JP3300469B2 - Liquid developer for electrostatic photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is an electric resistance 10 ⁹ [Omega] cm or more, and relates to an electrostatic photographic liquid developer formed by dispersing at least resin dielectric constant of 3.5 or less of the carrier liquid, especially redispersion And a liquid developer having excellent resist properties.

[0002]

2. Description of the Related Art A general liquid developer for electrophotography uses 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 as a petroleum-based liquid developer. Dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and added with a polarity controlling agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, and vinylpyrrolidone. .

[0003] 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 nm. It is important that the particles do not agglomerate or precipitate, and if they are not satisfied, it will lead to failure of the developing machine such as poor reproducibility of the image area, contamination of the non-image area, or clogging of the liquid feed pump of the developing device. Would.

[0004] As these improvements, non-aqueous dispersion polymerization methods for obtaining insoluble latex particles having a fine particle size and good monodispersity have been proposed, and various studies have been made.
For example, U.S. Patent Nos. 3,990,980 and 4,61.
8,557, JP-A-1-257969, 2-74
No. 956, No. 1-282566, No. 2-173667
Nos. 4,313,763 and 4,45,455, and the like, a method of improving with a soluble dispersion stabilizing resin is disclosed in U.S. Pat. No. 4,842,975, and JP-A-62-151868.
JP-A-1-237668 and JP-A-2-168276
No. 2,139,973, No. 2-81054 and the like describe a method of modifying the surface of latex particles by coexisting an insolubilizing monomer and another compound having a physicochemical interaction. It is disclosed that the dispersibility, particle size, redispersibility, and storage stability of the polymer can be improved.

[0005]

On the other hand, in recent years, the practical use or development of a direct lithographic printing system to which the electrophotographic technique is applied has been actively performed. These systems are
After a toner image portion is formed on the surface of an electrophotographic photosensitive material by electrophotography, the non-image portion is converted into hydrophilic by processing, thereby obtaining a lithographic printing original plate. As a method for hydrophilizing the non-image portion, a method in which the portion is eluted with a processing solution and the hydrophilicity of the surface of the support of the electrophotographic photosensitive layer is used, or the surface portion of the non-image portion of the photosensitive layer is used. The main method is a method of modifying lipophilicity to hydrophilicity.

In recent years, the latter method has been disclosed in Japanese Patent Application Laid-Open Nos. 62-21669 and 1-19 as improvements of conventionally known methods for desensitizing photoconductive zinc oxide in a photosensitive layer.
No. 1157, No. 2-15277, etc., by converting the binder resin used for the photosensitive layer to hydrophilic by treatment,
It is disclosed that improvement in hydrophilicity is achieved.
In these systems, in the process of making the toner hydrophilic, it is important to maintain the image portion of the toner image portion without any change with respect to the processing liquid (hereinafter, referred to as resist properties for the processing liquid).

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, if the non-image area is sufficiently hydrophilized, the resist property of the toner image area becomes insufficient. However, there was a case where the image part was missing. In particular, this problem is remarkable in a place where the area of the toner image portion such as a thin line, a character, or a halftone dot portion is small, and the printed matter is deteriorated. Insoluble latex particles (for example, styrene-based latex) having high durability with respect to the processing solution have sufficient resist properties, but have poor charge stability and re-dispersibility as toner particles. Fixing of toner particles is inferior and sufficient fixing requires a long time with high heat and a long fixing time.

The present invention solves the above-mentioned problems of the conventional liquid developer. The purpose of the present invention is
An object of the present invention is to provide a liquid developer excellent in dispersion stability, redispersibility, fixing property, and resist property of a hydrophilic treatment liquid in an electrophotographic plate making system. Another object of the present invention is to provide a liquid developer capable of preparing 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 offset printing master having excellent printing ink oil sensitivity and printing durability by electrophotography. Still another object of the present invention is to provide a liquid developer capable of preparing an original plate for offset printing using a recording method of various recording processes such as ink jet recording, cathode ray tube recording and pressure change or electrostatic change. It is.

[0009]

The above objects of the present invention are:
Electric resistance 10 ⁹ [Omega] cm or more and a dielectric constant of 3.5 or less responsible
In a liquid developer for electrophotography comprising at least resin particles dispersed in a body fluid , the dispersed resin particles are insoluble in water.
A monofunctional monomer (A) which is soluble in a medium but insolubilized by polymerization, contains a specific substituent represented by the following general formula (I), and A copolymerizable monomer (C), a polyfunctional monomer (D) having two or more polymerizable functional groups copolymerizable with the monomer (A), a phosphono group, a carboxyl group, and a sulfo group. Group, hydroxyl group, formyl group, amino group, -P (=
O) (OH) R ¹ group [R ¹ represents a —R ² group or a —OR ² group,
R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂
A polymer component containing an NR ³ R ⁴ group (R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group) and at least one polar group selected from cyclic acid anhydride-containing groups And / or a block A containing at least one kind of polymer component corresponding to the monofunctional monomer (A) and the following general formula (I)
At least three AB-type block polymer chains composed of at least three AB-type block polymer chains composed of a block B containing at least one polymer component represented by I), and each AB-type block polymer The chain is bonded to the organic molecule at one end of the polymer main chain of block A opposite to the end bonded to block B, and has a weight average molecular weight of 2 × 10 ^4.
A polymer resin particle obtained by polymerizing a mixture containing at least one kind of a dispersion stabilizing resin [P] composed of a star-type copolymer, which is about 5 × 10 ^5. Achieved by electrostatographic liquid developers.

[0010]

Embedded image

In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0012]

Embedded image

In the formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same or different from each other, and each is -O-, -S-, -CO-,
—CO ₂ —, —OCO—, —SO ₂ —, —N (R ₂₂ ) —,
_{-CON (R 22) -, -} N (R 22) CO -, - N
_{(R 22) SO 2 -,} - SO 2 N (R 22) -, - NHCO 2
— Or —NHCONH— (where R ₂₂ is the above R
Indicates the same content as ₂₁ ). A ₁ and A ₂ may be the same or different from each other, each represents a hydrocarbon group having 1 to 18 carbon atoms, which may be substituted, or may have the following formula 7 in the bond of the main chain.

[0014]

Embedded image

[0015] Among of 7, B ₃ and B _4, which may be the same or different, indicates the B _1, B ₂ identical contents and, A ₄
Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ₂₃ has the same contents as R ₂₁ described 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. In the formula (I), U ¹ is -COO-, -CONH-,-
CON (E ² )-[E ² represents an aliphatic group or a substituent represented by the above general formula (III)], -OCO-,-
_{CONHCOO -, - CH 2 COO -} , - (CH 2) s OC
O- [where s represents an integer of 1 to 4], -O- or-
Represents C ₆ H ₄ —COO—. a ¹ and a ² may be the same or different, and each represents a hydrogen atom, an alkyl group,
O-E ³ or -CH ₂ COO-E ³ (where E ³ represents an aliphatic group).

[0016]

Embedded image

In the general formula (II), X ¹ is -COO-, -O
_{CO -, - (CH 2)} x COO -, - (CH 2) x OCO-
[Where x represents an integer of 1 to 3], or -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. b ¹ and b ²
May be the same or different from each other, and each may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ¹ ,
Or —COO—Z ¹ via a hydrocarbon group (where Z ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted).

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

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are used in a non-aqueous solvent to disperse the star-type block copolymer of the present invention. In the presence of the resin [P], at least one of a monofunctional monomer (A), at least one of a monomer (C) containing a specific substituent, and a polyfunctional monomer (D) It is polymerized and granulated by polymerizing at least one kind.

Here, as the non-aqueous solvent, basically,
Any material can be used as long as it is miscible with the carrier liquid of the liquid developer for electrostatography. That is, the solvent used in producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. Hydrogen and halogen-substituted products thereof are exemplified. For example, hexane,
Octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shellsol 70, Shellsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

Solvents that can be used by mixing with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.) and ketones (eg, acetone, methyl ethyl ketone, 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, Carbon tetrachloride, dichloroethane, methyl chloroform, etc.).

It is desirable that the non-aqueous solvent used by mixing these is distilled off under heating or under reduced pressure after the polymerization granulation. 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 Hydrocarbons and the like.

The monofunctional monomer (A) in the present invention comprises
Any monofunctional monomer that is soluble in a nonaqueous solvent but insolubilized by polymerization may be used. Specifically, for example, a monomer represented by the following general formula (IV) can be mentioned.

[0024]

Embedded image

In the formula (IV), T ¹ is -COO-, -OCO
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, - C
ONHCOO -, - CONHOCO -, - SO 2 -, -
CON (W ¹ ) —, —SO ₂ N (W ¹ ) —, or a phenylene group (hereinafter, a phenylene group is referred to as “—Ph—”.
The phenylene group includes a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. ]. Here, W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
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, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 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-carboxyamidoethyl group, 3
-Sulfamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

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

Specific monofunctional monomers (A) include:
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, C1-C4 alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (for example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-chloroethyl, 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-
Styrene derivatives (eg, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, “Polymer Data Handbook -Basic Part-”, edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986) ), For example, N-vinylpyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
And the like. Two or more monomers (A) may be used in combination.

Next, the monomer (C) containing a specific substituent represented by the general formula (I) used in the present invention will be further described.

[0030]

Embedded image

In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0032]

Embedded image

In the formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same or different from each other, and each is -O-, -S-, -CO-,
—CO ₂ —, —OCO—, —SO ₂ —, —N (R ₂₂ ) —,
_{-CON (R 22) -, -} N (R 22) CO -, - N
_{(R 22) SO 2 -,} - SO 2 N (R 22) -, - NHCO 2
— Or —NHCONH— (where R ₂₂ is the above R
Indicates the same content as ₂₁ ). A ₁ and A ₂ may be the same or different from each other, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following formula 12 intervening in the bond of the main chain.

[0034]

Embedded image

In Chemical Formula 12, B ₃ and B ₄ may be the same or different from each other, and have the same contents as B ₁ and B ₂ described above.
₄ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ₂₃ has the same contents as R ₂₁ described 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. In the formula (I), U ¹ is -COO-, -CONH-,-
CON (E ² )-[E ² represents an aliphatic group or a substituent represented by the above general formula (III)], -OCO-,-
_{CONHCOO -, - CH 2 COO -} , - (CH 2) s OC
O- [where s represents an integer of 1 to 4], -O- or-
Represents C ₆ H ₄ —COO—. a ¹ and a ² may be the same or different, and each represents a hydrogen atom, an alkyl group,
O-E ³ or -CH ₂ COO-E ³ (where E ³ represents an aliphatic group).

The case where E ¹ represents an aliphatic group having 8 or more carbon atoms in the monomer (C) represented by the general formula (I) will be described in detail. In the general formula (I), preferably,
E ¹ represents an alkyl group having a total of 10 or more carbon atoms which may be substituted or an alkenyl group having a total of 10 or more carbon atoms. U ¹
Preferably -COO-, -CONH-, -CON (E ² )
- [However, E ² is preferably an aliphatic group of 1 to 32 carbon atoms (for example an alkyl group as the aliphatic group, an alkenyl group or an aralkyl group)], --OCO -, - C
Represents H ₂ OCO— or —O—. a ¹ and a ² may be the same or different and are preferably a hydrogen atom, a methyl group,
Represents —COO-E ³ or —CH ₂ COO-E ³ [provided that E
³ preferably represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 1 to 32 carbon atoms. ]. Still more preferably, in formula (I), U ¹ is-
Represents COO—, —CONH—, or —CON (E ² ) —, a ¹ and a ² may be the same or different and represent a hydrogen atom or a methyl group, and E ² has the same content as described above. Represent.

In the monomer (C) represented by the above general formula (I), when E ¹ represents an aliphatic group having 8 or more carbon atoms, specific examples thereof include those having 10 to 32 carbon atoms in total. Aliphatic group (the aliphatic group may contain a substituent such as a halogen atom, a hydroxyl group, an amino group, an alkoxy group, or a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or the like; Acrylic acid, methacrylic acid, crotonic acid, maleic acid, which may have a carbon bond
Esters of unsaturated carboxylic acids such as itaconic acid (for example, aliphatic groups such as decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, dodecenyl group, hexadecenyl group,
Oleyl group, linoleyl group, docosenyl group, etc.); amides of the above-mentioned unsaturated carboxylic acids (the aliphatic groups are the same as those shown for esters); vinyl esters or allyl esters of higher fatty acids (higher fatty acids) For example, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc.) or vinyl ethers substituted with an aliphatic group having a total of 10 to 32 carbon atoms (the aliphatic group is the above-mentioned unsaturated carboxylic acid) And represents the same range as the aliphatic group of the acid).

The case where E ¹ in the monomer (C) represented by the general formula (I) represents a substituent represented by the general formula (III) will be described in detail. More specific examples of A ₁ and A ₂ include those represented by —C (R ₂₄ ) (R ₂₅ ) —
[R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group, a halogen atom, etc.],-(CHＣＨCH)-, a cyclohexylene group [hereinafter, a cyclohexylene group is represented by “-C ₆ H _10- ”, and “ —C ₆ H ₁₀ — ”is a 1,2-cyclohexylene group,
1,3-cyclohexylene group and 1,4-cyclohexylene group], and any combination of atomic groups such as the above formulas (12) and (13).

In the general formula (I), the bonding group: -U ^1- (A ₁ -B ₁ ) _m- (A ₂ -B ₂ ) _n -R ₂₁ , from U ¹ to R ₂₁ (that is, _{^{1, A 1, B 1,}} A 2,
B ₂ , R ₂₁ ) has a total number of atoms of 8
What is comprised from the above is preferable. Where U ¹ −
CON (E ² ) —, and E ² is a substituent represented by the general formula (III) [that is,-(A ₁ -B ₁ ) _m- (A ₂ -B ₂ ) _n
When it represents a -R _21], linked backbone consists of E ² are also included in the connecting backbone. Further, in the case where A ₁ and A ₂ are a hydrocarbon group which causes the chemical formula 12 to intervene in the bond of the main chain,-
B _3- (A ₄ -B ₄ ) _p -R ₂₃ is also included in the connecting main chain. As the number of atoms in the connecting main chain, for example, U ¹ is -CO
When representing O— or —CONH—, the oxo group (＝ O group) and the hydrogen atom are not included in the number of atoms, and the carbon atom, the ether-type oxygen atom, and the nitrogen atom constituting the connecting main chain are included in the number of atoms. It is. Therefore, -COO- and -CONH
-Is counted as 2 atoms. Similarly, when R ₂₁ is -C ₉
When H ₁₉ is represented, hydrogen atoms are not included in the number of atoms, and carbon atoms are included. Therefore, in this case, the number of atoms is 9
Counted as In the monomer (C) represented by the general formula (I) as described above, when E ¹ represents a substituent represented by the general formula (III), that is, when the monomer having a specific polar group is In this case, more specifically, the following compounds can be exemplified.

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

Next, a polymerizable functional group capable of copolymerizing with the monomer (A), which is used together with the monofunctional monomer (A) and the monomer (C) having a specific substituent, is used. (D) having at least one monomer (hereinafter also referred to as polyfunctional monomer (D))
Will be described. 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, the polymerizable functional group represented by the following general formula (V) The functional groups shown are mentioned.

[0047]

Embedded image

[0048] In the formula ^{(V), d 1, d} 2 and T ¹ have the same meanings as d ^1, d ² and T ¹ in the general formula (IV).

The polyfunctional monomer (D) may be a monomer having two or more of the same or different polymerizable functional groups, and the monomer (A) By co-polymerizing, a polymer insoluble in a non-aqueous solvent is formed.

Specific examples of the monomer (D) having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene as monomers having the same polymerizable functional group; Polyhydric alcohols (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 and the like, or polyhydroxyphenol (eg, hydroquinone, resorcinol, catechol and the like) 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) Vinyl esters, allyl esters, vinylamides or allylamides of itaconic acid; polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and vinyl Carboxylic acids having (e.g.,
Condensates with methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

As the monomer having a different polymerizable functional group, for example, a carboxylic acid having a vinyl group [eg,
Methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, a reactant of a carboxylic anhydride with an alcohol or an amine (eg, allyloxycarbonylpropionic acid, allyl Ester derivatives or amide derivatives containing a vinyl group such as oxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate) , Allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate,
Allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, allylamide methacryloylpropionate); or And amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and carboxylic acids containing vinyl groups.

The dispersing resin of the present invention comprises at least one of each of the monomers (A), (C) and (D). If the obtained resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, the monomer (A) to be insolubilized
With the monomer (C) represented by the general formula (I) in 0.1.
It is preferably used in an amount of 1 to 20% by weight, more preferably 0.3 to 8% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention accounts for 0.01 mol% or more and 20 mol% or less, preferably 0.1 mol% or less of all monomers.
It is used in an amount of from 05 mol% to 10 mol% 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 , more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

Next, the dispersion stabilizing resin [P] of the present invention will be described. The dispersion stabilizing agent of the present invention used to convert the solvent-insoluble polymer produced by polymerizing the monomers (A), (C) and (D) in a non-aqueous solvent into a stable resin dispersion. The resin [P] is a star copolymer having a weight-average molecular weight of 2 × 10 ^{4 to} 5 × 10 ⁵ , wherein at least three polymer chains of the AB block copolymer component are bonded in an organic molecule. It is. One block (block A) bonded to the organic molecule is a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, -P (= O) (O
H) R ¹ group [R ¹ represents a -R ² group or -OR ² group, R ² represents a hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ NR ³
A polymer component containing an R ⁴ group (R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), and at least one polar group selected from cyclic acid anhydride-containing groups; Alternatively, it is constituted by containing at least one polymer component corresponding to the monofunctional monomer (A). The other block (block B) contains at least one polymer component composed of a repeating unit represented by the general formula (II). Here, the order of the sequence in the polymer chain of the block A and the block B is such that the block A is one end of the polymer main chain opposite to the end bonded to the block B and is bonded to an organic molecule. The resin [P] is schematically shown as in the following formula (20).

[0054]

Embedded image

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

The proportion of the blocks A and B in the star-type copolymer is from 1/50/99 to 50 (weight ratio), and preferably from 5/40/95 to 60 (weight ratio). The specific polar group-containing polymer component contained in the block A is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the dispersion stabilizing resin [P]. When no specific polar group-containing polymer component is present in the block A, the polymer component corresponding to the monofunctional monomer (A) preferably has a content of 5 to 100 parts by weight of the resin [P]. It is 50 parts by weight, more preferably 10 to 40 parts by weight. The polymer component represented by the general formula (II) contained in the block B includes:
Preferably 50 in 100 parts by weight of the dispersion stabilizing resin [P].
To 99 parts by weight, more preferably 60 to 95 parts by weight. In the dispersion stabilizing resin [P], the above-mentioned predetermined existence ratio (that is, the above-mentioned block A and block B
, The proportion of the specific polar group-containing polymer component contained in the block A, and the proportion of the polymer component represented by the general formula (II) contained in the block B). The re-dispersion stability of the dispersed resin particles obtained by polymerizing the monofunctional monomer (A), the monomer (C) containing a specific substituent and the polyfunctional monomer (D) decreases. Resulting in.
On the other hand, when the ratio exceeds the predetermined ratio, the monomer (A),
The average particle size of the dispersed resin particles obtained by the polymerization reaction of the monomer (C) and the monomer (D) is increased, and the monodispersity of the particle distribution is reduced.

Dispersion stabilizing resin [P] used in the present invention
Is soluble in an organic solvent, and more specifically, it is sufficient that at least 5 parts by weight or more of the resin for dispersion stabilization is dissolved at 25 ° C. with respect to 100 parts by weight of a toluene solvent. The weight average molecular weight (Mw) of the dispersion stabilizing resin [P] of the present invention is 2 × 10 ^{4 to} 5 × 10 ⁵ , preferably 3 × 10 ⁴ to 1 × 10 ⁵ .

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

In a specific polar group, -P (= O) (OH) R ¹
In the group, R ¹ is shows a -R ² group or -OR ² group, R ²
Represents a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group for R ^2, an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a butenyl group, a pentenyl group, A hexenyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, and the like; and an optionally substituted aromatic group (for example, a phenyl group, a tolyl group) Group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

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

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

Further, among the specific polar groups, the amino group is
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ and R ⁶ are
Represents a hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms. More preferably represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, include those of the same contents as the hydrocarbon group represented by R ^2.

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

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

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

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

Next, the block B of the dispersion stabilizing resin [P] is used.
The repeating unit represented by the general formula (II) constituting the following will be described in detail. In the general formula (II), X ¹ preferably represents -COO-, -OCO- or -O-. Y ¹
Preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
And linolel groups.

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

Specifically, Z ¹ is, in addition to a hydrogen atom, a preferred hydrocarbon group such as an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group). 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-bromoethyl group Cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3
-Bromopropyl group, etc.), and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group) , A 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linolel group, etc.),
An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, An ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group or the like, an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, cyclohexyl group,
-Cyclohexylethyl group, 2-cyclopentylethyl group and the like, and 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, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxy Carbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecylylamidophenyl group, etc.).

The block B of the dispersion stabilizing resin used in the present invention may contain another repeating unit as a copolymer component together with the repeating unit represented by the general formula (II). The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). However, it is preferable not to contain other components, and it is used in an amount not exceeding 20 parts by weight in the block B at most. If the amount exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles will be deteriorated. In the block B, two or more kinds of repeating units represented by the general formula (II) may be used in combination.

On the other hand, the organic molecule according to the present invention comprising at least three polymer chains bonded is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. As an example, a trivalent hydrocarbon residue represented by the following formula 24 may be mentioned.

[0074]

Embedded image

[Here, r ^{1 to} r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, at least one of r ¹ and r ² is connected to the polymer chain, and at least one of r ^{3 to} r ⁶ is connected to the polymer chain. These organic residues are composed of a single compound or an arbitrary combination thereof, and in the case of a combination, -O-, -S-, -N
^{(R 7) -, - COO} -, - CON (r 7) -, - SO
_{2 -, - SO 2 N (} r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO -, - NHCONH
-A heterocycle containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or the like (for example, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine ring) Etc.) may be included.

Examples of other organic molecules that bind the polymer chains include those composed of a combination of the following chemical formulas and the above-mentioned binding units. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0077]

Embedded image

The star-type copolymer [P] of the present invention can be synthesized using a conventionally known method of synthesizing a star-type polymer of a monomer containing a polar group and having a polymerizable double bond group. it can. For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morton,
TE Helminiak et al “J. Polym. Sci.” 57, 471 (19
62), B. Gordon III, M, Blumenthal, JE Loftus et
al “Polym. Bull.” 11,349 (1984), RB Bates, W.
A. Beavers et al “J. Org. Chem.” 44, 3800 (1979)
Can be synthesized according to the method described in (1). However, when this reaction is used, the “specific polar group” of the present invention is used as a protected functional group, polymerized, and then the protective group is eliminated. The protection of the specific polar group by the protecting group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references. Furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977)
TW Greene “Protective Groups in Organic S”
ynthesis ”(JohnWiley & Sons, 1981), JFW Mc
Omic “Protective Groups in Organic Chemistry” (Pl
enum Press, 1973) and the like.

Another method is to use a specific polar group of the present invention.
Using unprotected monomer
And / or contains a xanthate group
Using the compound as an initiator, perform a polymerization reaction under light irradiation
It can also be synthesized. For example, Takayuki Otsu “Polymer”Three
7, 248 (1988), Shunichi Himori, Ryuichi Otsu “Polym. Rep. Ja
p. ”37, 3508 (1988), JP-A-64-111,
64-26619, Nobuyuki Higashi, "Polymer Preprints, J
apan ”36 (6), 1511 (1987), M. Niwa, N. Higashi et.
 al “J. Macromol. Sci. Chem.”A24(5), 567 (198
7) can be synthesized according to the synthesis method described in
You.

In order to produce the dispersed resin particles (latex particles) used in the present invention, the dispersion stabilizing resin [P], the monofunctional monomer (A), and the specific substituent as described above are generally used. Containing monomer (C) and polyfunctional monomer (D)
May be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution containing the dispersion stabilizing resin [P], the monomer (A), the monomer (C) and the monomer (D), A method in which the monomer (A), the monomer (C) and the monomer (D) are dropped together with a polymerization initiator into a solution in which the stabilizing resin [P] is dissolved, P] In a solution containing the total amount and a portion of the monomers (A), (C) and (D), the remaining monomers (A) and ( C) and the monomer (D) are arbitrarily added, or the dispersion stabilizing resin [P], the monomer (A), the monomer (C) and the monomer (D) are added in a non-aqueous solvent. And the like. A method of arbitrarily adding the mixed solution together with the polymerization initiator, and the like, can be used by any method.

The total amount of the monomer (A), the monomer (C) and the monomer (D) is 5 to 8 with respect to 100 parts by weight of the non-aqueous solvent.
It is about 0 parts by weight, preferably 10 to 50 parts by weight. The soluble resin as the dispersion stabilizing resin [P] is used in an amount of 1 to 100 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total monomers used above. The amount of the polymerization initiator is suitably from 0.1 to 5% by weight based on the total amount of the monomers. Further, the polymerization temperature is about 50 to 180 ° C, preferably 60 to 120 ° C. The reaction time is preferably 1 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination with the non-aqueous solvent used in the reaction, or when the monomer (A) to be polymerized and granulated, When the unreacted product of the compound (C) or the monomer (D) remains, the solvent or the monomer (A) or the monomer (C)
It is preferable to remove the solvent by heating it to a temperature higher than the boiling point of the monomer (D) or distilling it off, or distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above are present as fine particles having a uniform particle size distribution and exhibit extremely stable dispersibility. However, it has good dispersibility and does not show any aggregation or precipitation in the developing device. Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited. Further, when the liquid developer of the present invention is used in a plate making system,
The toner image portion had excellent resist properties even after the non-image portion hydrophilizing step, and showed excellent original image reproducibility of the printed image portion.

The liquid developer of the present invention having the above-mentioned effects can be obtained by using a star type copolymer comprising specific blocks used together with the monomers (A), (C) and (D) to be insolubilized. It depends on the polymer. That is, the dispersion stabilizing resin [P] of the present invention has a block B composed of a long-chain aliphatic group-containing polymer component having a high affinity for the non-aqueous solvent and a small affinity for the non-aqueous solvent. At least three or more polymer chains of an AB type block in which a block A composed of a polymer component having an affinity for the insolubilizing monomer (A) is bonded in an organic molecule, It is a star type copolymer. This allows
The block A portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the block B portion having a high affinity for the non-aqueous dispersion medium has a sufficient solvent for the solvent. Since there are at least three or more polymer chains that act sufficiently and have a three-dimensional repulsion effect (so-called tail-like adsorption), the adsorption effect and the three-dimensional repulsion effect can be sufficiently efficiently exhibited. It is estimated that the effects of the present invention have been achieved.

On the other hand, in the conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, a high-concentration component in which the component serving as the adsorbed portion is solvated is used. Adhesion to the dispersed resin particles is not sufficient because they are randomly bonded in the molecular chain, and furthermore, the adsorption pattern becomes a loop, so that the steric repulsion effect is also excluded, and the dispersion stability is sufficient. Was not. Further, A composed of block A and block B
A -B type block copolymer was developed, and the effect of improving dispersion stability was recognized as compared with the above random copolymer. However, in recent years, the effect of dispersion stability has not been sufficient for increasing the development speed of a plate making machine.

On the other hand, the insoluble resin particles of the present invention are improved in the monodispersibility and redispersibility of the particles by polymerizing and granulating using the monomer (C) having a specific substituent. .
That is, the monomer (C) is copolymerized with the monomer (A) which is insolubilized during polymerization granulation, but the specific substituent portion contained in the monomer (C) is non-aqueous dispersion polymerized. Since the particles are formed by the, the affinity with the non-aqueous solvent is designed to be good, so that the solvation with the dispersion medium is better than that penetrating into the inside of the particle structure, It is presumed that the particles are oriented at the interface (surface) of the particle structure, and as a result, the affinity of the particle surface with the dispersion medium is improved, and the effect of preventing aggregation between the particles is significantly enhanced.

At the same time, the dispersed resin particles of the present invention are characterized in that the particles form a crosslinked structure by polymerization and granulation using a polyfunctional monomer (D). As a result, even after an image is formed as toner particles and after a hydrophilic treatment process for forming a printing original plate, the suitability of the processing liquid (resist property) is improved, and breakage of the toner image area is significantly reduced. It has become possible. Further, in order to ease the fixing conditions, it is important for the apparatus to have a resin structure having a low glass transition point as the insoluble resin particles, and these resins having a low glass transition point include, for example, an ester structure,
Since a polar structure such as an ether structure or an amide structure is contained, the compound is easily dissolved in a treatment liquid in the hydrophilic treatment step, and as a result, the resist property of the toner portion on the image portion is reduced. This undesirable phenomenon can be significantly suppressed by partially crosslinking the inside of the resin particles. The dispersed resin particles of the present invention bring about the effects of the present invention by these effects.

In the liquid developer of the present invention, a coloring agent may be used if desired. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used. In the case of coloring the dispersion resin itself, for example, as one of the coloring methods, there is a method of physically dispersing the dispersion resin in a dispersion resin using a pigment or a dye. I have. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red,
And phthalocyanine blue. As another method of coloring, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. Alternatively, another method is disclosed in
As disclosed in JP-A-54029, there is a method in which a dispersing resin and a dye are chemically bonded, or as described in JP-B-44-22955, etc. In addition, there is a method of using a monomer containing a dye in advance to obtain a dye-containing copolymer.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing the charging characteristics or improving the image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol. What is specifically described in No. 2, p. 44 is used. For example, a copolymer containing a metal salt of di-2-ethylhexyl sulfosuccinic acid, a metal salt of naphthenic acid, a metal salt of a higher fatty acid, lecithin, poly (vinylpyrrolidone), and a hemimaleamide component;
Examples include polyethers and waxes. But,
It is not limited to these.

The amount of each of the main components of the liquid developer of the present invention will be described below. The toner particles mainly composed of a resin (and a coloring agent used as desired) are used in an amount of 0.5 parts by weight to 1000 parts by weight of the carrier liquid.
50 parts by weight are preferred. If the amount is less than 0.5 parts by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is apt to occur. Further, the carrier liquid soluble resin for dispersion stabilization is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 1000 parts by weight of the carrier liquid. The charge control agent as described above is a carrier liquid 100
0.001 part by weight to 1.0 part by weight based on 0 part by weight is preferred. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, if the electric resistance of the liquid developer from which the toner particles have been removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, the amount of each additive is controlled within this limit. It is necessary.

[0091]

EXAMPLES The production examples of the dispersion stabilizing resin of the present invention, the production examples of latex particles and the examples are shown below, and the effects of the present invention will be described in more detail. However, the present invention is not limited to these examples. Absent.

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

[0093]

Embedded image

[0094]

Embedded image

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

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

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

[0101]

[Table 5]

[0102]

[Table 6]

[0103]

[Table 7]

[0104]

[Table 8]

Preparation Example of Latex Particle 1: Latex Particle D-1 20 g of dispersion stabilizing resin [P-1], vinyl acetate 80
g, styrene 20 g, octadecyl methacrylate2.
5 g, divinyl adipate 5 g and Isopar H
4 g of the mixed solution was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.2 g of 2,2'-azobis (isovaleronitrile) (abbreviated AIVN) as a polymerization initiator
In addition, the reaction was performed for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Further, after adding 0.5 g of an initiator and reacting for 2 hours, the temperature was raised to 100 ° C.
And stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 90% and an average particle size of 0.18 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

Latex Particle Production Examples 2 to 24: Latex Particles D-2 to D-24 In latex particle production example 1, the dispersion stabilizing resin [P-1], octadecyl methacrylate [namely, monomer (C) ] And divinyl adipate [namely, monomer (D)], except that the dispersion stabilizing resin, monomer (C) and monomer (D) shown in Table-C below were used. The latex particles D-2 to D-24 of the present invention were produced in exactly the same manner as in Production Example 1. The polymerization rate of each obtained latex particle is 85 to 90%, and the average particle size is 0.15 to
The monodispersity was good within the range of 0.25 μm.

[0107]

[Table 9]

[0108]

[Table 10]

[0109]

[Table 11]

Production Example 25 of Latex Particles: Latex Particle D-25 20 g of dispersion stabilizing resin [P-7], 80 g of methyl methacrylate, 20 g of ethyl acrylate, 4 g of dodecyl acrylate, and 1 g of ethylene glycol diacrylate.
A mixed solution of 3 g and 375 g of Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. A. I. V.
N. Was added and reacted for 4 hours. I. V.
N. Was added and reacted for 4 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 98% and an average particle size of 0.25 μm.

Production Example 26 of Latex Particles: Latex Particles D-26 A mixed solution of 18 g of dispersion stabilizing resin [P-21] and 177 g of Isopar H was stirred at a temperature of 60 under a nitrogen stream.
Warmed to ° C. 60 g of methyl methacrylate, 40 g of methyl acrylate, 3 g of octadecyl acrylate, 2 g of ethylene glycol diacrylate, 200 g of Isopar G and A.I. I. V. N. Was added dropwise over 2 hours, followed by stirring for 2 hours. Further, A.
I. V. N. Was added and stirred for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 99% and an average particle size of 0.20 μm.

Latex Particle Production Examples 27 to 33: Latex Particles D-27 to D-33 Monomer (A) (namely, methyl methacrylate and methyl acrylate) used in Latex Particle Production Example 26, for dispersion stabilization Resin [P-21], monomer (C)
Latex particles were prepared in the same manner as in Production Example 26, except that the compounds shown in Table D below were used instead of (ie, octadecyl acrylate) and monomer (D) (ie, ethylene glycol diacrylate). Was manufactured. The polymerization rate of each obtained latex particle is 95-9.
At 9%, the average particle size was in the range of 0.18 to 0.30 μm and the monodispersity was good.

[0113]

[Table 12]

[0114]

[Table 13]

Production Example 34 of Latex Particles: (Comparative Example A) 20 g of a dispersion stabilizing resin [RP-1] having the following structure, 80 g of methyl methacrylate, 20 g of ethyl acrylate, 1.3 g of ethylene glycol diacrylate and 375 g of Isopar H Latex particles having a polymerization rate of 98% and an average particle size of 0.23 μm were obtained in exactly the same manner as in Production Example 25 of latex particles except that the mixture was used. (JP-A-4-
(Equivalent to 313763)

[0116]

Embedded image

Production Example 35 of Latex Particles: (Comparative Example B) A mixture of 20 g of the dispersion stabilizing resin [RP-1], 80 g of methyl methacrylate, 20 g of ethyl acrylate, 4 g of dodecyl acrylate and 375 g of Isopar H was used. In the same manner as in Production Example 25 of latex particles, latex particles having a polymerization rate of 97% and an average particle size of 0.25 μm were obtained. (Equivalent to JP-A-4-45455)

Production Example 36 of Latex Particles: (Comparative Example C) Production Example 25 was the same as Production Example 25 of latex particles except that 1.3 g of ethylene glycol diacrylate was omitted.
A latex was synthesized in exactly the same manner as described above. The obtained latex had a polymerization rate of 98% and an average particle size of 0.23 μm.

Example 1 10 g of a dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 95/5 by weight), 10 g of nigrosine and 30 g of Isopar G were placed on a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads. Put it in for 4 hours,
A fine dispersion of nigrosine was obtained. 6 g of the resin particles of Production Example D-25 of latex particles (as solid content), 2.5 g of the above nigrosine dispersion, 15 g of branched octadecyl alcohol FOC-1800 (manufactured by Nissan Chemical Industries, Ltd.),
A liquid developer for electrostatography was prepared by diluting 0.07 g of octadecene-half-maleic acid octadecylamide copolymer into 1 liter of Isopar G.

(Preparation of Comparative Developers A to C) In the production of the above liquid developer, the resin particles D-25 were replaced with the following resin dispersions (6 g each as resin particles). , B and C were prepared. Comparative liquid developer A: resin dispersion of Production Example 34 of latex particles. Comparative liquid developer B: resin dispersion of Production Example 35 of latex particles. Comparative liquid developer C: resin dispersion of Production Example 36 of latex particles.

Using these liquid developers for an electrophotographic plate making system, various characteristics were evaluated, and the results are shown in Table-E.

[0122]

[Table 14]

The measurement of each evaluation item in Table-E was performed as follows. (Note 1) Stain on the developing device and plate image of the 2000th sheet: ELP404V, a fully automatic plate making machine (manufactured by Fuji Photo Film Co., Ltd.), and ELP Master II type electrophotographic photosensitive material using liquid developer (Fuji Photo Film Co., Ltd.) was exposed and developed. Plate making speed is 7
Performed at plate / min. Further, the presence or absence of toner adhesion stains on the developing device after processing 2,000 sheets of the ELP Master II type was observed. The blackening rate (image area) of the copied image is 30
% Of the manuscript.

(Note 2) Fixing property of image: Liquid developer was used as EL
A plate was prepared using the electrophotographic photosensitive material P-1 prepared as described below, using the developer of P404V, 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 as a reference for evaluation. <Preparation of electrophotographic photosensitive material P-1> 34 g of binder resin B-1 having the following structure, 6 g of binder resin B-2 having the following structure, 200 g of photoconductive zinc oxide, 0.03 g of uranine, and 0 Rose Bengal A mixture of 0.06 g, 0.02 g of tetrabromophenol blue, 0.30 g of phthalic anhydride, 0.01 g of o-chlorophenol and 300 g of toluene was treated with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.
The dispersion was performed at a rotation speed of pm for 10 minutes. This dispersion for forming a photosensitive layer was applied to a conductive treated paper with a wire bar so as to have a dry adhesion amount of 26 g / m ² , dried at 100 ° C. for 30 seconds, and then heated at 120 ° C. for 1 hour. Then 2 in the dark
The mixture was allowed to stand for 24 hours at 0 ° C. and 65% RH to produce an electrophotographic photosensitive material P-1.

[0125]

Embedded image

(Note 3) Resist properties of toner image: An etching machine was used to make a plate-making master using a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions as in (Note 2) above. Was passed through once, immersed in a hydrophilic treatment solution E-1 of a photoconductive layer binder resin having the following formulation for 5 minutes, and then 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 to the image portion was visually evaluated. <Preparation of Hydrophilizing Solution E-1> Monoethanolamine 8
0 g, Newcol B4SN (Nippon Emulsifier Co., Ltd.) 8
g and 100 g of benzyl alcohol in distilled water.
After adjusting to liter, the pH was adjusted to 11.0 with potassium hydroxide to prepare a treatment liquid E-1.

(Note 4) Printing durability: The printing plate subjected to plate making and hydrophilization treatment under the conditions of (Note 3) was diluted 20 times with distilled water as a fountain solution. Using a solution and a neutral paper as a base paper for printing, under the condition that a printing machine Hamadaster 800SX (manufactured by Hamadastar Co., Ltd.) is used.
And the number of printed sheets in which the image portion of the printed matter was not lost was examined.

From the results shown in Table-E, the developers of the present invention and Comparative Example C did not cause stains on the developing device, and the image on the 2000th plate was clear, showing good results. This indicates that the dispersibility and the redispersibility are good. On the other hand, in the developers of Comparative Examples A and B, the redispersibility deteriorated, and the reproducibility of the actual copied image was adversely affected. 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 had practically sufficient fixability.

Further, when the zinc oxide and the binder resin B-1 in the non-image area of the plate surface after plate making are converted into hydrophilic by chemical treatment, the image area is sufficiently resisted by the toner layer, and the image area is deficient. It was examined under forced conditions whether or not the toner particles were generated. As a result, defects other than the toner particles of the present invention and Comparative Example A occurred in a fine area of the toner image portion such as a thin line or a thin character. In addition, when processed under normal desensitizing conditions and printed as an offset master plate, clear prints were obtained with only the present invention even after printing 5,000 sheets. In Comparative Examples A and B, a decrease in the reproducibility of the copied image during plate making appeared on the printed material as it was, and the lack of fine lines and fine characters was observed from the start of printing. In Comparative Example C, two minutes after printing
About 1,000 sheets were missing of fine lines and characters. As described above, only the liquid developer of the present invention satisfies excellent dispersibility / redispersibility and printing durability in an electrophotographic plate making system using an electrophotographic photoreceptor having improved printing characteristics. there were.

Example 2 Preparation of Latex Particles 6 g (as solid content) of the resin particles of Example D-25 were mixed with branched hexadecyl alcohol FOC-
A liquid developer for electrostatography was prepared by diluting 10 g of 1600 (manufactured by Nissan Chemical Industries, Ltd.) and 0.06 g of octadecyl vinyl ether / half-maleic acid dodecylamide copolymer into 1 liter of Isopar G.

(Preparation of Comparative Developers D and E) In the production of the above liquid developer, the resin particles D-25 were replaced with the following resin dispersions (6 g each as resin particles). And E were produced. Comparative liquid developer D: resin dispersion of Production Example 34 of latex particles. Comparative liquid developer E: resin dispersion of Production Example 36 of latex particles.

Using these liquid developers for an electrophotographic plate making system, various characteristics were evaluated, and the results are shown in Table-F.

[0133]

[Table 15]

In Table-F, it is shown that the developing device
The measurement of the evaluation items of the 00th plate image was performed in Example 1.
Was performed in the same manner as described above. The other evaluation items were measured as follows. (Note 5) Resist property of toner image: Electrophotographic photosensitive material P-2 prepared according to the following prescription was used in a dark place with a surface potential of +450 V.
2.8-mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780)
nm) on the photosensitive material surface using 60 erg / cm
Under the irradiation amount of ² , 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 above liquid developers. Further, the toner image was fixed by heating at 100 ° C. for 1 minute.

<Preparation of Electrophotographic Photosensitive Material P-2> X-type metal-free phthalocyanine (manufactured by Dainippon Ink KK) as an organic photoconductive compound was 1.9 parts by weight, and as an additive, thiobarbitur having the following structure was used. 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 part by weight of a mixed solution of tetrahydrofuran / cyclohexane in an 8/2 weight ratio.
00 parts by weight were put together with glass beads in a glass container of 500 ml and dispersed with a paint shaker for 60 minutes. Then, the glass beads were separated by filtration to obtain a dispersion for a photoconductive layer. Next, the dispersion liquid for a photoconductive layer is coated on 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.

[0136]

Embedded image

Each of the master plates thus obtained was immersed in a processing solution E-2 having the following formulation for 30 seconds to remove the non-image portion of the photoconductive layer, washed with water for 30 seconds, and then dried with a drier. 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 / fine characters in the image portion of this printing original plate was checked with a 60-fold loupe (PEAK ( Co., Ltd.).

(Note 6) Printing durability: Offset printing original plates prepared by operating each photosensitive material under the same conditions as in (Note 5) above were gummed, and then subjected to an offset printing machine (Sakurai Seisakusho Co., Ltd.). ) Oliver 52 type) indicates the number of sheets that can be printed without causing any problem in background stain on the non-image area of the printed matter and the image quality of the image area (the larger the number of printed sheets, the better the printing durability).

From the results shown in Table-F, the liquid developers of the present invention and Comparative Example E showed good redispersibility, and the image on the plate after 2,000 sheets was also good. However, Comparative Example D
Toner scum was generated, the developing portion was stained, and the plate image was also missing after 2000 sheets of fine lines and fine characters.

Next, the non-image portion of the plate after plate making was eluted with an alkaline processing solution to obtain an offset master plate. At this time, in Comparative Example E, 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 properties of the toner layer with respect to the processing liquid were not sufficient, and the toner layer was dissolved and eluted during the processing. On the other hand, in the present invention and Comparative Example D, these phenomena were not observed, and sufficient resist properties were shown.

Further, as an offset master master,
As a result of actual printing, the image quality of the printed matter of the present invention was clear even after printing 100,000 sheets or more. However, Comparative Example D had poor copy image reproducibility at the time of plate making, and Comparative Example E had insufficient resist properties to a processing solution for dissolving and removing non-image portions. Since high image reproducibility was not obtained, the image quality of the printed matter was deteriorated from the start of printing, and a printed matter having a sufficient image quality was not obtained.

As described above, only the liquid developer of the present invention
In an electrophotographic plate making system in which a non-image portion was eluted to be a printing original plate, excellent dispersibility, re-dispersibility and printing durability were satisfied.

Example 3 10 g of a tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 95/5 by weight), 10 g of alkali blue and 30 g of Isopar G were mixed with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.). ) And put 4
The mixture was dispersed for a time to obtain a fine dispersion of alkali blue. 6 g of the resin particles of Production Example D-26 of latex particles (as solid content), 2.5 g of the above-mentioned alkali blue dispersion,
A liquid developer for electrostatography was prepared by diluting 0.06 g of hexadecene / hemat maleic acid octadecylamide copolymer and 20 g of FOC-1800 to 1 liter of Isopar G.

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

Next, the electrophotographic photosensitive material P-3 prepared according to the following prescription was charged to -6 kV in a dark place, and a 2.0 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) was used as a light source. And a pitch of 25 μm on a photosensitive material surface under an irradiation dose of 45 erg / cm ^2.
After exposure at a scanning speed of m and a scanning speed of 330 m / sec, development was performed using the liquid developer of the present invention, and further heating at 60 ° C. for 30 seconds to obtain a toner image.

<Preparation of Electrophotographic Photosensitive Material P-3> 25 g of a binder resin B-4 having the following structure was prepared.
5, 9 g of 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, 0.018 of cyanine dye A having the following structure
g and 300 g of toluene were dispersed at a rotation speed of 1 × 10 ⁴ rpm for 10 minutes using a homogenizer to prepare a dispersion for forming a photosensitive layer. This was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 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 allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours.
-3 was prepared.

[0147]

Embedded image

[0148]

Embedded image

The master thus obtained was passed through an etching machine once using ELP-EX, and then immersed for 3 minutes in a photoconductive layer binder resin hydrophilizing solution E-3 having the following formulation. Then, it was washed with water and dried. <Preparation of treatment liquid E-3> 80 g of diethanolamine, 5 g of Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) and 80 g of methyl ethyl ketone 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 prepared.

Observation of the image portion of the obtained printing original plate with an optical microscope revealed that there were no defects such as fine lines and fine characters in the toner image portion, and the resist properties of the toner particles of the present invention were good. Next, the printing durability was the same as in Example 1, except that the above-mentioned master was used as an offset master master, and a solution obtained by diluting the processing solution E-3 ten times with distilled water was used as a dampening solution. As a result, 3,000 prints having good print quality were obtained.

Examples 4 to 19 The procedure of Example 1 was repeated, except that the latex particles D-25 of the liquid developer of the present invention were replaced by the latex particles shown in Table G below. To prepare each liquid developer.

[0152]

[Table 16]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1 to examine the performance. Each liquid developer shows the same performance as in Example 1,
Redispersibility, fixability, resistability and printing durability were all good.

Examples 20 to 35 The procedure of Example 2 was repeated, except that the latex particles shown in Table H below were used instead of the latex particles D-25 of the liquid developer of the present invention. To prepare each liquid developer.

[0155]

[Table 17]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 to examine the performance. Each liquid developer shows the same performance as in Example 2,
Redispersibility, resist properties and printing durability were all good.

Example 36 A mixture of 100 g of the white resin dispersion obtained in Production Example 30 of latex particles and 1.5 g of Sumicalon Black was heated to a temperature of 100 ° C., and heated and stirred for 4 hours. After cooling to room temperature, the remaining dye was removed by passing through a 200-mesh nylon cloth to obtain a black resin dispersion having an average particle size of 0.21 μm. A liquid developer was prepared by diluting 30 g of the above black resin dispersion and 0.05 g of zirconium naphthenate into 1 liter of Shellsol 71. When this was developed by the same apparatus as in Example 1, no toner stain was generated on the apparatus even after 2,000 sheets were developed. Also, in the same manner as in Example 1, the plate was made into a plate for offset master by performing plate making and etching treatment.
The printed matter after 3,000 sheets was a printed matter of clear image quality.

Example 37 A mixture of 100 g of the white resin dispersion obtained in Production Example 31 of latex particles 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, the remaining dye was removed through a 200-mesh nylon cloth to obtain 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 g of zirconium naphthenate to 1 liter of Isopar H. When this was developed by the same apparatus as in Example 3, no toner adhesion stains were observed on the apparatus even after 2,000 sheets were developed. or,
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.

[0159]

According to the present invention, a liquid developer having excellent dispersion stability, redispersibility and fixability was obtained. In particular, as a developer for an electrophotographic plate making system, the resist properties of the toner image portion were excellent, and thus the printing durability of the obtained offset master plate was remarkably improved.

Claims (2)

(57) [Claims] 1. A resistance 10 ⁹ [Omega] cm or more and a dielectric constant of 3.5 or less of the carrier liquid, the liquid developer for electrostatic photography composed by dispersing at least resin particles, the dispersion resin particles, non-aqueous A monofunctional monomer (A) which is soluble in a solvent but insolubilized by polymerization, contains a specific substituent represented by the following general formula (I), and contains the monomer (A) A copolymerizable monomer (C), a polyfunctional monomer (D) having two or more polymerizable functional groups copolymerizable with the monomer (A), a phosphono group, a carboxyl group, a sulfo group, group, a hydroxyl group, a formyl group, an amino group, -P (= O) (OH ) R 1 group [R ¹ is -
Represents an R ² group or an —OR ² group, wherein R ² represents a hydrocarbon group], a —CONR ³ R ⁴ group, a —SO ₂ NR ³ R ⁴ group [R ³ and R ⁴ are each independently a hydrogen atom Or a hydrocarbon group], and a polymer component containing at least one polar group selected from cyclic acid anhydride-containing groups and / or a polymer component corresponding to the monofunctional monomer (A) At least one
An AB type block polymer chain composed of a seed-containing block A and a block B containing at least one polymer component represented by the following general formula (II) is bonded to at least three organic molecules. And, each AB type block polymer chain is bonded to the organic molecule at one end opposite to the end bonded to block B of the polymer main chain of block A,
And a dispersion stabilizing resin [P] composed of a star copolymer having a weight average molecular weight of 2 × 10 ^{4 to} 5 × 10 ^5.
Is a polymer resin particle obtained by polymerizing a mixture containing at least one of each of the following. Embedded image In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms or a substituent selected from the substituents represented by the following general formula (III). Embedded image In the formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same or different from each other, and are each —O—, —S—, —CO—, —CO ₂ —,
_{-OCO -, - SO 2 -,} - N (R 22) -, - CON
_{(R 22) -, - N} (R 22) CO -, - N (R 22) SO 2
—, —SO ₂ N (R ₂₂ ) —, —NHCO ₂ — or —N
It represents a HCONH- (wherein R ₂₂ represents the same meaning as above R _21). A ₁ and A ₂ may be the same or different from each other, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following formula 3 intervening in the bond of the main chain. Embedded image In Chemical Formula 3, 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 above, and A ₄ represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted. And R ₂₃ has the same contents as R ₂₁ described above. m, n and p may be the same or different and represent an integer of 0 to 4, respectively. However, m, n and p do not become 0 at the same time. formula
In (I), U ¹ represents -COO-, -CONH-, -CON.
(E ²⁾ - [wherein E ² represents an aliphatic group or the general formula (II
Represents a substituent represented by I)], -OCO-, -CONH
_{COO -, - CH 2 COO -} , - (CH 2) s OCO- [where s represents an integer of 1 to 4], -O- or -C ₆ H ₄ -
Represents COO-. a ¹ and a ² may be the same or different from each other, and each represents a hydrogen atom, an alkyl group, —COO-E ³
Or —CH ₂ COO—E ³ (where E ³ represents an aliphatic group)
Represents Embedded image In the general formula (II), X ¹ represents -COO-, -OCO-,-(C
_{H 2) x COO -, -} (CH 2) x OCO- [where x is 1 to
Represents an integer of 3] or -O-. Y ¹ has 8 carbon atoms
Represents the above aliphatic group. b ¹ and b ^2, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ^1, or a hydrocarbon -COO-Z ¹ via a hydrogen group (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted). 2. In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 50.
The liquid developer for electrostatography according to claim 1, wherein the liquid developer has a weight ratio of / 99 to 50 (weight ratio).