarbon group represented by ² .

The monomer capable of inducing the "polymer component containing a specific polar group" as described above is, for example, a polymer component constituting another block component of the AB block copolymer of the present invention. Any vinyl compound that is copolymerizable with the vinyl compound corresponding to [the repeating unit represented by the general formula (II)] and contains a polar group can be used. For example, "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science, Baifukan (1986)
Etc. 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-bromo form , Α-fluoro body, α
-Tributylsilyl body, α-cyano body, β-chloro body,
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 (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, vinyl Benzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid,
Examples thereof include half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, ester derivatives of these carboxylic acids or sulfonic acids, and compounds having the polar group in the substituent of an amide derivative.

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
COOCH ₃ or indicates -CH ₂ COOH, f represents -H or -CH _3, n is an integer of 2 to 18, m is 1
Shows an integer of -12, p shows an integer of 1-4.

[0083]

[Chemical formula 24]

[0084]

[Chemical 25]

[0085]

[Chemical formula 26]

[0086]

[Chemical 27]

[0087]

[Chemical 28]

[0088]

[Chemical 29]

[0089]

[Chemical 30]

[0090]

[Chemical 31]

[0091]

[Chemical 32]

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

The block B is composed of at least a polymer component composed of a repeating unit represented by the general formula (II). In the general formula (II), X ¹ is —COO—, —OC.
O -, - O -, - CO -, - (CH 2) x -OCO-,
- (CH _{2) x} -COO- [x represents an integer of 1 to _{3], -SO 2 -, - CON (} R 11) -, - SO 2 N
(R ¹¹ )-[R ¹¹ represents a hydrogen atom or a hydrocarbon group],
-CONHCOO-, -CONHCONH-, or -P
represents h- (phenylene group).

Here, R ¹¹ is not only a hydrogen atom, but also a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). Group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms 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, etc.), an aralkyl group having 7 to 12 carbon atoms which may be substituted (eg, 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.), Or
An optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, 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, a dodecyloylamidophenyl group and the like).

When X ¹ represents -Ph- (phenylene group), the benzene ring may have a substituent. As the substituent, 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 group, propioxy group, butoxy group, etc.) and the like.

Y ¹ represents a hydrocarbon group, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms 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-
A hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a 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.),
An alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.), an aromatic group having 6 to 12 carbon atoms which may be substituted ( For example, phenyl group, naphthyl group,
Tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, Acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

B ¹ and b ² may be the same 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 4
Alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-Z ¹ or -COO-Z ¹ via a hydrocarbon (wherein Z ¹ is preferably a hydrogen atom or a carbon number). 1 to 18 represents an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically has the same contents as those described for R ¹¹ above. ) Is represented. Examples of the hydrocarbon in the -COO-Z ¹ group through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (II),
X ¹ is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
Represents-, or -Ph-, and b ¹ and b ² may be the same or different from each other, and each is a hydrogen atom, a methyl group, or -C.
Represents OOZ ¹ or —CH ₂ COOZ ¹ . Where Z
¹ more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Even more preferably, ^one of b ¹ and b ² represents a hydrogen atom.

Further, as a polymer component contained in the block B, acrylonitrile or methacrylonitrile is used as a monomer corresponding to another repeating unit copolymerizable with the polymer component represented by the formula (II). Nitriles, heterocyclic vinyls (eg vinyl pyridine, vinyl imidazole,
Vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) and the like. These other monomers are used in an amount not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of block B. Further, it is preferable that the block B does not contain a polymer component containing a polar group which is a constituent of the block A.

In the monofunctional macromonomer (M) used in the graft copolymer of the present invention, the abundance ratio of block A and block B in the AB block copolymer is
It is preferably 1 to 50/99 to 50 (weight ratio). The specific polar group-containing polymer component contained in the block A is preferably the dispersion stabilizing resin [P] 1
1 to 30 parts by weight in 00 parts by weight, more preferably 1 to 1
5 parts by weight.

The macromonomer (M) of the present invention is an AB type composed of a block A consisting of the above-mentioned component containing a polar group and a block B consisting of the polymer component represented by the general formula (II). A monofunctional macromonomer that forms a block copolymer and has a polymerizable double bond group bonded to one end of the polymer main chain of block B opposite to the end adjacent to block A. . The polymerizable double bond group linked to one end of the block B will be described. Specific examples thereof include a polymerizable double bond group represented by the following general formula (VII).

[0102]

[Chemical 33]

In the general formula (VII), X ³ is X ¹ in the formula (II).
Represents the same content as. f ¹ and f ² may be the same as or different from each other, and have the same contents as b ¹ and b ² in the formula (II). That is, as the polymerizable double bond group represented by the general formula (VII), more specifically, CH ₂ ═CH—CO—O.
_{-, CH 2 = C (CH} 3) -CO-O-, CH 3 -CH
= CH-CO-O-, CH 2 = C (CH 2 COOH) -
_{CO-O-, CH 2 = C} (CH 2 COOCH 3) -CO
_{-O-, CH 2 = CH-CONH-} , CH 2 = C (CH
_{3) -CONH-, CH 3 -CH =} CH-CONH-,
_{CH 2 = CH-O-CO-} , CH 2 = CH-CH 2 -O
_{-CO-, CH 2 = CH-O-} , CH 2 = C (COO
_{H) -CH 2 -CO-O-,} CH 2 = C (COOC
_{H 3) -CH 2 -CO-O-} , CH 2 = CH-Ph-,
_{CH 2 = CH- (CH 2)} 2 -COO-, CH 2 = CH
_{-CO-, CH 2 = CH- (CH} 2) 2 -O-CO- and the like.

The macromonomer (M) provided in the present invention has the general formula (V) at one end of the block B as described above.
The polymerizable double bond group represented by II) is directly bonded,
Alternatively, it has a chemical structure bound by an arbitrary linking group. As the linking group, carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (as a hetero atom, for example, oxygen atom, sulfur atom, nitrogen atom, silicon atom, etc.), hetero atom-hetero atom bond It is composed of any combination of atomic groups. That is, specifically, a mere bond or —CR ¹² R ¹³ — [R ¹² , R
¹³ represents a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (a methyl group, an ethyl group, a propyl group, etc.), respectively, and-(CH = _{CH) -, - C 6 H} 10 - ( i.e., cyclohexylene), - Ph -, - O -, - S -, - CO
^{-, - NR 14 -, -} COO -, - CS -, - SO 2 -,
_{^{-CONR 14 -, - SO 2 NR}} 14 -, - NHCOO-,
^{-NHCONH -, - SiR 14 R 15} - [R ^14, R ¹⁵ are,
Each of which represents a hydrogen atom, a hydrocarbon group having the same content as R ² in the polar group, or the like], or a combination of two or more arbitrary atomic groups. A linking group is mentioned.

The weight average molecular weight of the macromonomer (M) is 1 × 10 ³ to 2 × 10 ⁴ . Weight average molecular weight is 2 ×
When it exceeds 10 ⁴ , the copolymerizability with the monomer (B) decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so 1 × 10 ³ or more is preferable.

The macromonomer (M) 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, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium halide, etc.) or Ion polymerization reaction with hydrogen iodide / iodine system, photopolymerization reaction using porphyrin metal complex as catalyst,
Alternatively, an AB type block copolymer is synthesized by a known so-called living polymerization reaction such as a group transfer polymerization reaction, and then various reagents are reacted with the ends of the living polymer to introduce a polymerizable double bond group. Then, a method of forming a polar group by carrying out a deprotection reaction of a functional group having a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photolysis reaction, or the like can be mentioned. One example thereof is shown in the following reaction scheme (1).

[0107]

[Chemical 34]

[0108]

[Chemical 35]

For example, P. Lutz, P .; Masson
et al, "Polym. Bull." 12 , 79.
(1984), B.I. C. Anderson, G.M. D. A
ndrews et al, “Macromoleculecu
les " 14 , 1601 (1981), K. Hatad.
a, K. Ute, et al, "Polym. J." 1
7 , 977 (1985), 18 , 1837 (198).
6), Koichi Right Hand, Koichi Hatada "Polymer Processing" 36 , 366
(1987), Toshinobu Higashimura, Mitsuo Sawamoto "Polymer Papers" 4
6 , 189 (1989), M.S. Kuroki, T .; Ai
da, "J. Am. Chem. Soc." 109 , 47.
37 (1987), Takuzo Aida, Shohei Inoue "Organic Synthetic Chemistry" 43 , 300 (1985), D.M. Y. Sogah,
W. R. Hertler et al, “Macrom
olecules ” 20 , 1473 (1987), etc., a living polymer can be easily synthesized. Further, as a method for introducing a polymerizable double bond group to the end of the living polymer, a conventionally known method is known. The macromonomer of the present invention can be easily obtained according to the method for synthesizing the macromonomer.

Specifically, P.I. Dreyfuss, R.A.
P. Quirk, "Encycl. Poly. Sci.
Eng. , 7 , 551 (1987), PF Remp.
p, E. Franta, "Advances in P"
polymer Science " 58 , 1 (198
4), V. Percec, "Applied Poly"
mer Science " 285 , 95 (1984),
R. Asami, M .; TakaRi, “Makvamo
l. Chem. Suppl. " 12 , 163 (198
5), P. Rempp et al, “Makvamo
l. Chem. Suppl. " 8 , 3 (1984), Yusuke Kawakami" Chemical Industry " 38 , 56 (1987), Yuya Yamashita" Polymer " 31 , 988 (1982), Shiro Kobayashi" Polymer " 30 , 625 (1981), Shun Higashimura. General reviews of Nobu “Japan Adhesive Association Magazine” 18 , 536 (1982), Koichi Ito “Polymer Processing” 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda “Functional Materials” 1987 , No. 10, 5, etc. It can be synthesized according to the method described in the cited documents and patents.

The protecting group for protecting the specific polar group of the present invention 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-mentioned references, and further, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha Co., Ltd. (1977), T.S. W. Greene, “Prot
active Groups in Organic
Synthesis ”John Wiley & So
ns (1981), J. F. W. McOmie, "P
Protective Groups in Organ
ic Chemistry "Plenum Pres
s, (1973), etc., the method described in detail in the review can be appropriately selected and performed.

As another method for synthesizing the AB block copolymer, a photoiniferter polymerization method using a dithiocarbamate compound as an initiator can be used. For example, Takayuki Otsu "Polymer" 37 , 248 (1988),
Shunichi Hinomori, Ryuichi Otsu, “Polym. Rep. Ja
p. 37 , 3508 (1988), JP-A-64-11.
No. 1, JP-A-1-26619, and the like. The macromonomer of the present invention can be obtained by utilizing the above-described macromonomer synthesis method.

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these. In the following specific examples, a ₁ , a ₂ and a ₃ are -H,
It represents -CH ₃ or -CH ₂ COOCH _3; a ₄ is -H
Or represents -CH _3; R ₁ is -C _n H _{2n + 1} [n is 1-1
8 _{integer], - (CH 2) m -C} 6 H 5 [-C ₆ H ₅ is a phenyl radical, n is an integer of 1 to 3], -Ph-X [Ph is a phenylene group, X is -H, -Cl, -Br, -CH _3,
-OCH ₃ or -COCH _3], or - (CH _{2) p} -
C ₁₀ H ₈ [-C ₁₀ H ₈ is 1- or 2-naphthyl group, p is an integer of 1 to 3] represents; R ₂ is -C _q H _{2q + 1} [q is 1
8 integer], or _{- (CH 2) r -C 6} H 5 [r is 1
An integer of 8]; Y ₁ is —OH, —COOH, —SO
₃ H, -OP (= O) (OH) ₂ , or -OP (=
O) represents _{(OH) (OCH 3);} Y 2 is -COOH,
_{-SO 3 H, -O-P (} = O) (OH) 2, or -O-
It represents P (= O) (OH) (OCH 3); s is 2 to 12
Represents an integer; and t represents an integer of 2 to 6. -B- represents a block bond.

[0114]

[Chemical 36]

[0115]

[Chemical 37]

[0116]

[Chemical 38]

[0117]

[Chemical Formula 39]

[0118]

[Chemical 40]

The dispersion-stabilizing resin [P] of the present invention comprises a graft containing the monofunctional macromonomer (M) and at least one monomer (B) represented by the general formula (III). Type copolymer. In the general formula (III),
X ² is preferably -COO-, -OCO-, or-.
Represents O-. Y ² represents an aliphatic group having 8 or more carbon atoms, preferably an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched.
Specific examples thereof include a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosanyl group, a docosanyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, and a linolel group. . d ¹ and d ² may be the same or different from each other, and preferably each is a hydrogen atom,
It represents a halogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
Specific examples include a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group and a propyl group.

The proportion of the monomer selected from the group of monomers represented by the general formula (III) as a copolymerization component of the graft copolymer is 40 to 99 parts by weight, preferably 6 parts by weight.
0 to 95 parts by weight. Further, as a component of the graft copolymer of the present invention, the macromonomer (M) and the monomer (B) represented by the formula (III) may be contained together with other monomers copolymerizable therewith. Although it is good, the proportion thereof is 20% by weight or less, preferably 15% by weight or less.

The weight average molecular weight of the dispersion stabilizing resin [P] of the present invention is preferably 1.5 × 10 ^{4 to} 3 × 10 ⁵ , and more preferably 2 × 10 ⁴ to 1 × 10 ⁵ . The dispersion stabilizing resin [P] used in the present invention is soluble in an organic solvent. Specifically, at least 5 parts by weight or more of the dispersion stabilizing resin is added to 100 parts by weight of a toluene solvent at a temperature of 25 ° C. Any substance that dissolves may be used.

To produce the dispersion resin particles used in the present invention, generally, the dispersion stabilizing resin [P], the monofunctional monomer (A), the oligomer (B), and the polyfunctional resin as described above are used. The monomer (D) may be polymerized by heating in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium. Specifically, a method for adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin [P], the monomer (A), the oligomer (B) and the monomer (D), the dispersion stabilizing resin [P ], The monomer (A), the oligomer (B) and the monomer (D) are added dropwise together with the polymerization initiator, or the total amount of the dispersion stabilizing resin [P] and the monomer ( The remaining monomer (A), oligomer (B) and monomer (D) may be optionally added together with the polymerization initiator in the mixed solution containing A), the oligomer (B) and a part of the monomer (D). In addition to the polymerization initiator, a mixed solution of the dispersion-stabilizing resin [P], the monomer (A), the oligomer (B) and the monomer (D) can be optionally added to the non-aqueous solvent. There is a method of adding to
It can be manufactured by any method.

The total amount of the monomer (A), the oligomer (B) and the monomer (D) is 5 to 100 parts by weight of the non-aqueous solvent.
The amount is about 80 parts by weight, preferably 10 to 50 parts by weight. The amount of the oligomer (B) is about 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the monomer (A). The soluble resin which is the dispersion stabilizing resin [P] is 1 to 1 with respect to 100 parts by weight of all the monomers [monomer (A) and monomer (D)] used above.
The amount is 00 parts by weight, preferably 5 to 50 parts by weight.
The amount of the polymerization initiator is appropriately 0.1 to 15% by weight based on the total amount of the monomers. The polymerization temperature is about 50 to 180 ° C,
It is preferably 60 to 120 ° C. Reaction time is 1-15
Time is preferred.

When a polar solvent such as the alcohols, ketones, ethers and esters described above is used in combination with the non-aqueous solvent used in the reaction, or the monomer (A) or a single amount to be polymerized and granulated is used. When the unreacted substance of the body (D) remains, it is removed by heating the solvent or above the boiling point of the monomer (A) or the monomer (D) and then distilling off or distilling under reduced pressure. Is preferred.

The non-aqueous latex particles produced as described above are present as fine particles having a uniform particle size distribution and, at the same time, exhibit extremely stable dispersibility, and particularly, they can be repeatedly used for a long time in a developing device. However, the dispersibility is good and no aggregation or precipitation is observed in the developing 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, when used in a plate making system,
Even after undergoing the hydrophilic treatment process of the non-image area, it has excellent resist property of the toner image area and shows excellent original image reproducibility of the image area of the printed matter.

The liquid developer of the present invention that brings about the above effects is made possible by the insoluble latex provided by the present invention. That is, the dispersion stabilizing resin [P] of the present invention
Is 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 monomer (A) having a low affinity for the non-aqueous solvent and becoming insoluble. Is a graft-type copolymer in which a terminal block of a graft portion composed of a polymer component having an affinity for is bonded. Thereby, for the dispersed resin particles,
The block B portion of the graft portion is sufficiently adsorbed by physicochemical interactions during polymerization granulation, and the polymer main chain portion having a large affinity for the non-aqueous dispersion medium is sufficiently solvated with the solvent. It is presumed that the three-dimensional repulsion effect is sufficiently exerted (so-called tail-like adsorption) and the effect of the present invention is achieved. On the other hand, in the conventional random copolymer of the polymer component used in the block A and the polymer component used in the block B, in the polymer chain composed of the component that becomes the adsorbed portion is solvated Adhesion to the dispersed resin particles is not sufficient because they are randomly bonded to each other, and the steric repulsion effect is also excluded due to the adsorption pattern becoming a loop, and the dispersion stability was not sufficient. .

Further, the high printing durability without deterioration of the toner image portion when printed as the offset master original plate, the insolubilizing monomer (A) and the dispersion polymer adsorbed thereto have good compatibility with each other. It is presumed that this is achieved by sufficiently compatibilizing even under mild fixing conditions and forming a uniform and strong film. It is considered that these factors suppress the aggregation / precipitation of the insoluble particles and significantly improve the redispersibility.

Further, when the dispersion stabilizing resin [P] of the present invention is used, the dispersion stability is improved, the dispersion stabilization can be achieved with a small amount used, and the resin [P] not adsorbed on the particles is reduced. It can be mentioned. These are concentrated in the developer when the liquid developer is repeatedly used for a long period of time, and the concern that various problems may occur is improved.

On the other hand, the insoluble resin particles of the present invention are characterized in that the particles are polymerized and granulated using the polyfunctional monomer (D) to form a crosslinked structure. This allows
After forming an image as toner particles, even after a hydrophilic treatment step for making a printing original plate, the suitability for the treatment liquid (resist property) is improved, and the damage of the toner image portion can be remarkably reduced. It was Further, in order to alleviate the fixing conditions, it is important in the apparatus that the insoluble resin particles have a resin structure having a low glass transition point. These resins having a low glass transition point are, for example, ester structures, Since it contains a polar structure such as an ether structure or an amide structure, it easily dissolves in the treatment liquid in the hydrophilic treatment step, and as a result, the resist property of the toner portion on the image portion deteriorates. This undesired phenomenon can be remarkably suppressed by partially crosslinking the inside of the resin particles. These effects of the dispersed resin particles of the present invention bring about the effects of the present invention.

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. 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 JP-A-54029, or in the case of producing by a polymerization granulation method as described in JP-B-44-22955. There is a method of preparing a dye-containing copolymer by using a monomer containing a dye in advance.

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, and higher alcohols,
Examples thereof include polyethers and waxes. But,
It is not limited to these.

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 also used as necessary, and can be added in an amount of about 0.5 to 100 parts by weight with respect 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 parts by weight is preferable with respect to 0 parts 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 good quality continuous tone image. Therefore, each addition amount of each additive is controlled within this limit. It is necessary.

[0133]

EXAMPLES The following will describe the effects of the present invention in more detail by showing Production Examples of dispersion stabilizing resin, latex particles and Examples of the present invention, but the present invention is not limited to these. Absent.

Production Example of Oligomer (B) 1: Oligomer B-12,3-Diacetoxypropylmethacrylate 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.

[0135]

[Chemical 41]

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.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

Production Example 32 of Oligomer (B): Oligomer B-32 100 g of 2- (n-nonylcarbonyloxy) ethyl crotonate, 150 g of toluene, and 50 g of ethanol
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.

[0142]

[Chemical 42]

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.

[0144]

[Table 5]

[0145]

[Table 6]

Synthesis Example 1 of Macromonomer (M) 1: Macromonomer M-101 A mixed solution of 30 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream to give -20.
Cooled to ° C. 1,1-diphenylbutyllithium 2g
Was added and reacted for 10 hours. Further, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was thoroughly degassed in a nitrogen stream, added to this mixed solution, and further reacted for 10 hours. After the mixture was brought to 0 ° C., carbon dioxide gas was adjusted to 60 °
The polymerization reaction was stopped by bubbling at a flow rate of milliliter / minute for 30 minutes. The reaction solution obtained is stirred at a temperature of 25 ° C.
Then, 6 g of 2-hydroxyethyl methacrylate was added, and further 5 g of dicyclohexylcarbodiimide, 4-
A mixed solution of 0.2 g of N, N-dimethylaminopyridine and 10 g of methylene chloride was added dropwise over 30 minutes, and the mixture was kept at 3
Stir for hours. The precipitated insoluble material was filtered off, 10 ml of a 30% hydrogen chloride ethanol solution was added to this mixed solution, and the mixture was stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The weight average molecular weight (abbreviated as Mw) of the polymer obtained by collecting the precipitate and drying it under reduced pressure was 6.5 × 10 ³ , and the yield was 56 g.

[0147]

[Chemical 43]

Synthesis Example 2 of Macromonomer (M): Macromonomer M-102 A mixed solution of 5 g of benzyl methacrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. .
This was irradiated with 300 W-xenon lamp light from a distance of 25 cm through a glass filter and reacted for 12 hours. 45 g of butyl methacrylate was further added to this mixture, and the mixture was similarly irradiated with light for 8 hours, and then the reaction mixture was added with 4 g.
4 g of -bromomethylstyrene was added and the reaction was stopped by stirring for 30 minutes. Then Pd-C was added to the reaction mixture,
The catalytic reduction reaction was carried out at a temperature of 25 ° C. for 1 hour. The insoluble material was filtered off and then reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The yield of the obtained polymer is 3
The Mw was ³ × 10 ³ at 3 g.

[0149]

[Chemical 44]

Synthesis Example 3 of Macromonomer (M): Macromonomer M-103 A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C. 2 g of 1,1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of dodecyl methacrylate and 100 g of toluene was thoroughly degassed in a nitrogen stream, and then added to this mixture and reacted for 8 hours. Add 30 ml of ethylene oxide to this reaction mixture while stirring thoroughly.
After ventilating at a flow rate of 30 minutes for 30 minutes, the temperature was cooled to 15 ° C., 10 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. Then 30% in this reaction mixture
After adding 10 g of hydrogen chloride ethanol solution and stirring at 25 ° C. for 1 hour, the precipitate was reprecipitated in 1 liter of petroleum ether, and the collected precipitate was diluted with 300 ml of diethyl ether to 2 ml.
Washed twice and dried. The polymer obtained had a yield of 55 g and M
w was 7.8 × 10 ³ .

[0151]

[Chemical formula 45]

Synthesis Example 4 of Macromonomer (M): Macromonomer M-104 40 g of triphenylmethyl acrylate and toluene 1
Thoroughly degas the mixed solution of 00g under a nitrogen stream, and
Cooled to ° C. 0.2 g of sec-butyllithium was added and reacted for 10 hours. Next, to this mixed solution, a mixed solution of 60 g of octadecyl vinyl ether and 100 g of toluene was thoroughly degassed under a nitrogen stream, and then added and reacted for 12 hours. After this mixture was heated to 0 ° C., 4 g of benzyl bromide was added and reacted for 1 hour and further reacted at a temperature of 25 ° C. for 2 hours. 10 g of a 30% hydrogen chloride-containing ethanol solution was added to this reaction mixture, and the mixture was stirred for 2 hours. The insoluble matter was separated by filtration and then reprecipitated in 1 liter of n-hexane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer is 58 g.
The Mw was 4.5 × 10 ³ .

[0153]

[Chemical formula 46]

Synthesis Example 5 of Macromonomer (M): Macromonomer M-105 Octadecyl methacrylate 70 g, benzyl-N-hydroxyethyl-N-ethyldithiocarbamate 4.8
The mixture of g was sealed in a container under a nitrogen stream and the temperature was 60 ° C.
Warmed to. To this, 10cm with 400W high pressure mercury lamp
Photopolymerization was performed by irradiating with light from a distance of 10 through the glass filter for 10 hours. After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. To the resulting reaction mixture, 6 g of 2-isocyanatoethyl methacrylate was added dropwise 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 1.5 liters of hexane, collected, and dried. The yield of the obtained polymer was 68 g, and the Mw was 6.0 × 10 ³ .

[0155]

[Chemical 47]

Synthesis Example of Dispersion Stabilizing Resin [P] 1: Resin P
-1 Octadecyl methacrylate 80g, macromonomer M
A mixed solution of 20 g of −101 and 150 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was used as 6
g and reacted for 4 hours. I. B. N.
2 g was added and reacted for 6 hours. The Mw of the obtained copolymer was 5 × 10 ⁴ .

[0157]

[Chemical 48]

Synthesis Examples 2 to 12 of Dispersion Stabilizing Resin [P]:
Resins P-2 to P-12 The following table shows the same polymerization method as in Synthesis Example 1 of the dispersion stabilizing resin.
A polymer of C was synthesized. The Mw of each polymer obtained was 3 ×
It was 10 ^{4 to} 6 × 10 ⁴ .

[0159]

[Table 7]

[0160]

[Table 8]

Synthesis Examples 13 to 3 of Dispersion Stabilizing Resin [P]
5: Resins P-13 to P-35 Similar to Synthesis Example 1 except that another macromonomer (M) was used in place of Macromonomer M-101 in Synthesis Example 1 of dispersion stabilizing resin [P]. The copolymers shown in Table D below were synthesized under the polymerization conditions. The Mw of each polymer obtained was 3 × 1.
It was 0 ^{4 to} 7 × 10 ⁴ .

[0162]

[Table 9]

[0163]

[Table 10]

[0164]

[Table 11]

[0165]

[Table 12]

[0166]

[Table 13]

[0167]

[Table 14]

Production Example 1 of Latex Particles: Latex Particle D-1 20 g of dispersion stabilizing resin P-22 and 17 of Isopar H
7 g of the mixed solution was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. Methyl methacrylate 50 g, methyl acrylate 50 g, oligomer B-19 2.4 g, ethylene glycol diacrylate 5 g and Isopar G 2
00g and A. I. V. N. 1.0 g of the mixed solution 2
The mixture was added dropwise over time, and the mixture was stirred as it was for 2 hours. Furthermore, A. I.
V. N. 0.5 g was added and stirred for 3 hours. 20 after cooling
The resulting white dispersion was a latex having a polymerization rate of 95% and an average particle size of 0.25 μm. The particle size is CAPA-500 (manufactured by Horiba, Ltd.)
It was measured at.

Production Examples 2 to 21 of Latex Particles: Latex Particles D-2 to D-21 In Production Example 1 of latex particles, the resin P for dispersion stabilization is used.
-22, oligomer B-19, and ethylene glycol diacrylate were replaced with the above-mentioned Production Example 1 except that the dispersion stabilizing resin, oligomer (B) and monomer (D) shown in Table E below were used. By operating in exactly the same manner, latex particles D-2 to D-21 of the present invention were produced. The degree of polymerization of each latex particle obtained was 85 to 90%, and the average particle diameter was 0.1.
Within the range of 15 to 0.25 μm, the monodispersity was good.

[0170]

[Table 15]

[0171]

[Table 16]

Production Example 22 of Latex Particles: Latex Particle D-22 12 g of dispersion stabilizing resin P-1 and 100 g of vinyl acetate,
A mixed solution of 2 g of oligomer B-2, 5 g of divinyl adipate and 384 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. 2, as a polymerization initiator
2'-azobis (isovaleronitrile) (abbreviation AI
V. N. ) Was added thereto and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred 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 was a latex having a polymerization rate of 90% and an average particle size of 0.22 μm.

Production Examples 23-29 of Latex Particles: Latex Particles D-23 to D-29 Monomer (A) (that is, methyl methacrylate and methyl acrylate) and oligomer B-used in Production Example 1 of latex particles. 19, dispersion stabilizing resin P-22
Latex particles were produced in the same manner as in Production Example 1 except that the compounds shown in Table F below were used instead of the monomer (D) (that is, ethylene glycol diacrylate). The obtained latex particles had a polymerization rate of 85 to 98% and an average particle diameter of 0.15 to 0.25 μm.
And the monodispersity was also good.

[0174]

[Table 17]

[0175]

[Table 18]

Production Example 30 of Latex Particles: (Comparative Example A) The same procedure as in Production Example 1 except that 5 g of ethylene glycol diacrylate as the monomer (D) was removed from Production Example 1 of latex particles. A white dispersion was obtained which was latex particles having a polymerization rate of 98% and an average particle size of 0.23 μm.

Production Example 31 of Latex Particles: (Comparative Example B) Production Example 2 except that 5 g of divinyl adipate as the monomer (D) was removed from Production Example 22 of latex particles.
In exactly the same manner as in 2, the polymerization rate is 90% and the average particle size is 0.22
A white dispersion of latex particles of μm was obtained.

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 Isopar G were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads. Put in, disperse for 4 hours,
A fine dispersion of nigrosine was obtained. Preparation Example 1 of Latex Particles
g, 2.5 g of the above nigrosine dispersion, branched octadecyl alcohol FOC-1800 (manufactured by Nissan Chemical Industries, Ltd.) 1
A liquid developer for electrostatic photography was prepared by diluting 5 g of octadecene-half-maleic acid octadecylamide copolymer with 1 liter of Isopar G.

(Preparation of Comparative Developer A) A liquid developer A for comparison was prepared by replacing the resin dispersion with the following resin dispersion in the production of the above liquid developer. Comparative Liquid Developer A: Resin dispersion of Preparation Example 30 of latex particles.

Various properties were evaluated by using these liquid developers for an electrophotographic plate making system, and the results are shown in Table-G.

[0181]

[Table 19]

The measurement of each evaluation item in Table-G was carried out as follows. (Note 1) Dirt on developing device and 2000th plate image: Liquid developer was used as a developer for fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.), and ELP master II type electrophotographic photosensitive material was used. (Fuji Photo Film Co., Ltd.) was exposed and developed. Plate making speed is 7
Plates / minute. Furthermore, after processing 2000 sheets of ELP master II type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image is 30
% Manuscript was used.

(Note 2) Image fixability: EL liquid developer
The electrophotographic photosensitive material P-1 prepared as described below was used as a developer of P404V to make a plate, and the strength of the image area was visually evaluated using a friction tester. A liquid developer ELP-T (manufactured by Fuji Photo Film Co., Ltd.), which has practically sufficient fixability, was used as a liquid developer serving as a reference for evaluation. <Production of Electrophotographic Photosensitive Material P-1> 34 g of a binder resin B-1 having the following structure, 6 g of a binder resin B-2 having the following structure, 200 g of photoconductive zinc oxide, 0.03 g of uranine, and rose bengal 0. 0.06 g, tetrabromophenol blue 0.02 g, phthalic anhydride 0.30 g, o-chlorophenol 0.01 g, and toluene 300 g were mixed with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.
Dispersion was performed for 10 minutes at a rotation speed of pm. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 26 g / m ² , dried at 100 ° C. for 30 seconds, and then heated at 120 ° C. for 1 hour. Then in the dark 2
The electrophotographic photosensitive material P-1 was produced by leaving it under conditions of 0 ° C. and 65% RH for 24 hours.

[0184]

[Chemical 49]

(Note 3) Toner image resist property: An original plate prepared by the same method as the above (Note 2) was etched using a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.). After passing through once, it was dipped in the hydrophilic treatment liquid E-1 for the photoconductive layer binder resin having the following formulation for 5 minutes, washed with water and dried. The image portion of the obtained printing original plate was observed with an optical microscope, and the presence or absence of damage in the image portion was visually evaluated. <Preparation of Hydrophilization Treatment Liquid E-1> Monoethanolamine 8
0g, Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8
g and 80 g of benzyl alcohol were dissolved in distilled water to make 1 liter, and the pH was adjusted to 11.0 with potassium hydroxide to prepare a treatment liquid E-1.

(Note 4) Printing durability: The printing plate precursor that was subjected to plate making and hydrophilic treatment according to the conditions of (Note 3) above was used as fountain solution, and the hydrophilic treatment liquid E-1 was diluted 20 times with distilled water. Printer Hamada Star 800SX type (manufactured by Hamada Star Co., Ltd.) under the condition that the solution is used and the neutral paper is used as the base paper for printing.
Was used to check the number of printed sheets that did not cause loss of the image portion of the printed matter.

From the results shown in Table-G, the developers of the present invention and Comparative Example A did not cause stains on the developing device and the image on the 2000th plate was clear, showing good results.
This shows that the dispersibility and redispersibility are good. In addition, when the mechanical strength of the toner image area was evaluated by forcibly rubbing, each toner particle was good. That is, it was confirmed that the particles of the present invention have a sufficient fixability in practice.

Further, when the zinc oxide and the binder resin B-1 in the non-image area of the plate surface after the plate making are chemically treated to be hydrophilic, the image area is sufficiently resisted by the toner layer and the image area is deficient. When it was examined under a forced condition whether or not the toner particles did not occur, defects other than the toner particles of the present invention occurred in the fine areas of the toner image portion such as fine lines and fine characters. Further, when printing was carried out as an offset master original plate after processing under ordinary desensitizing processing conditions, a clear printed matter was obtained only after printing 5,000 sheets of the present invention. In Comparative Example A, the reduction in reproducibility of the copied image at the time of plate making appeared on the printed matter as it was, and thin lines, fine characters and the like were found from the imprinting.

As described above, only the liquid developer of the present invention is
In an electrophotographic plate making system using an electrophotographic photosensitive member having improved printing characteristics, excellent dispersibility / redispersibility and printing durability were satisfied.

Example 2 Production Example 22 of Latex Particles: 30 g of a resin dispersion of D-22, branched hexadecyl alcohol FOC-1600.
(Nissan Chemical Co., Ltd.) 10 g, and octadecyl vinyl ether / semi-maleic acid dodecylamide copolymer 0.0
A liquid developer for electrostatic photography was prepared by diluting 6 g to 1 liter of Isopar G.

(Production of Comparative Developer B) A liquid developer B for comparison was produced by replacing the resin dispersion with the following resin dispersion in the production of the above liquid developer. Comparative liquid developer B: resin dispersion of Production Example 31 of latex particles.

Various characteristics were evaluated by using these liquid developers for an electrophotographic plate making system, and the results are shown in Table-H.

[0193]

[Table 20]

In Table-H, the developing device contamination and 20
The measurement of the evaluation items of the 00th plate image is performed in the first embodiment.
I went in the same way. The other evaluation items were measured as follows. (Note 5) Toner image resisting property: electrophotographic photosensitive material P-2 prepared according to the following formulation, surface potential +450 V in dark place
After being charged to 280 mW, a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780
nm) on the surface of the light-sensitive material at 60 erg / cm
² irradiation amount, pitch 25μm and scanning speed 3
After exposure at a speed of 00 m / sec, a toner image was obtained by applying a bias voltage of 30 V to the counter electrode and developing using each of the liquid developers described above. Further, the toner image was fixed by heating at 100 ° C. for 1 minute.

<Preparation of Electrophotographic Photosensitive Material P-2> 1.9 parts by weight of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) as an organic photoconductive compound and Thiobarbitur of the following structure as an additive 0.15 parts by weight of an acid compound, 17 parts by weight of a binder resin B-3 having the following structure, and 1: 1 of a mixed solution of tetrahydrofuran / cyclohexane in an 8/2 weight ratio.
00 parts by weight was put into a 500 ml glass container together with glass beads and dispersed for 60 minutes with a paint shaker, and then the glass beads were filtered to obtain a dispersion liquid for a photoconductive layer. Next, this photoconductive layer dispersion is applied onto a grained aluminum plate having a thickness of 0.25 mm and dried to obtain an electrophotographic printing plate precursor having a photoconductive layer having a dry film thickness of 6.0 μm. It was adjusted.

[0196]

[Chemical 50]

Each of the original plates thus obtained was immersed in the processing liquid E-2 having the following formulation for 30 seconds to remove the photoconductive layer in the non-image area, washed with water for 30 seconds, and then dried with a dryer. Air dried. <Prescription of Treatment Liquid E-2> Potassium silicate 40 g Potassium hydroxide 10 g Ethanol 100 g Water 800 g The presence or absence of fine lines and fine characters in the image portion of this printing plate was checked with a magnifying glass (PEAK (PEAK ( Manufactured by K.K.).

(Note 6) Printing durability: An offset printing original plate prepared by operating each light-sensitive material under the same conditions as in (Note 5) was gummed and then subjected to an offset printing machine (Sakurai Seisakusho Co., Ltd. ) Manufactured by Oliver 52 type) indicates the number of sheets that can be printed without causing a background stain on the non-image portion of the printed matter and on the image quality of the image portion (the larger the number of printed sheets, the better the printing durability).

From the results shown in Table H, the liquid developers of the present invention and Comparative Example B showed good redispersibility, and the image of the plate after 2000 sheets was also good. Next, the plate after plate making was made to elute the non-image area by using an alkaline processing liquid to obtain a master plate for offset master. At this time, in Comparative Example B, a small area portion of the toner image portion such as a thin line or a thin character was missing. This indicates that the resist property of the toner layer with respect to the treatment liquid was not sufficient, and the toner layer was dissolved and eluted during the treatment. On the other hand, in the present invention, these phenomena were not observed and sufficient resist properties were exhibited. Further, when actually printing as an offset master original plate, the product of the present invention shows 10
Even after printing over 10,000 sheets, the image quality of the printed matter was clear. However, in Comparative Example B, the resist property to the processing liquid for dissolving and removing the non-image portion is not sufficient, and sufficient image reproducibility is not obtained as the offset master original plate, so that the image quality of the printed matter deteriorates after printing. A printed matter with sufficient image quality could not be obtained. As described above, only the liquid developer of the present invention satisfies excellent dispersibility / redispersibility and printing durability in an electrophotographic plate making system in which a non-image area is eluted to be a printing original plate. It was

Example 3 10 g of tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), and nigrosine 1
0 g and 30 g of Isopar G were put 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. Production Example 23 of Latex Particles: 30 g of the resin dispersion of D-23, 2.5 g of the above nigrosine dispersion, and 0.0% of hexadecene / half-maleic acid octadecylamide copolymer.
6 g and 20 g of FOC-1800 to 1 of Isopar G
A liquid developer for electrostatic photography was prepared by diluting to 1 liter.

The obtained liquid developer of the present invention was used in Example 1
When the dirt on the developing device and the 2000th plate image were evaluated under the same conditions as (Note 1) of the evaluation item (1), good results were obtained in the same manner as in Example 1.

Next, the electrophotographic photosensitive material P-3 prepared according to the following formulation was charged to -6 kV in the dark, and a 2.0 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) was used as a light source. Using a pitch of 25μ on the surface of the photosensitive material under the irradiation amount of 45 erg / cm ^2.
m and a scanning speed of 330 m / sec, the film was exposed, developed with the liquid developer of the present invention, and further heated at 60 ° C. for 30 seconds to obtain a toner image.

<Production of Electrophotographic Photosensitive Material P-3> 25 g of Binder Resin B-4 having the following structure, Binder Resin B- having the following structure
5 g, 6 g of the binder resin B-6 having the following structure, 200 g of photoconductive zinc oxide, 0.3 g of phthalic anhydride, 0.01 g of phenol, and 0.018 of the cyanine dye A having the following structure.
A mixture of g and 300 g of toluene was dispersed for 10 minutes at a rotation speed of 1 × 10 ⁴ rpm using a homogenizer to prepare a photosensitive layer forming dispersion. This is applied to a conductively treated paper with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dried at 100 ° C for 20 seconds, and further dried at 120 ° C for 1 second.
Heated for hours. Then, the electrophotographic photosensitive material P is left in the dark at 20 ° C. and 65% RH for 24 hours.
-3 was produced.

[0204]

[Chemical 51]

The original plate thus obtained was passed through an etching machine once using ELP-EX, and then immersed in a hydrophilic treatment liquid E-3 for a photoconductive layer binder resin having the following formulation for 3 minutes. After that, it was washed with water and dried. <Preparation of Treatment Liquid E-3> Diethanolamine 80 g, Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 5 g and methyl ethyl ketone 80 g were dissolved in distilled water to make 1 liter, and the pH was adjusted to 11.0 with potassium hydroxide. Treatment liquid E-3
Was produced.

When the image area of the obtained printing plate precursor was observed with an optical microscope, no defects such as fine lines or fine characters in the toner image area were observed, and the toner particles of the present invention had good resist properties. Next, printing was carried out in the same manner as in Example 1 except that the above original plate was used as an original plate for offset master, and the dampening water used was a solution prepared by diluting the above processing liquid E-3 with distilled water 10 times. When the property was evaluated, 3,000 prints with good print quality were obtained.

Examples 4 to 15 Same as Example 1 except that latex particles shown in Table I below were used in place of the latex particles D-1 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0208]

[Table 21]

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,
The redispersibility, fixability, resist property, and printing durability were good.

Examples 16 to 25 Similar to Example 2 except that the latex particles shown in Table J below were used in place of the latex particles D-22 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0211]

[Table 22]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 and its performance was examined. Each liquid developer exhibits the same performance as in Example 2,
The redispersibility, resist property, and printing durability were good.

Example 26 Production Example 27 of Latex Particles A mixture of 100 g of the white resin dispersion obtained in D-27 and 1.5 g of sumicarone black was heated to a temperature of 100 ° C. and heated and stirred for 4 hours.
After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove residual dye, whereby a black resin dispersion having an average particle size of 0.21 μm was obtained. 30 g of the above black resin dispersion and 0.05 g of zirconium naphthenate were added to Shellsol 7
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 the development of 2000 sheets, the toner adhesion stain on the apparatus did not occur at all. Further, in the same manner as in Example 1, printing was performed as a master plate for offset master by plate making and etching treatment, and after 3000 sheets, the printed matter had clear image quality.

Example 27 Production Example 29 of Latex Particles A mixture of 100 g of the white resin dispersion obtained in D-29 and 3 g of Victoria Blue B was heated to a temperature of 70 ° C. to 80 ° C. and stirred for 6 hours.
After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the residual dye, thereby obtaining a blue resin dispersion having an average particle size of 0.25 μm. A liquid developer was prepared by diluting 32 g of the blue resin dispersion and 0.05 of zirconium naphthenate to 1 liter of Isopar H. When this was developed by the same apparatus as in Example 3, no toner adhesion stain was found on the apparatus even after development of 2000 sheets. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 3,000 sheets was also very clear.

[0215]

According to the present invention, a liquid developer having excellent dispersion stability, redispersibility and fixability can be obtained. In particular, as a developer for an electrophotographic plate making system, it has excellent resist properties in the toner image area, and thus markedly improves the printing durability of the obtained offset master original plate.

Claims (1)

[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 the repeating unit 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)], 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 Fewer polymerizable functional groups copolymerizable with A) Polymer resin particles obtained by polymerizing a solution containing at least one polyfunctional monomer (D) having at least two and at least one dispersion-stabilizing resin [P] having the following content. Is a liquid developer for electrostatic photography. As the dispersion stabilizing resin [P]: (i) Phosphono group, carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, -P (= O) (O
H) R ¹ group [R ¹ represents an -R ² group or an -OR ² group,
R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -S
O ₂ NR ³ R ⁴ group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a polymer containing at least one polar group selected from cyclic acid anhydride-containing groups A composed of a block A containing a component and / or a polymer component corresponding to the monofunctional monomer (A) and a block B containing at least a polymer component represented by the following general formula (II). A weight average molecular weight of 1 ×, which forms a block copolymer B and has a polymerizable double bond group bonded to one end of the polymer main chain of block B opposite to the end adjacent to block A. Obtained by polymerizing a solution containing at least one of 10 ^{3 to} 2 × 10 ⁴ monofunctional macromonomers (M) and (ii) a monomer (B) represented by the following general formula (III). Is a graft-type copolymer, which is a dispersion-stabilizing resin soluble in the non-aqueous solvent. It [Chemical 1] In formula (I), V ⁰ is -COO-, -OCO-,-(CH
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 is the number of hydrogen atoms or carbon 1-2
2 represents a hydrocarbon group, and r represents an integer of 1 to 4). a
¹ and a 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, or -CO.
O-D ^12, or represents a -COO-D ¹² through 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 (IV). [Chemical 2] In formula (IV), 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 as or different from each other, and each is —O—, —CO—, —CO ₂ —, —.
_{OCO -, - SO 2 -,} - N (D 22) -, - CON (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 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 1 carbon atoms.
Represents 18 hydrocarbon groups. [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 formula (II), X ¹ is —COO—, —OCO—, — (CH
_{2) x OCO -, - (} CH 2) x COO- [where x is an integer of 1 to _{3], -O -, - SO 2 -} , - CO
^{-, - CON (R 11)} -, - SO 2 N (R 11) - [wherein R ¹¹ represents a hydrogen atom or a hydrocarbon group], -CONH
It represents COO-, -CONHCONH-, or a phenylene group. Y ¹ represents a hydrocarbon group. 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 having 1 to 8 carbon atoms, or —COO.
-Z ¹ or -COO via a hydrocarbon group having 1 to 8 carbon atoms
-Z ¹ (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). [Chemical 5] In formula (III), X ² is —COO—, —OCO—, — (CH
_{2) y OCO -, - (} CH 2) y COO- [where y represents an integer of 1 to 3], or represent -O-. Y ² represents an aliphatic group having 8 or more carbon atoms. d ¹ and d ² may be the same as or different from each other and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.