JP3300484B2 - 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. 3-12666, 4-313763, 3
JP-A-225353 and JP-A-4-46353 disclose a method of improving with a soluble dispersion stabilizing resin.
42,975, JP-A-62-151868, JP-A-1-237668, JP-A-2-168276, and 3-7.
Nos. 1152 and 3-95565 describe a method of modifying the surface of latex particles by coexisting a monomer to be insolubilized and another compound having a physicochemical interaction. It is disclosed that the diameter, redispersibility and storage stability 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 is insolubilized by polymerization; a polymer comprising a repeating unit represented by the following general formula (I): A monofunctional macromonomer (MA) having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the formula (II), and capable of copolymerizing with the monomer (A) A polyfunctional monomer (D) having two or more polymerizable functional groups,
And 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; Or a block A containing at least one kind of polymer component corresponding to the monofunctional monomer (A) and the following general formula (III)
And at least three AB-type block polymer chains composed of a block B containing at least one type of polymer component represented by the following formula: At one end of the polymer main chain of block A opposite to the end bonded to block B, is bonded to the organic molecule, and has a weight average molecular weight of 2 × 10 ⁴ to
A polymer resin particle obtained by polymerizing a mixture containing at least one dispersion stabilizing resin [P] composed of a star copolymer, which is 1 × 10 ^5. Achieved by electrographic liquid developers.

[0010]

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In the formula (I), V⁰Is -COO-, -OCO
-,-(CH_Two)_rCOO-,-(CH _Two)_rOCO-, -O
-, -SO_Two-, -CONHCOO-, -CONHCO
NH-, -COND¹¹-, -SO_TwoND¹¹-Or Fe
Nylene group [hereinafter, phenylene group is referred to as "-Ph-"
And -Ph- is a 1,2-phenylene group,
It includes a nylene group and a 1,4-phenylene group. ]
You. Where D¹¹Is a hydrogen atom or a hydrocarbon having 1 to 22 carbon atoms
And r represents an integer of 1 to 4. a¹And a^TwoIs
May be the same or different, and each represents a hydrogen atom,
Atom, cyano group, hydrocarbon group, -COO-D¹²Or
-COO-D via a hydrocarbon group¹²Represents Where D¹²
Represents a hydrogen atom or a hydrocarbon group which may be substituted. D
⁰Is a hydrocarbon group having 1 to 22 carbon atoms, or the following general formula (I
Represents a substituent selected from the substituents represented by V).

[0012]

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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 are each -O-, -CO-, -CO
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ representing a CO-. Here D ²² denote the same contents as the D ^21. A ¹ and A ² may be the same or different from each other, and each may be substituted;
Alternatively, it represents a hydrocarbon group having 1 to 18 carbon atoms which may be represented by the following formula 8 in the bond of the main chain.

[0014]

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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 B ¹ and B ² described above.
⁴ represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, D ²³ represent the same contents as the D ^21. 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]

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In the formula (II), V ¹ has the same content as V ⁰ in the formula (I). b ¹ and b ² may be the same or different from each other, and represent the same contents as a ¹ and a ² in the formula (I).

[0018]

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

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 also referred to as latex particles), which are the most important constituents in the present invention, are prepared by dispersing a non-aqueous solvent into a dispersion-stabilizing resin [P In the presence of at least one monofunctional monomer (A), at least one monofunctional macromonomer (MA), and at least one polyfunctional monomer (D). It is granulated.

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 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 (V) can be mentioned.

[0026]

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In the formula (V), 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 (—Ph—). W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl Group, 2
-Hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group,
Fluorobenzyl group, 2-methoxyethyl group, 3-methoxypropyl group, 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.).

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

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 monofunctional macromonomer (MA) used in the present invention will be further described. The monofunctional macromonomer (MA) has a polymerizable double bond group represented by the following general formula (II) only at one end of the main chain of a polymer comprising a repeating unit represented by the following general formula (I). It is a macromonomer having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding.

[0032]

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

[0034]

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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 are each -O-, -CO-, -CO
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ representing a CO-. Here D ²² denote the same contents as the D ^21. A ¹ and A ² may be the same or different from each other, and each may be substituted;
Alternatively, it represents a hydrocarbon group having 1 to 18 carbon atoms which may have the following formula 14 intervening in the bond of the main chain.

[0036]

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In 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 described above.
⁴ represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, D ²³ represent the same contents as the D ^21. 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.

[0038]

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In the formula (II), V ¹ has the same content as V ⁰ in the formula (I). b ¹ and b ² may be the same or different from each other, and represent the same contents as a ¹ and a ² in the formula (I).

In the general formulas (I) and (II), a ¹ ,
The hydrocarbon groups contained in a ² , V ⁰ , D ⁰ , b ¹ , b ² and V ¹ each have the indicated carbon number (as an unsubstituted hydrocarbon group), but these hydrocarbon groups are substituted. It may be.

In the general formula (I), D ¹¹ in the substituent represented by V ⁰ is not only a hydrogen atom, but also a preferable hydrocarbon group is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, Methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl,
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 optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl- 2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.), carbon Number 7-1
2 optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group and the like, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexyl) An ethyl group, a 2-cyclopentylethyl group, or the like), or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
A bromophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, a dodecyloylamidophenyl group, etc.).

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

A ¹ and a 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-D ¹³ or -CH ₂ COO-D
¹³ (D ¹³ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,
Represents an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically,
Represents a represents) the same contents as those described above D ^11.

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

The case where D ⁰ represents a substituent represented by formula (IV) will be described in detail. A ¹ and A ² may be the same or different from each other, and each may be substituted;
Or a hydrocarbon group having 1 to 18 carbon atoms (the alkyl group may be an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group; examples represent specific examples include the same contents as) listed in D ^11. More specific examples of A ¹ and A ² include those represented by —C (D ³¹ ) (D
³² )-[D ³¹ and D ³² represent a hydrogen atom, an alkyl group, a halogen atom, etc.],-(CH = CH)-, a phenylene group (-Ph-), a cyclohexylene group [hereinafter, a cyclohexylene group is referred to as " -C ₆ H ₁₀ - expressed in "" - C ₆ H ₁₀ - "includes 1,2-cyclohexylene group, 1,3-cyclohexylene, 1,4-cyclohexylene group. ], And any combination of atomic groups such as Chemical formula 14.

Further, in the bonding group in the general formula (I): -V ^0- (A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹ , V ⁰ to D ²¹ (that is, V ⁰ , A ¹ , B ¹ , A ² ,
B ² , D ²¹ ) have a total number of atoms of 8
What is comprised from the above is preferable. Where A ¹ , A ²
There in the case of the hydrocarbon group 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 connecting backbone. As the number of atoms in the connecting main chain, for example, V
^{When 0} represents —COO— 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 the atoms. Included as a number. Therefore, -COO-
And -CONH- are counted as 2 atoms. Similarly,
If D ²¹ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included. Therefore, in this case, it is counted as 9 atoms.

In the above-mentioned repeating unit represented by the general formula (I), when D ⁰ represents a substituent represented by the above-mentioned general formula (IV), that is, at least two or more of the repeating unit components in the molecule are used. 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 C ₁ -C ₁₈ alkyl group; R 'is a hydrogen atom or an alkyl group having _{C 1 ~C 18; k 1,} k 2 each 1 to 1
M ₁ represents an integer of ₁ to 100;

[0048]

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[0049]

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[0050]

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[0051]

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The macromonomer (MA) used in the present invention
As described above, the polymerizable double bond group represented by the general formula (II) is directly bonded to only one terminal of the polymer main chain composed of the repeating unit represented by the general formula (I), Alternatively, it has a chemical structure linked via an arbitrary linking group.

In the formula (II), V ¹ has the same meaning as V ⁰ in the formula (I), b ¹ and b ² may be the same or different from each other, and a ¹ in the above formula (I) or it is synonymous with a ^2. The preferred ranges of V ¹ , b ¹ and b ² are the same as those described for V ⁰ , a ¹ and a ² , respectively. More preferably, ^one of b ¹ and b ^{2 in} the formula (II) is a hydrogen atom.

The group linking the components of the formula (I) and the component of the formula (II) includes a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom and sulfur atom). Atoms, nitrogen atoms, silicon atoms, etc.) and any combination of heteroatom-heteroatom bond atomic groups. Preferred among the macromonomers (MA) of the present invention are those represented by the following general formula (VI).

[0055]

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In the general formula (VI), contents other than Z represent the same contents as those in the formulas (I) and (II). Z is a mere bond or -C (D ⁴¹ ) (D ⁴² )-[D ⁴¹ and D ⁴² are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), cyano indicating group, a hydroxyl group, an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) and the like], - (CH = CH) - , - C 6 H 10
- (cyclohexylene group), - Ph- (phenylene group), - O -, - S -, - CO -, - N (D 43) -, -
_{COO -, - SO 2 -,} - CON (D 43) -, - SO 2 N
(D ⁴³ )-, -NHCOO-, -NHCONH-, -S
i (D ⁴³ ) (D ⁴⁴ )-[D ⁴³ and D ⁴⁴ each independently represent a hydrogen atom or a hydrocarbon group having the same content as that of D ¹¹ above], a linking group represented by the following chemical formula 21, Represents a single linking group selected from atomic groups such as the above, or a linking group composed of an arbitrary combination.

[0057]

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In the formula (VI), a ¹ , a ² , b ¹ , b ² ,
Particularly preferred examples of each of V ⁰ and V ¹ are shown below. As V ⁰ , -COO-, -OCO-, -O-,
—CH ₂ COO— or —CH ₂ OCO— is the same as above for V ¹ (however, D ¹¹ is a hydrogen atom)
There, the ^{a 1, a 2, b 1} , b 2 include a hydrogen atom or a methyl group. Hereinafter, specific examples of the portion represented by the following general formula (II ′) in the general formula (VI) are shown. However, the present invention is not limited to these.

[0059]

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In the following, b represents -H or -CH
₃ ; m ₁ represents an integer of ₁ to 12; n ₁ represents an integer of 2 to 12;

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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Further, the macromonomer (M
In A), another repeating unit may be contained as a copolymerization component together with the repeating unit represented by the general formula (I). As the other copolymer component, any compound may be used 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 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,
Heterocyclic compounds containing an unsaturated bond group are exemplified. Specifically, for example, the compounds exemplified for the above-mentioned monomer (A) and the like can be mentioned, but it should not be construed that the invention is limited thereto.

In the sum of the repeating units of the macromonomer (MA), the repeating unit component represented by the general formula (I) is
Preferably, the content is 40% by weight or more of the whole,
More preferably, it is 60 to 100% by weight. When the content of the component represented by the general formula (I) is less than 40% by weight, the mechanical strength of the image area formed by the dispersed resin particles is not sufficiently maintained, and therefore, the printing durability when used as an offset original plate The effect of improvement cannot be seen. The macromonomer (MA) of the present invention has a number average molecular weight of 1 × 10 ^3.
１1 × 10 ⁴ , preferably 2 × 10 ³ -9 × 10 ³
Is more preferred. If the upper limit of the number average molecular weight of the macromonomer (MA) exceeds 1 × 10 ⁴ , the printing durability will decrease. On the other hand, if the molecular weight is too small, there is a tendency for stains to occur,
It is preferably at least 1 × 10 ³ .

The macromonomer (MA) of the present invention has been
It can be produced by a known synthesis method. For example,
Obtained by anionic or cationic polymerization
By reacting various reagents with the terminals of the living polymer,
Chromomerization, ionic polymerization method, in the molecule
Reaction of carboxyl group, hydroxy group, amino group, etc.
Using a polymerization initiator and / or a chain transfer agent containing a functional group
Of the terminal reactive group bond obtained by radical polymerization
Reacts the Gomer with various reagents to form a macromer.
Method by dical polymerization, polyaddition or polycondensation reaction
To the oligomer obtained by the above-mentioned radical polymerization method.
In the same manner, the polyaddition condensation method of introducing a polymerizable double bond group
And the like. Specifically, P.S. Dreyf
uss & R.S. P. Quirk, Encycl. Po
lym. Sci. Eng. ,7, 551 (1987),
P. F. Rempp & E. Franta, Adv.
Polym. Sci. ,58, 1 (1984); P
ersec, Appl. Polym. Sci. ,28
5, 95 (1984); Asami & M. Ta
kaRi, Makvamol. Chem. Suppl
n.12, 163 (1985); Remp. et
 al, Makvamol. Chem. Suppln.
8, 3 (1984), Yusuke Kawakami, Chemical Industry,38, 56
(1987), Yuya Yamashita, Polymer,31, 988 (19)
82), Shiro Kobayashi, Polymer,30, 625 (198
1), Toshinobu Higashimura, Journal of the Japan Adhesive Society,18, 536 (19
82), Koichi Ito, Polymer Processing, 35, 262 (198)
6), Kishiro Higashi, Takashi Tsuda, Functional Materials,1987, No.
Described in reviews such as 10, 5 etc. and references and patents cited therein
Can be synthesized according to the following method.

Examples of the polymerization initiator containing a specific reactive group in the molecule include 4,4'-azobis (4-cyanovaleric acid) and 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-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis [2-
(5-hydroxy-3,4,5,6-tetrapyrimidin-2-yl) propane], 2,2'-azobis {2-
[1- (2-hydroxyethyl) -2-imidazoline-
2-yl] propane}, 2,2'-azobis [N- (2
-Hydroxyethyl) -2-methyl-propionamidine] and azobis compounds such as 2,2'-azobis [N- (4-aminophenyl) -2-methylpropionamidine].

Further, as a chain transfer agent containing a specific reactive group in the molecule, for example, a mercapto compound (for example, thioglycolic acid, thiomalic acid) containing the reactive group or a substituent capable of being induced to the reactive group , Thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-mercaptonicotinic acid
[N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino]
Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-
1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, or the above reactivity Examples include an iodized alkyl compound containing a group or a substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, and the like). Preferably, a mercapto compound is used.

These chain transfer agents or polymerization initiators are monomers 1 each corresponding to a repeating unit of the general formula (I).
It is preferable to use 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 00 parts by weight.

Next, the monomer (A) used together with the monofunctional monomer (A) and the monofunctional macromonomer (MA)
A monomer (D) having two or more polymerizable functional groups capable of copolymerizing with (hereinafter, also referred to as a 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 (VII) The functional groups shown are mentioned.

[0074]

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[0075] In the formula ^{(VII), 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 any monomer having two or more of the same or different polymerizable functional groups. And polymerize with the monofunctional macromonomer (MA) to form a polymer that is insoluble in non-aqueous solvents.

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.).

Further, as a monomer having a different polymerizable functional group, for example, a carboxylic acid having a vinyl group [for example,
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 dispersion resin of the present invention comprises at least one of each of the monomer (A), the monofunctional macromonomer (MA) and the monomer (D). If the resin synthesized from the monofunctional macromonomer is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, the monofunctional macromonomer (MA) is preferably used in an amount of 0.1 to 20% by weight, more preferably 0.3 to 20% by weight, based on the insoluble monomer (A).
8% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention accounts for 20 mol% or less, preferably 10 mol% of all monomers (including the monofunctional macromonomer (MA)). Used in the following amounts to polymerize 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
１1 × 10 ⁶ .

Next, the dispersion stabilizing resin [P] of the present invention will be described. In order to form a stable resin dispersion from the solvent-insoluble polymer formed by polymerizing the monomer (A), the monofunctional macromonomer (MA) and the monomer (D) in a non-aqueous solvent, The dispersion stabilizing resin [P] of the present invention used is A-
A weight average molecular weight of 2 × 10 ⁴ , wherein at least three polymer chains of the B-type block copolymer component are bonded in an organic molecule;
ス タ ー 1 × 10 ⁶ star copolymer. 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, a —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) Is contained. The other block (block B) contains at least one polymer component comprising a repeating unit represented by the above general formula (III). 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 30.

[0081]

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In formula 30, 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 copolymer is from 1/50/99 to 50 (weight ratio), 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 (III) contained in the block B,
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
And 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 (III) contained in the block B). The re-dispersion stability of the dispersed resin particles obtained by polymerizing the monofunctional monomer (A), the monofunctional macromonomer (MA) and the polyfunctional monomer (D) is reduced. On the other hand,
When the content exceeds a predetermined ratio, the average particle size of the dispersed resin particles obtained by the polymerization reaction of the monofunctional monomer (A), the macromonomer (MA) and the monomer (D) becomes coarse, 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 1 × 10 ⁶ , 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 represented by -N
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ and R ⁶ represent 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 group of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is 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 polymer component containing the 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.

[0093]

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[0094]

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[0095]

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Next, the block B of the dispersion stabilizing resin [P] is used.
The repeating unit represented by the general formula (III) constituting the formula (III) will be described in detail. In the general formula (III), 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, and these may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc. .

D ¹ and d 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 C 1-3 carbon atom.
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- 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 (III). 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 (III). 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 (III) may be used in combination.

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

[0101]

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Wherein 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 consist structure alone or any combination thereof, in the case of combination, -O -, - S -, - N (r 7) -, - COO -, - C
^{ON (r 7) -, -} SO 2 -, - SO 2 N (r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO
-, -NHCONH-, an oxygen atom, a sulfur atom, a hetero ring containing a hetero atom such as a nitrogen atom (for example, a thiophene ring,
A combination of bonding units such as a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring, a piperidine ring, a pyrazine ring, a pyrrole ring, and a piperazine ring) may be included.

Examples of other organic molecules that bind the polymer chain 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.

[0104]

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The star-type copolymer [P] of the present invention can be synthesized by using a conventionally known method for synthesizing a star-type polymer of a monomer having 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 latex particles used in the present invention, generally, the dispersion stabilizing resin [P],
Monofunctional monomer (A), monofunctional macromonomer (M
A) and the 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 of a dispersion stabilizing resin [P], a monomer (A), a macromonomer (MA) and a monomer (D), a dispersion stabilizing resin [ P], a method of dropping the monomer (A), the macromonomer (MA) and the monomer (D) together with the polymerization initiator in a solution in which the solution [P] is dissolved. In a solution containing the monomer (A), the macromonomer (MA) and a part of the monomer (D), the remaining monomer (A), the macromonomer (MA) and the monomer ( A method of optionally adding D), and further, polymerizing a mixed solution of a dispersion stabilizing resin [P], a monomer (A), a macromonomer (MA) and a monomer (D) in a non-aqueous solvent. There is a method of arbitrarily adding it together with the initiator, and any of these methods can be used for production.

The total amount of the monomer (A), macromonomer (MA) and monomer (D) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the non-aqueous solvent. Department. The soluble resin as the dispersion stabilizing resin [P] is used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of all the monomers (including the macromonomer (MA)) used above. Department. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the monomers including the macromonomer (MA).
Is appropriate. Further, the polymerization temperature is about 50 to 180 ° C, preferably 60 to 120 ° C. Reaction time is 1 to
15 hours is preferred.

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) or monomer When the unreacted product of the compound (D) remains, the solvent or the monomer (A) or the monomer (A) is removed by heating to a boiling point or higher or by distillation under reduced pressure. Is preferred.

The non-aqueous latex particles produced as described above exist as fine particles having a uniform particle size distribution, and at the same time, 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 according to the present invention having the above-mentioned effects can be obtained by insolubilizing the monomer (A) and the macromonomer (M
It depends on a star-type copolymer composed of specific blocks used together with A) and monomer (D). 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. Thereby, the block A portion is sufficiently adsorbed by the physicochemical interaction at the time of polymerization granulation with respect to the dispersed resin particles, and the block B portion having a high affinity for the non-aqueous dispersion medium is formed with respect to the solvent. Since there are at least three or more polymer chains that sufficiently solvate and have a sufficient steric repulsion effect (so-called tail-like adsorption), the adsorption effect and the steric repulsion effect are sufficiently efficiently exhibited. It is presumed that the effect of the present invention has 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 a solvate component 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 characterized in that the particles form a crosslinked structure by polymerization and granulation using a polyfunctional monomer (D). This allows
After forming an image as toner particles, even after going through a hydrophilization treatment step to make a printing original plate, the suitability of the processing liquid (resist property) is improved, and damage to the toner image area can be significantly reduced. Was. 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 charge 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 amounts of the main components of the liquid developer of the present invention will be described below. The toner particles mainly composed of a resin (and a coloring agent 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.

[0117]

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.

Production Example 1 of Macromonomer (MA) A mixed solution of 100 g of macromonomer MA-1 methyl methacrylate, 5 g of 3-mercaptopropionic acid and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. . 2,2 '
-Azobis (isobutyronitrile) (abbreviated as AIB.
N. ) Was added and reacted for 4 hours. I. B.
N. Was added for 3 hours, and A. I. B. N. Was added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution.
Was added and stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. The number average molecular weight of the polymer is 6,500
Met.

[0119]

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Preparation Examples 2 to 39 of Macromonomer (MA): Macromonomer MA-2 to MA-39 In Preparation Example 1 of macromonomer (MA), only methyl methacrylate was replaced with a compound corresponding to the following Table-A. Otherwise, the reaction was carried out in the same manner as in Production Example 1, and the macromonomer MA-
2-MA-39 was synthesized. The number average molecular weight of each obtained macromonomer was in the range of 5,000 to 7000.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

Preparation Example 40 of Macromonomer (MA) Macromonomer MA-40 2,3-dipropoxypropyl methacrylate 96
g, 4 g of thioethanol and 200 g of toluene were heated to a temperature of 70 ° C. while stirring under a nitrogen stream.
A. I. B. N. Was added and reacted for 4 hours. Further, A. I. B. N. Was added for 3 hours, and then A. I. B. N. Was added and reacted for 3 hours. The reaction solution was cooled to room temperature, 16.2 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 60 g of methylene chloride was added dropwise over 1 hour. . t-
1.0 g of butyl hydroquinone was added, and the mixture was stirred for 4 hours. The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was collected by decantation, dissolved in 150 ml of methylene chloride, and reprecipitated in 1 liter of methanol. The oil was collected and dried under reduced pressure to obtain a polymer having a number average molecular weight of 6.30 × 10 ^{3 in} a yield of 54 g.

[0126]

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Preparation Examples of Macromonomers (MA) 41 to 46: Macromonomers MA-41 to MA-46 In the preparation examples of macromonomer MA-40, methacrylate monomers (corresponding to 2,3-dipropoxypropyl methacrylate) and Each of the unsaturated carboxylic acids (corresponding to 2-carboxyethyl methacrylate) was replaced with MA-4
In the same manner as in Production Example 0, the macromonomers shown in Table-B below were produced. The yield was 96 g, and the number average molecular weight of each obtained macromonomer was in the range of 5 × 10 ³ to 8 × 10 ³ .

[0128]

[Table 5]

[0129]

[Table 6]

Production Example 47 of Macromonomer (MA): Macromonomer MA-47 2,3-diacetoxypropyl methacrylate 100
g, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol in a nitrogen stream at a temperature of 75 ° C.
Was heated. 4,4'-azobis (4-cyanovaleric acid)
(Abbreviation: A.C.V.) 4.0 g and reacted for 5 hours,
Further, A. C. V. Was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liters of methanol, and the oil was collected by decantation and dried under reduced pressure. The yield was 85 g. 50 g of this oil, 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 2,2'-methylenebis (6-t
-Butyl-p-cresol) at a temperature of 10
Stirred at 0 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in 1 liter of petroleum ether to obtain 63 g of a white powder. The number average molecular weight was 6,200.

[0131]

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Synthesis Example 1 of Dispersion Stabilizing Resin [P] Resin [P-1] Methyl methacrylate 50 g, methyl acrylate 50
g, a mixture of 7.8 g of an initiator [I-1] having the following structure and 100 g of tetrahydrofuran 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.

[0133]

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[0134]

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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]
Was synthesized in the same manner as in Synthesis Example 1 except that 0.011 mol of an initiator shown in Table-C 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 .

[0136]

[Table 7]

[0137]

[Table 8]

[0138]

[Table 9]

[0139]

[Table 10]

Synthesis Examples 15 to 28 of Dispersion Stabilizing Resin [P]: Resins [P-15] to [P-28] Each monomer corresponding to the polymer component of block A shown in Table D below; A mixture of 0.01 mol of the initiator [I-7] and 100 g of tetrahydrofuran 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-D and each monomer corresponding to the polymer component of block B shown in Table-D below as Table-D
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.

[0141]

[Table 11]

[0142]

[Table 12]

[0143]

[Table 13]

[0144]

[Table 14]

Production Example 1 of Latex Particle 1: Latex Particle D-1 20 g of dispersion stabilizing resin [P-1], 50 g of methyl methacrylate, 50 g of methyl acrylate, 1.2 g of monofunctional macromonomer MA-10, 1.2 g of ethylene glycol A mixed solution of 3 g of dimethacrylate and 384 g of Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2′-azobis (isovaleronitrile) (abbreviated AIVN) was added as a polymerization initiator,
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, the initiator is added to 0.1.
After adding 5 g and reacting for 2 hours, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours under a reduced pressure of 20 mmHg to distill off unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was 98% polymerized and had an average particle size of 0.24 μm.
Latex. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

Latex Particle Production Examples 2 to 21: Latex Particles D-2 to D-21 In the latex particle production example 1, a dispersion stabilizing resin [P-1], a monofunctional macromonomer MA-10, and ethylene Except for using the dispersion stabilizing resin, monofunctional macromonomer (MA) and monomer (D) shown in Table-E below in place of glycol dimethacrylate, the same operation as in Production Example 1 was carried out. Latex particles D-2 to D of the present invention
-21 was produced. The polymerization rate of each of the obtained latex particles is 95 to 98%, and the average particle size is 0.15 to 0.25 μm.
And the monodispersity was good.

[0147]

[Table 15]

[0148]

[Table 16]

Production Example 22 of Latex Particles: Latex Particle D-22 18 g of dispersion stabilizing resin [P-18], vinyl acetate 10
A mixed solution of 0 g, 1 g of the monofunctional macromonomer MA-30, 5 g of divinyl adipate and 375 g of Isopar H was heated to a temperature of 40 ° C. while stirring under a nitrogen stream. A. I. V. N. Was added and reacted for 3 hours.
Further, A. I. V. N. Was added and reacted for 3 hours. Further, the mixture was stirred at a temperature of 100 ° C. for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 93% and an average particle size of 0.18 μm.

Latex Particle Production Examples 23 to 30: Latex Particles D-23 to D-30 Monomer (A) (ie, vinyl acetate), monofunctional macromonomer MA used in Latex Particle Production Example 22 -30, except that the compounds described in Table-F below were used instead of the dispersion stabilizing resin [P-18] and the monomer (D) (that is, divinyl adipate), respectively. Latex particles were produced in the same manner. The polymerization rate of each of the obtained latex particles was 90 to 98%, the average particle size was in the range of 0.15 to 0.30 μm, and the monodispersity was good.

[0151]

[Table 17]

Production Example 31 of Latex Particles: (Comparative Example A) Dispersion stabilizing resin [RP-1] having the following structure synthesized by the method disclosed in JP-A-3-225353 was prepared using 20
g, 50 g of methyl methacrylate, 50 g of methyl acrylate and 380 g of Isopar H, except that a mixed solution of 380 g was used.
A white dispersion as latex particles having a polymerization rate of 98% and an average particle size of 0.30 μm was obtained.

[0153]

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Production Example 32 of Latex Particles: (Comparative Example B) The same treatment as in Production Example 31 except that 1.2 g of macromonomer MA-10 was further added in Production Example 31 of Latex Particles (Comparative Example A). Thus, a white dispersion as latex particles having a polymerization rate of 98% and an average particle size of 0.28 μm was obtained. (JP-A-4-46353)

Production Example 33 of Latex Particles: (Comparative Example C) The same treatment as in Production Example 31 was performed except that 3 g of ethylene glycol dimethacrylate was added in Production Example 31 of Latex Particles (Comparative Example A), A white dispersion as latex particles having a polymerization rate of 98% and an average particle size of 0.30 μm was obtained.

Production Example 34 of Latex Particles: (Comparative Example D) A dispersion stabilizing resin [RP-2] having the following structure, which was synthesized by the method disclosed in
g, 100 g of vinyl acetate, 5 g of divinyl adipate, and 375 g of Isopar H, were treated in the same manner as in Production Example 22 of the above-mentioned latex particles, and the white particles were latex particles having a polymerization rate of 92% and an average particle diameter of 0.23 μm. A dispersion was obtained.

[0157]

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Production Example 35 of Latex Particles: (Comparative Example E) In Production Example 34 of latex particles (Comparative Example D), the macromonomer MA-21 was used instead of divinyl adipate.
Was treated in the same manner as in Production Example 34 except that 1.2 g of
A white dispersion as latex particles having a polymerization rate of 91% and an average particle size of 0.23 μm was obtained.

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. 30 g of the resin dispersion of Production Example 1 for latex particles, 2.5 g of the above nigrosine dispersion, and branched octadecyl alcohol FOC-180
0 (manufactured by Nissan Chemical Industries, Ltd.) and 0.07 g of an octadecene-half-maleic acid octadecylamide copolymer were diluted to 1 liter of Isopar G to prepare a liquid developer for electrostatography.

(Preparation of Comparative Developers A to C) Three kinds of liquid developers A, B and C for comparison were prepared by replacing the resin dispersion in the production of the above liquid developer with the following resin dispersion. . Comparative liquid developer A: resin dispersion of Production Example 31 of latex particles. Comparative liquid developer B: resin dispersion of Production Example 32 of latex particles. Comparative liquid developer C: resin dispersion of Production Example 33 of latex particles.

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

[0162]

[Table 18]

The measurement of each evaluation item in Table-G 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 for 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.

[0165]

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(Note 3) Resist property of toner image: The plate-making original plate was etched using a desensitizing liquid 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 1 liter, the pH was adjusted to 13.0 with potassium hydroxide to prepare a treatment liquid E-1.

(Note 4) Printing durability: The printing plate precursor subjected to plate making and hydrophilizing treatment under the conditions of the above (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 in Table-G, it can be seen that the present invention and Comparative Example B
Of the developer does not cause stains on the developing device,
The image of the second plate was clear and showed good results. This indicates that the dispersibility and the redispersibility are good. On the other hand, in the developers of Comparative Examples A and C, the redispersibility deteriorated, and the reproducibility of an actual copied image was adversely affected.

Further, when the mechanical strength of the toner image area was evaluated by forcibly rubbing, all the toner particles were 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 any toner particles occurred. Only the toner particles of the present invention and Comparative Example B were good.
In other cases, defects occurred in a fine area of the toner image portion such as a fine line or a fine character. In addition, when processed under normal desensitization processing conditions and printed as an offset master master,
Clear prints were obtained with only the present invention even after printing 5,000 sheets. In Comparative Examples A and C, 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, fine characters, and the like was observed from the start of printing. Further, in Comparative Example B, at the time of printing, thin lines, fine characters, and the like were missing on about 2,000 sheets from the start of printing.

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

Example 2 30 g of the resin dispersion of Production Example 22 of latex particles, 10 g of branched hexadecyl alcohol FOC-1600 (manufactured by Nissan Chemical Industries, Ltd.), and octadecyl vinyl ether /
A liquid developer for electrostatography was prepared by diluting 0.08 g of the hemi-maleic acid dodecylamide copolymer into 1 liter of Isopar G.

(Preparation of Comparative Developers D and E) Two kinds of liquid developers D and E for comparison were prepared by replacing the resin dispersion in the production of the liquid developer described above with the following resin dispersion. Comparative liquid developer D: resin dispersion of Production Example 34 of latex particles. Comparative liquid developer E: resin dispersion of Production Example 35 of latex particles.

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

[0175]

[Table 19]

In Table H, the contamination of the developing device and
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.

[0178]

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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-H, 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 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.

Furthermore, 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 40,000 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), 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. 30 g of the resin dispersion of Production Example 24 of latex particles, 2.5 g of the above nigrosine dispersion, 0.06 g of a hexadecene / half-maleic acid octadecylamide copolymer, and FOC-18
A liquid developer for electrostatography was prepared by diluting 20 g of 00 into 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 formulation 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.

[0189]

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[0190]

Embedded image

The original plate thus obtained was passed through an etching machine once using ELP-EX, and then immersed in a photoconductive layer binder resin hydrophilizing solution E-3 having the following formulation for 3 minutes. 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 13.5 with potassium hydroxide. Treatment liquid E-3
Was prepared.

When the image portion of the obtained printing original plate was observed with an optical microscope, no loss of fine lines or characters in the toner image portion was observed, 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 15 The procedure of Example 1 was repeated, except that the 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. To prepare each liquid developer.

[0194]

[Table 20]

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 16 to 25 The procedure of Example 2 was repeated, except that the latex particles D-22 of the liquid developer of the present invention were replaced with the latex particles shown in Table J below. To prepare each liquid developer.

[0197]

[Table 21]

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 26 A mixture of 100 g of the white resin dispersion obtained in Production Example 25 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 27 A mixture of 100 g of the white resin dispersion obtained in Production Example 26 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.

[0201]

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.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/13 G03G 9/135

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 is insolubilized by polymerization; and only one terminal of the main chain of a polymer comprising a repeating unit represented by the following general formula (I): A monofunctional macromonomer (M) having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the general formula (II)
A), a polyfunctional monomer (D) having two or more polymerizable functional groups copolymerizable with the monomer (A), and a phosphono group, a carboxyl group, a sulfo 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 (III) is bonded to at least three organic molecules. And each AB-type block polymer 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 Is 2 × 10 ⁴ to 1 × 10 ⁵ , a dispersion stabilizing resin [P] comprising a star copolymer
Is a polymer resin particle obtained by polymerizing a mixture containing at least one of each of the following. Embedded image In the formula (I), V ⁰ is -COO-, -OCO-,-(C
_{H 2) r COO -, -} (CH 2) r OCO -, - O -, - S
O ₂ —, —CONHCOO—, —CONHCONH—,
Represents —COND ¹¹ —, —SO ₂ ND ¹¹ —, or a phenylene group (where 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 represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—
D ¹² or —COO-D ¹² via a hydrocarbon group (where D ¹² represents a hydrogen atom or a hydrocarbon group which may be substituted). D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms or a substituent selected from substituents represented by the following general formula (IV). Embedded image 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 are each —O—, CO—, —CO ₂ —, —OCO
_{-, - SO 2 -, -} N (D 22) -, - CON (D 22) -
Or —N (D ²² ) CO— (where D ²² is the above D
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 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 is a hydrocarbon group having 1 to 18 carbon atoms which may be substituted. shows, D ²³ represent the same contents as the D ^21. 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. Embedded image Wherein (II), V1 represents the same content as V ⁰ which in formula (I). b ¹ and b ² may be the same or different from each other, and represent the same contents as a ¹ and a ² in the formula (I). Embedded image In the general formula (III), X ¹ represents -COO-, -OCO-,-(C
H ₂ ) _x COO-,-(CH ₂ ) _x OCO- [where x is 1
Represents an integer of to 3], or represents -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. d ¹ and d ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-Z ¹ , or —COO-Z ¹ via a hydrocarbon group (here, Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 2. In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 50.
The liquid developer for electrostatography according to claim 1, wherein the liquid developer has a weight ratio of / 99 to 50 (weight ratio).