JP2001098199A - Oily ink for electrostatic type ink jet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oily ink which is used for electrostatic type ink jets, has excellent ink extrusion stability and excellent brilliant image-forming property, gives images having excellent strengths, and enables the formation of printing plates that can form many printed products having brilliant images. SOLUTION: This oily ink for electrostatic ink jet is obtained by dispersing copolymer resin particles in a non-aqueous carrier liquid having an electric resistance of >=109 Ω.cm and a dielectric constant of <=3.5. The copolymer resin particles are obtained by subjecting a solution containing (A) a monofunctional monomer which is soluble in non-aqueous solvents but can be polymerized into a polymer insoluble in the solvents, (B) a monofunctional monomer which contains an amino group and can be copolymerized with the monomer (A), (C) a monofunctional monomer which contains a SO3H group and/or a SO2H group and can be copolymerized with the monomer (A), (MA) a monofunctional macromonomer in which a polymerizable double bond group is bound to only one end of the main chain of a polymer containing specific structure repeating units, and (P) a dispersion-stabilizing resin which contains a component for solubilizing the resin in a dispersing solvent, to a copolymerizing and particularizing treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based ink for an electrostatic ink jet used for forming an image by an electrostatic (electrostatic attraction or electrostatic attraction) ink jet recording system.

[0002]

2. Description of the Related Art Ink jet recording is a recording method capable of high-speed printing with low noise, and is a recording method that has been rapidly spreading recently. Ink jet recording is a method in which a liquid ink having a high fluidity is ejected from fine nozzles and is recorded on recording paper, and there are an on-demand (optional ejection) and a continuous (continuous ejection) method. Further, a recording method called an electrostatic method (Sweet type or Hertz type) is known as a continuous type, and a piezo piezoelectric method, a thermal inkjet method, or an electrostatic acceleration type is known as an on-demand type.

As an on-demand type ink jet system using electrostatic force, Susumu Ichinose, Yuji Ohba, IEICE Transactions vol.J66-C (No.1), p47 (1983), Tadayoshi Ohno, Mamoru Mizuguchi, The Institute of Image Electronics Engineers of Japan Magazine vol. 10, (No. 3), p157 (1981), etc., a method called an electrostatic acceleration type ink jet or a slit jet is known.Specific embodiments are, for example, JP-A-56-170, No. 56-4467, No. 5
No. 7,151,374. This involves supplying ink to a slit-shaped ink chamber in which a large number of electrodes are arranged on the inner surface of a slit-shaped ink holding unit from an ink tank, and selectively applying a high voltage to these electrodes to form a slit-shaped ink chamber. Ink is recorded by ejecting ink near the electrodes onto the recording paper that is in close proximity.

As another system which does not use a slit-shaped recording head, Japanese Patent Application Laid-Open No. 61-2111048 discloses a method in which ink is filled in a hole of a film-shaped ink support having a plurality of minute holes and a multi-needle is provided. There is disclosed means for selectively applying a voltage by an electrode to move ink in a hole to recording paper.

[0005] The principle of the flight of these inks is that a high voltage applied to the arranged electrodes causes electric charges to be injected into the ink in contact with the electrodes, and the ink near the electrodes to be charged, thereby generating an electrostatic force. It is interpreted that ink is ejected. Therefore, the ink is not normally charged, and only when a voltage is applied, the ink near the electrodes is charged by energization to obtain a discharging force. Inks used in these methods have an electric resistance of about 10 ⁶ to 10 ⁸ Ω · cm. Since water has a low electric resistance, a material in which a colorant composed of a dye is dispersed in an oily solvent with a dispersing aid such as a surfactant to adjust the electric resistance is generally used.

Further, a method of controlling the viscosity and specific resistance of the oil-based ink used (Japanese Patent Publication No. 52-13127).
), A method of controlling the relative permittivity of the dispersion medium used for the ink and the specific resistance of the ink (JP-A-53-29808), changing the type of the dispersion medium of the oil-based ink, or using a specific compound as the ink composition. Method for containing (JP-A-3-79
677, JP-A-3-64377, JP-A-4-202
386, JP-A-7-109431) and the like. However, these prior arts are not suitable for the storage stability of oil-based ink, the reproducibility of recorded images after repeated use, the bleeding resistance of the ink on the ink receiving material, the clogging resistance in the nozzle and the ink supply path, and the ink. Discharge stability and the like are not yet sufficiently satisfactory, and further improvement in performance is desired.

On the other hand, another electrostatic ink jet technology is
It is disclosed in WO93 / 11866. In this method, an insulating liquid is supplied to an ink ejection device with ink in which charged particles or particles exhibiting chargeability under an electric field are dispersed, and an ink meniscus is formed at an ejection electrode tip for ejecting the ink. It has a series of steps of forming an electric field between a counter electrode on which a recording medium is mounted and an ejection electrode to fly aggregated particles by electrophoresis and concentrating the particle concentration in the ink meniscus. I have.

[0008] Unlike the conventional method, the feature of this method that does not require an ink nozzle structure is that an ink containing dispersed particles such as a pigment can be ejected in a fine droplet size of about several μm. It is possible to change the dot size of an image by changing the droplet size by controlling the ejection signal, and the like. Accordingly, it is possible to draw an image based on the light- and water-resistant pigment and form a clear image of a continuous halftone image at high resolution and high density.

The oily ink used has an electric resistance value of 1
0 ⁹ Ω · cm while more insulating liquid and chargeable particles insoluble ones of the content containing the charge agent WO95 / 1404
No. WO 96/10058. Further, the charge amount of the charged particles or the average particle size of the particles is specified (JP-A-9-193389 and JP-A-8-29126).
No. 7) or one in which the thermophysical properties of a dried ink composition are specified (Japanese Patent Application Laid-Open No. 9-137094).

However, when ink-jet recording is performed using these oil-based inks, instability of ink ejection or insufficient concentration of pigment particles in the ink occurs, resulting in lack of formed images and blurring of images. Or an insufficient image density (particularly, a solid image portion). In addition, when the ink that has been stored for a long time is used, the ejection conditions (applied voltage, etc.) vary with the case of using fresh ink, and the ratio of concentrated and ejected ink changes significantly. In such a case, a problem such as change occurs.

On the other hand, with the recent development of office equipment and the progress of OA, in the field of light printing, lithographic printing plate precursors having an image receiving layer on a water-resistant support are subjected to plate making, that is, image formation by various methods. A plate making method for creating an offset printing plate has become widespread, and as one of the plate making methods, plate making is performed by an ink jet method. Using a conventional oil-based ink, when a printing plate on which a clear image was formed was actually printed, the number of prints at which a clear printed matter could be obtained without missing the image portion was at most several hundred sheets,
It was not enough. That is, the offset printing has a problem that the fixing strength of an image composed of ink particles is insufficient.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an oil-based ink for electrostatic ink jet which is excellent in ink ejection stability, clear image forming property and image strength. Another object of the present invention is to provide an oil-based ink for an electrostatic inkjet that can form a printing plate capable of printing a large number of printed images with clear images. Another object of the present invention is to provide an oil-based ink for electrostatic ink jet which is excellent in dispersibility and storage stability of dispersed particles, does not clog in an ink supply path, and has stable ink ejection.

[0013]

It has been found that the above-mentioned object is achieved by the following constitutions.

(1) An oil-based ink for electrostatic ink-jet ink comprising at least charged resin particles dispersed in a non-aqueous carrier liquid having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less. The resin particles are soluble in a non-aqueous solvent and contain at least one monofunctional monomer (A) which becomes insoluble by polymerization, and an amino group represented by the general formula (I), at least one monomer (a) copolymerizable with the monofunctional monomer (B), containing a -SO ₃ H group and / or -SO ₂ H group, copolymerized with the monomer (a) At least one of the possible monofunctional monomers (C), a polymer containing a repeating unit corresponding to the monomer represented by the following general formula (II), and only one terminal of the main chain of the polymer represented by the following general formula (IIc) ) Having a weight average molecular weight of 2 × 10 ⁴ or less At least one monofunctional macromonomer (MA)
And copolymer resin particles obtained by polymerizing and granulating a solution containing at least one dispersion stabilizing resin (P) containing at least a component represented by the following general formula (PI). Oil ink for electrostatic inkjet.

[0015]

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In the general formula (I), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or R ¹ and R ² are bonded to each other. A ring may be formed together with the nitrogen atom.

[0017]

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In the general formula (II): U ⁰ is —COO—, —O
_{CO -, - (CH 2)} r COO -, - (CH 2) r OCO-,
_{-O -, - SO 2 -,} - CONHCOO -, - CONH
^{CONH -, - CON (D 11} ) -, - SO 2 N (D 11)
Or represents a phenylene group (where D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents 1 to 4
Is an integer). a ¹ and a 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 having 1 to 7 carbon atoms, —COO-D ¹² , or — It represents a COO-D ¹² (where D
¹² represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). D ⁰ represents a hydrocarbon group having 8 to 22 carbon atoms or a substituent represented by the following general formula (IIa) having a total of 8 or more atoms (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom). . Formula ^{(IIa) - (A 1 -B} 1) m - (A 2 -B 2) in _n -D ²¹ formula (IIa), D ²¹ 1 to 22 hydrogen atoms or carbon atoms
Represents a hydrocarbon group. 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) -, - C
ON (D ²²⁾ - or -N represents a (D ²²⁾ CO- (wherein D ²² has the same meaning as above D ^21). m and n may be the same or different, and each represents an integer of 0 to 4. However, m and n do not become 0 at the same time.
A ¹ and A ² may be the same or different from each other, and each has a group represented by the following general formula (IIb) and a carbon number of 1 to
Represents at least one group selected from 18 hydrocarbon groups.

[0019]

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In the general formula (IIb), B ³ and B ⁴ may be the same or different from each other, and have the same meaning as B ¹ and B ² described above, and A ⁴ is a hydrocarbon group having 1 to 18 carbon atoms. Show, D
²³ has the same meaning as above D ^21. p represents an integer of 0 to 4.

[0021]

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In the general formula (IIc), U ¹ is -COO-,-
CONHCOO-, -CONHCONH-, -CONH
— Or a phenylene group. a ¹¹ and a ¹² may be the same or different and have the same meaning as a ¹ and a ² in the formula (II).

[0023]

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In the general formula (PI), A ¹ represents —COO—,
_{OCO -, - (CH 2)} a COO -, - (CH 2) a OCO
-, -O-, or

[0025]

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(Where E is a mere tangential bond, -O-, -O
CO- or -COO-). a represents an integer of 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. p ¹ and p ² may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms,-
COO-D ¹ , or —COO-D ¹ via a hydrocarbon group
(Where D ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms).

(2) In the dispersion stabilizing resin (P), a polymerizable double bond represented by the following general formula (PII) is contained in one terminal of the polymer main chain or in a substituent of a polymer copolymer component. 3. The oil-based ink for electrostatic ink jet according to claim 1, wherein the oil-based ink is formed by bonding groups.

[0028]

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In the general formula (PII), A ² represents —COO—,
_{OCO -, - (CH 2)} b COO -, - (CH 2) b OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - CON (E 1} ) -, - SO 2 N
(E ¹⁾ - or a phenylene group (E ^1, where represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, b is 1
Represents an integer of ４4). q ¹ and q ² may be the same or different from each other, and have the same meanings as p ¹ and p ^{2 in} formula (PI).

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The oil-based ink for electrostatic ink jet of the present invention will be described below. The non-aqueous carrier liquid having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. Hydrogen, halogen-substituted forms of these hydrocarbons, and silicone liquids;
Examples include silicone solvents such as silicone oil.

For example, hydrocarbon solvents include pentane, isoheptane, octane, isooctane, decane,
Isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane,
Benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isoper; trade name of Exxon), Shellsol 70,
Shellsol 71 (Shellsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits) and the like.

As the halogen-substituted hydrocarbon solvent, there is a fluorocarbon solvent. For example, perfluoroalkanes represented by C _n F _{2n + 2} such as C ₇ F ₁₆ and C ₈ F ₁₈ (“Fluorinert” manufactured by Sumitomo 3M) PF5080 "," Florinert PF5070 "(trade name), fluorinated inert liquid (" Fluorinert FC series "(trade name) manufactured by Sumitomo 3M), fluorocarbons (" Crytox GPL series manufactured by DuPont Japan Limited ") "(Trade name) etc.), CFCs (" HCF "manufactured by Daikin Industries, Ltd.)
C-141b "(trade name), _{etc.), [F (CF 2)} 4 CH 2 C
Iodinated fluorocarbons such as [H ₂ I] and [F (CF ₂ ) ₆ I] (“I-14 manufactured by Daikin Fine Chemical Laboratory)
20 "," I-1600 "(product name) and the like.

As the silicone solvent for the silicone liquid and silicone oil, dialkylpolysiloxanes (for example, hexamethyldisiloxane, tetramethyldisiloxane, octamethyltrisiloxane, hexamethyltrisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, Trifluoropropyl heptamethyltrisiloxane, diethyltetramethyldisiloxane, etc.), cyclic dialkylpolysiloxane (for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane,
Examples thereof include tetra (trifluoropropyl) tetramethylcyclotetrasiloxane and the like, methylphenyl silicone oil (for example, KF56, KF58 (trade name, manufactured by Shin-Etsu Silicon Co., Ltd.)) and the like.

In the present invention, these solvents are used alone or as a mixture. The upper limit of the electric resistance of such a nonaqueous carrier liquid is preferably about 10 ¹⁶ Ω · cm, and the lower limit of the dielectric constant is preferably about 1.80.

The resin particles (hereinafter sometimes referred to as “non-aqueous dispersed resin particles”, “dispersed resin particles” or “latex particles”), which are the most important components in the oil-based ink of the present invention, are non-aqueous solvents. In the presence of a dispersion stabilizing resin (P) having a specific structure (formula (PI)), at least one of the monofunctional monomers (A) and an amino group represented by the general formula (I) at least one monofunctional monomer containing (B), -SO ₃ H groups and / or -S
Only at one end of the main chain of a polymer containing at least one monofunctional monomer (C) containing an O ₂ H group and a repeating unit corresponding to the monomer represented by the general formula (II) It is obtained by polymerizing and granulating at least one monofunctional macromonomer (MA) having a mass average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the general formula (IIc).

Here, as the non-aqueous solvent, basically,
Any ink that can be mixed with the non-aqueous carrier liquid of the oil-based ink can be used.

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. Group hydrocarbons and their halogen-substituted products. For example, octane, isooctane, decane, isodecane, decalin, nonane,
Dodecane, isododecane, isoper E, isoper G, isoper H, isoper L, shelsol 70,
Shellsol 71, AMSCO OMS, AMSCO 460 solvent and the like are used alone or in combination.

Organic solvents which can be used in combination with these non-aqueous solvents include alcohols (for example, ethyl alcohol, propyl alcohol, butyl alcohol, and the like).
Ethylene glycol monomethyl ether, fluorinated alcohols, etc., ketones (eg, methyl ethyl ketone, acetophenone, cyclohexanone, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate) , Ethylene glycol monomethyl ether acetate, etc.), ethers (eg, dipropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg,
Chloroform, dichloroethane, methyl chloroform and the like).

It is desirable that the organic solvent used by mixing these is distilled off under heating or under reduced pressure after the polymerization granulation. However, even if the organic solvent is brought into the oil-based ink as a latex particle dispersion, the resistance of the ink is reduced. There is no problem as long as the conditions satisfy the conditions of 10 ⁹ Ω · cm or more and the dielectric constant of 3.5 or more.

In general, it is preferable to use the same solvent as the carrier liquid at the stage of preparing the resin dispersion. As described above, a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon,
Examples include aromatic hydrocarbons and halogenated hydrocarbons.

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. Specific examples include a monomer represented by the following general formula (III).

[0042]

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In the general formula (III), V ¹ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-CONHCOO-, -CONHOCO-, -SO
^{_{2 -, - CON (Q 1}} ) -, - SO 2 N (Q 1) -., Or a phenylene group (hereinafter sometimes to be referred to as a phenylene group and "-Ph-" Incidentally, phenylene group 1,2 -, 1,
Includes 3- and 1,4-phenylene groups. ). Here, Q ¹ represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
-Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxy Ethyl group, 3-methoxypropyl group, etc.).

T represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2,2-dichloroethyl, 2-bromoethyl 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, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2- Carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-carboxyamidoethyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl 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 carbon number of 1 to 3.
Alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), - COO-Q ² or -CH ^₂ -COO-Q ₂ [wherein Q ² is 1 hydrogen atom or a carbon atoms which may be substituted,
And 0 or less hydrocarbon groups (for example, representing an alkyl group, an alkenyl group, an aralkyl group, an aryl group, etc.).

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, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid Alkyl esters or amides of a carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-hydroxy group) Ethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-
Benzenesulfonylethyl group, 2-carboxyethyl group, 4-carboxybutyl group, 3-chloropropyl group,
2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-carboxyamidoethyl group, etc.);

Styrene derivatives (for example, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Vinylbenzenecarboxylic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); acrylic acid, methacrylic acid, crotonic acid,
Unsaturated carboxylic acids such as maleic acid and itaconic acid; cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile;
Methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, described in “Polymer Data Handbook -Basic Edition-” edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986)) (E.g., N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.). Two or more monomers (A) may be used in combination.

Next, the monofunctional monomer (B) which is copolymerizable with the monomer (A) used in the present invention and has an amino group represented by the general formula (I) will be described. In the monofunctional monomer (B), the polymerizable double bond and the amino group are not directly bonded.

In the formula (I), R ¹ and R ² may be the same or different and are preferably a hydrogen atom or a C ¹ -C 1.
22 optionally substituted alkyl groups (for example, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl) ,
Octadecyl group, eicosyl group, docosyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms Optionally substituted alkenyl group (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, linolenyl group, etc.),

An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methyl A benzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc., an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, A cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl) , Methoxyphenyl, ethoxyphenyl, butoxyphenyl, decylio Shifeniru group, chlorophenyl group,
Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propionamidophenyl, dodecyloylamidophenyl, etc.)
Is mentioned.

R ¹ and R ² each represent an organic residue which forms a ring together with a nitrogen atom. The organic residue further includes a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom, etc.)
Containing. Examples of the formed cyclic group include a morpholino group, a piperidino group, a pyridyl group, an imidazolyl group,
And a quinolyl group. A plurality of amino groups may be contained in the molecule of the monomer (B). The resin particles of the present invention contain an amino group-containing monomer (B) as a copolymerization component, so that the particles have an electric detection property, the charge amount of the particles increases, and environmental conditions (low temperature / low humidity to low high temperature·
The change in charging characteristics is remarkably reduced even when the humidity changes or when stored for a long period of time, and as a result, an image to be formed can have stable image quality. The monomer (B) is preferably used in an amount of 1 to 45% by mass, more preferably 5 to 30% by mass, based on the total amount of the monomer (A).

The specific examples of the monomer (B) are shown below.
The present invention is not limited to this.

[0053]

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Next, the monofunctional monomer (C) used in the present invention will be described. The monofunctional monomer (C) is-
It is a monomer containing an acidic group selected from SO ₃ H group and —SO ₂ H group and copolymerizable with the monomer (A). The monomer (C) may contain a plurality of the above acidic groups in the molecule. The monomer (C) complements the effect of the monomer (B), further improves the charge characteristics of the resin particles, and acts to always provide a stable and excellent image. The monomer (C) is preferably used in a molar ratio of monomer (B) / monomer (C) of preferably 0.1%.
It is used in the range of 2 to 2.5, more preferably 0.5 to 2.0.

Specific examples of the monomer (C) are shown below.
The present invention is not limited to these.

[0056]

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[0057]

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Next, the monofunctional macromonomer (MA) used in the present invention will be described.

The monofunctional macromonomer (MA) has the above-mentioned general formula (IIc) only at one end of the main chain of a polymer comprising a repeating unit corresponding to the monomer represented by the general formula (II).
Is a macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by

[0060] Formula (II) and a ¹ in ^{(IIc), a 2, U} 0, D 0, a 11 and a ^{1 2} hydrocarbon groups contained in each indicated number of carbon atoms (unsubstituted hydrocarbon These hydrocarbon groups are substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, an aryl group which may be substituted with an alkyl or haloalkyl, an amide group and the like. You may.

In the general formula (II), the hydrocarbon group of D ^{11 in} the substituent represented by U ⁰ preferably has 1 to 1 carbon atoms.
22 optionally substituted alkyl groups (eg, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl) ,
Octadecyl group, eicosyl group, docosyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 18 carbon atoms Optionally substituted alkenyl group (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 , A dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linolenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms ( For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propionamidophenyl group, dodecylylamidophenyl group, etc.). .

When U ⁰ represents -Ph- (phenylene group), the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.) and an alkyl group (eg, 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 (for example, 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 represents a hydrogen atom or an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 18 or less carbon atoms, more preferably 12 or less carbon atoms, and these may be substituted. manner to represent the D ¹¹ is similar to that described).

When D ⁰ represents a hydrocarbon group having 8 to 22 carbon atoms, it is specifically the same as that described for D ¹¹ above.

The case where D ⁰ represents a substituent represented by the formula (IIa) having a total number of atoms of 8 or more (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom) will be described in detail.

A ¹ and A ² are a group represented by the above formula (IIb) and a hydrocarbon group having 1 to 18 carbon atoms (an example of the hydrocarbon group includes an alkyl group, an alkenyl group, an aralkyl group and an alicyclic group). is, specific examples represents at least one group selected from among the specific examples include the same) listed in D ¹¹ (where two or more cases of these formulas (IIb) groups And / or any combination of hydrocarbon groups).

More specific examples of A ¹ and A ² include those represented by —C (D ³¹ ) (D ³² ) — [D ³¹ , D ³²
Represents a hydrogen atom, an alkyl group, a halogen atom, etc.],-
(CH = CH) -, a phenylene group (-Ph-), a cyclohexylene group [hereinafter, "-C ₆ H a cyclohexylene
₁₀ - expressed in "" - C ₆ H ₁₀ - "includes 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene xylene group], the formula (IIb ) And any combination of atomic groups such as a group represented by).

When D ⁰ represents a substituent represented by the general formula (IIa) having a total number of atoms of 8 or more, the bonding group [-U ⁰ in the formula (II)
-(A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹ ], U ⁰ to D ²¹ (that is, U ⁰ , A ¹ , B ¹ ,
The “linking main chain” composed of A ² , B ² and D ²¹ ) preferably has a total of 8 or more atoms constituting the linking main chain.

Here, the number of atoms constituting the “linking main chain” means, for example, when U ⁰ represents —COO— or —CONH—, an oxo group (＝ O group) or a hydrogen atom The carbon atoms, ether-type oxygen atoms, and nitrogen atoms that constitute the connecting main chain are included in the number of atoms. Therefore, -COO- and -CONH- have 2 atoms.
Counted as At the same time, when D ²¹ represents —C ₉ H ₁₉ , the number of hydrogen atoms is not included, and the number of carbon atoms is included. Therefore, in this case, it is counted as 9 atoms.

In the case where A ¹ and A ² have a group represented by the above formula (IIb), [-B ^3- (A ⁴ -B ⁴ ) _p
-D ²³ ] group is also included in the aforementioned “linking main chain”.

In the above monomer represented by the general formula (II), when D ⁰ represents a substituent represented by the general formula (IIa), specifically, the following monomers are exemplified. Can be mentioned. In the following formulas (1) to (19), each symbol represents the following.

R ₁ : —H, —CH ₃ , —Cl or —C
N, r _2: -H or -CH ₃ l: 2 to 10 integer, p: 2 to 6 integer, q: 2 to 4 integer, m: 1 to 12 integer, n: 4 to 18 integer ,

[0073]

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[0074]

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[0075]

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The macromonomer (MA) used in the present invention
Is, as described above, a polymerizable double bond group represented by the general formula (IIc) only at one end of a polymer main chain comprising a repeating unit corresponding to the monomer represented by the general formula (II) But,
It has a chemical structure directly bonded or bonded via an arbitrary linking group.

In the formula (IIc), U ¹ represents —COO—, —C
ONHCOO-, -CONHCONH-, -CONH-
Or represents a phenylene group. Here, the specific embodiment of the phenylene group is the same as the phenylene group for U ⁰ in formula (II).

A ¹¹ and a ¹² may be the same or different and have the same meaning as a ¹ or a ² in the formula (II). More preferably, one of a ¹¹ and a ^{12 in} the formula (IIc) is a hydrogen atom.

The group connecting the component of the formula (II) and the component of the formula (IIc) includes a carbon atom-carbon atom bond (single bond or double bond) and a carbon atom-hetero atom bond (hetero atoms such as oxygen Atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and any combination of heteroatom-heteroatom bond atomic groups.

Preferred examples of the macromonomer (MA) of the present invention are those represented by the following general formula (MA-a).

[0081]

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In the general formula (MA-a), except for Z, the formula (I-I)
It is synonymous with each symbol in I) and (IIc).

Z is a mere bond or —C (D ⁴¹ )
(D ⁴²⁾ - [D ^41, D ⁴² are each a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.),
A cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.),-(CH = C
_{H) -, - C 6 H} 10 - ( cyclohexylene group), - Ph
-(Phenylene group), -O-, -S-, -CO-, -N
^{(D 43) -, - COO} -, - SO -, - CON (D 43)
-, -SON (D ⁴³ )-, -NHCOO-, -NHCO
^{NH -, - Si (D 43} ) (D 44) - [D ^43, D ⁴⁴ represents each a hydrogen atom, the same hydrocarbon group as the D ^11],
It represents a single linking group selected from atomic groups such as the following linking groups, or a linking group composed of any combination of two or more of these atom groups.

[0084]

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In the formula (MA-a), a ¹ , a ² , a
^11, for each of a ^12, U ⁰ and U ^1, shown below Particularly preferred examples.

As U ⁰ , -COO-, -OCO-,
-O -, - CH ₂ COO- or -CH ₂ OCO- is,
As U ¹ , all of the above are a ¹ , a ² , a ¹¹ ,
The a ¹² 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 (MA-a) will be shown.
However, the present invention is not limited to these.

[0088]

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In the following, b is -H or -CH
₃ ; m1 represents an integer of 1 to 12; n1 represents an integer of 2 to 12;

[0090]

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[0091]

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[0092]

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[0093]

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The macromonomer (MA) used in the present invention may contain other repeating units as copolymerization components together with the repeating units corresponding to the monomer represented by the general formula (II).

The other copolymer component may be any compound as long as it is a monomer copolymerizable with the monomer of the general formula (II). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, and 4-pentenoic acid, and esters or amides of these unsaturated carboxylic acids, and fatty acids having 1 to 22 carbon atoms Examples include vinyl esters or allyl esters, vinyl ethers, styrene and styrene derivatives, and heterocyclic compounds containing a polymerizable double bond group.

Specifically, for example, the aforementioned monomer (A)
And the like, but are not limited thereto.

In the total of the repeating units of the macromonomer (MA), the repeating unit component corresponding to the monomer represented by the general formula (II) is preferably contained in an amount of at least 60% by mass, more preferably 80 to 100% by mass.

The macromonomer (MA) of the present invention preferably has a mass average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ ,
3 × 10 ^{3 to} 1.5 × 10 ⁴ is more preferable.

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

More specifically, P.S. Dreyfuss &
R. P. Quirk, Encycl. Polym. Sc
i. Eng. , 7 , 551 (1987); Re
mpp & E. Franta, Adv. Polym.
Sci. 58 , 1 (1984); Persec,
Appl. Polym. Sci. , 285 , 95 (19
84); Asami, M .; Takaki, Makr
omol. Chem. Suppl. , 12 , 163 (1
985), p. Rempp et al, Makrom
ol. Chem. Suppl. , 8 , 3 (1984),
Yusuke Kawakami "Chemical Industry" 38 , 56 (1987), Yuya Yamashita "Polymer" 31 , 988 (1982), Shiro Kobayashi "Polymer" 30 , 625 (1981), Toshinobu Higashimura "Journal of the Japan Adhesion Association" 18 , 536 (1982), Koichi Ito "Polymer Processing" 35 , 262 (1986), Higashi Kishiro, Tsuda Takashi "Functional Materials" 1987 , No. It can be synthesized according to the methods described in reviews such as 10, 5 and literatures and patents cited therein.

Examples of the polymerization initiator containing a reactive group in the molecule include, for example, 4,4'-azobis (4-cyanovaleric acid) and 4,4'-azobis (4-cyanovaleric 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-amidinopropane), 2,2'-
Azobis [2-methyl-N- (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-tetrahydropyrimidin-2-yl) propane],
2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,
2'-azobis [N- (2-hydroxyethyl) -2-
Azobis compounds such as methyl-propionamidine] and 2,2'-azobis [N- (4-aminophenyl) -2-methylpropionamidine].

Examples of the chain transfer agent having a specific reactive group in the molecule include, for example, a mercapto compound containing the reactive group or a substituent capable of being induced to the reactive group (for example, thioglycolic acid, Thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid,
3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, −
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, etc.), or the reactive group or an iodized alkyl compound containing a substituent capable of being induced to the reactive group (for example,
Iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

The amount of each of these chain transfer agents or polymerization initiators is 0.5 to 100 parts by weight of the total monomers.
To 20 parts by mass, preferably 1 to 10 parts by mass. The use of the macromonomer (MA) improves the dispersion stability and redispersibility of the resin particles. That is, when the dispersed resin particles are formed by the polymerization reaction, the polymerization component of the macromonomer (MA) is oriented to the particle surface portion due to its high affinity with the dispersion medium, thereby dispersing the surface of the particle itself. It is presumed that the affinity for the medium increases and the aggregation and precipitation of the particles are suppressed.

The macromonomer (MA) is composed of 10 total monomers.
0.5 to 20 parts by mass, preferably 1 to 15 parts by mass in 0 parts by mass
Use parts by mass. The monomer (A), the monomer (B), the monomer (C) and the macromonomer (MA) used in the present invention are copolymerized by a polymerization reaction to form resin particles insoluble in a non-aqueous solvent. .

Next, the dispersion stabilizing resin (P) used in the present invention will be described.

In the present invention, the dispersion stabilizing resin (P) used to convert a non-aqueous solvent-insoluble polymer produced by polymerizing a monomer in a non-aqueous solvent into a stable resin dispersion is
It is a polymer soluble in a non-aqueous solvent containing at least one kind of the repeating unit represented by the general formula (PI). The component represented by the general formula (PI) is a component that becomes soluble in the dispersion medium used in the oil-based ink.

In the formula (PI), A ¹ is preferably -CO
O -, - OCO -, - CH 2 COO -, - CH 2 OCO-
Or -O-, more preferably -COO-, -OC
O -, - represents a CH ₂ COO-.

L preferably represents an alkyl or alkenyl group having 8 to 32 carbon atoms which may be substituted. Examples of the substituent include a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom, ^{etc.), - O-D 2,} -COO-D 2,
—OCO—D ² (where D ² represents an alkyl group having 6 to 22 carbon atoms, for example, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.) and the like. . More preferably, L represents an alkyl or alkenyl group having 10 to 22 carbon atoms. For example, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosyl, eicosyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,
And a docosenyl group.

P ¹ and p ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, and a C 1 -C 1 atom. 3 alkyl groups, —COO—D ³ or —CH ₂ COO—D ³ (where D ³ represents an aliphatic group having 1 to 22 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group , Hexyl group, octyl group, decyl group,
Dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosyl group, pentenyl group,
Hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc., and these aliphatic groups may have the same substituents as those represented by L above. ). More preferably, p ¹ and p ² are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), —COO—D ⁴ or —CH ₂
COO-D ⁴ (where D ⁴ represents an alkyl group or an alkenyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group Pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, and the like, and these alkyl groups and alkenyl groups may have the same substituents as those represented by L).

The dispersion stabilizing resin (P) of the present invention is preferably composed of a monomer corresponding to the repeating unit represented by the above general formula (PI), and another monomer copolymerizable with the monomer. It is a copolymer containing a copolymer component obtained by copolymerizing a copolymer.

Other monomers that can be copolymerized may be any as long as they contain a polymerizable double bond group. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; Ester derivatives or amide derivatives of unsaturated carboxylic acids having a number of 6 or less; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. . More specifically, the same compounds as those of the monomer (A) to be insolubilized as described above can be used.

In the polymer component of the dispersion stabilizing resin (P), the component of the repeating unit represented by the general formula (PI) is at least 50% by mass, preferably at least 60% by mass, based on all the components of the polymer. , More preferably 70% by mass or more. Further, in the dispersion stabilizing resin (P), another monomer (for example, insoluble in the dispersion medium) which is copolymerizable with the copolymerization component represented by the general formula (PI) which is soluble in the dispersion medium used for the oil-based ink. The term “polymerization component corresponding to the monomer (A)” may be any of random copolymerization and block copolymerization. Preferably, it is a block copolymer.

Further, as a preferred embodiment of the dispersion stabilizing resin (P) of the present invention, a polymerizable double-sided compound represented by the above general formula (PII) may be contained in one terminal of the polymer main chain or in a substituent of the polymer component. The polymerizable double bond group is formed by bonding a bonding group (sometimes referred to as a dispersion stabilizing resin (PG)), and the polymerizable double bonding group is copolymerized with the monomer (A) constituting the dispersion resin particles. May be a functional group.

In the formula (PII), A ² represents —COO—, —OC
_{O -, - (CH 2)} b COO -, - (CH 2) b OCO -, -
_{O -, - SO 2 -,} - CONHCOO -, - CONHC
Represents ONH—, —CONE ¹ —, —SO ₂ NE ¹ —, or a phenylene group (here, E 1 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and b represents an integer of 1 to 4). Further, a specific embodiment of the phenylene group is represented by the formula (P
The same as the phenylene group for A ¹ in I). .

Q ¹ and q ² may be the same or different and have the same meaning as p ¹ or p ^{2 in} formula (PI). Preferably, one of q ¹ and q ² is a hydrogen atom.

In A ² , -CONE ^1- , -S
E ¹ in the O ₂ NE ¹ — linking group is preferably a hydrogen atom or an alkyl such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group. Represents a group.

Examples of the resin (PG) bonded to one end of the polymer main chain include, for example, the following general formula (Pa).

[0118]

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In the general formula (Pa), except for G, the formula (PI)
And the same as each symbol in (PII). G represents a bond directly linked to one end of the polymer main chain, or a bonding group via an arbitrary linking group.

Examples of the bonding group include a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom, It is composed of any combination of atomic groups of atom-heteroatom bonds. For example,

[0121]

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Z ¹ and z ² are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ). z ³ and z ⁴ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a benzyl group, a phenethyl group, a phenyl group, tolyl) or -Oz ⁵ (z ⁵ represents the same meaning as the hydrocarbon group) in the z ^3), and the like.

With respect to the polymerizable double bond group represented by the general formula (PII) bonded to one terminal of the polymer main chain as described above,
The details are shown below. However, in the following specific examples,
A represents -H, a -CH ₃ or -CH ₂ COOCH _3,
B represents -H or -CH _3. Further, n represents an integer of 2 to 10, m represents 2 or 3, t represents 1, 2 or 3, p represents an integer of 1 to 4, and q represents 1 or 2.

[0124]

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[0125]

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[0126]

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[0127]

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The dispersion stabilizing resin (PG) of the present invention having a polymerizable double bond group bonded to one end of the polymer main chain can be prepared by known radical polymerization (for example, iniferter method), anionic polymerization or cationic polymerization. The terminal of the living polymer obtained by polymerization is reacted with a reagent containing various double bond groups, or a specific reactive group (for example, -OH, -COOH, -SO
_{3 H, -NH 2, -SH,} -PO 3 H 2, -NCO, -NC
S,

[0129]

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[0130] -COCl, after reacting the reagent containing -SO ₂ Cl, etc.), the method according to the method (ion polymerization method for introducing a polymerizable double bond group by a polymer reaction), or the specific in the molecule After radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group of
The polymer can be easily produced by a synthesis method such as a method of introducing a polymerizable double bond group by conducting a polymer reaction using a specific reactive group bonded only to one end of the polymer main chain.

More specifically, Takayuki Otsu, Polymer, 33 (No.
3), 222 (1984), P. Dreyfuss & RPQuirk, Encycl. P
olym. Sci. Eng., 7, 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30, 232 (1985), Akira Ueda, Susumu Nagai, "Chemistry and Industry," 60, 57 (1986), PFRempp & E.Frant
a, Advances in Polymer Science, 58, 1 (1984), Koichi Ito `` Polymer Processing '', 35, 262 (1986), V. Percec, Ap
A polymerizable double bond group can be introduced according to a method described in a review such as plied Polymer Science, 285, 97 (1984) and the references cited therein.

More specifically, (i) the general formula (P
A mixture of at least one monomer corresponding to the repeating unit represented by I) and a chain transfer agent having the above-mentioned specific reactive group in the molecule is polymerized with a polymerization initiator (for example, azobis compound, peroxide, etc.). (Ii) a method of polymerizing using a polymerization initiator containing the above-mentioned specific reactive group in the molecule without using the above-mentioned chain transfer agent, or (iii) a chain transfer agent and polymerization initiation A polymer in which a specific reactive group is bonded only to one end of the polymer main chain by a method using a compound containing the specific reactive group in the molecule for any of the agents, and the like. A method in which a polymerizable double bond is introduced by a polymer reaction using a specific reactive group is exemplified.

As the chain transfer agent to be used, for example, a mercapto compound containing a specific reactive group or a substituent capable of being induced to a specific reactive group {eg, thioglycolic acid,
Thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine,
2-mercaptonicotinic acid, 3- [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, 1-mercapto-2-propanol, 3
-Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol or the like, or containing a specific reactive group or a substituent capable of being induced to a specific reactive group (E.g., iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Examples of the polymerization initiator containing a specific reactive group or a substituent capable of deriving to a specific reactive group include:
For example, azobis compounds {eg, 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric chloride), 2,2′-azobis (2-cyanopropanol), , 2'-Azobis (2-cyanopentanol), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2-
Yl) propane], 2,2'-azobis {2-methyl-
N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide {, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2 , 2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis (2-amidinopropane)}, a thiocarbamate compound {eg, benzyl N
-Methyl-N-hydroxyethyldithiocarbamate,
2-carboxyethyl N, N-diethyldithiocarbamate, 3-hydroxypropyl N, N-dimethyldithiocarbamate} and the like.

The amount of use of these chain transfer agents or polymerization initiators is 0.05 to 100 parts by mass of all monomers.
It is 10 parts by mass, preferably 0.1 to 5 parts by mass.

Further, a specific embodiment of the resin (PG) containing a polymerizable double bond group in the substituent of the polymerization component in the polymer includes, for example, the following general formula (Pb).

[0137]

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In the formula (Pb), p ¹ , p ² , A ¹ , L, q ¹ ,
q ² are as defined above. Two or more types of the x component and the y component may be contained in the resin (P). t ¹ and t ² are p
¹ and p ² have the same meaning. A ³ and A ⁴ are each represented by the formula (PI
The same meaning as that of A ² in I). G ^O is composed of the bonding group A ³ and the bonding group A
And a group connecting ⁴ with at least one carbon atom, oxygen atom, sulfur atom, silicon atom or nitrogen atom.

As the bonding group, a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and the like), a hetero atom It is composed of any combination of atom groups, heteroatom bonds, and heterocyclic groups. For example, as the above atomic group,

[0140]

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[R ^{1 to} r ⁴ each represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
And a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.). r ^{5 to} r ⁷ each represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). r ⁸ ~r ⁹ each represents a hydrogen atom, a hydrocarbon group (e.g., methyl group having 1 to 8 carbon atoms, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a benzyl group, a phenethyl group, a phenyl group, Tol group, etc.) or -Or ¹⁰ (r ¹⁰ has the same meaning as the hydrocarbon group for r ⁸ ).

Examples of the heterocyclic group include heterocycles containing a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom (for example, a thiophene ring, a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring and a piperidine ring). ,
Pyrazine ring, pyrrole ring, piperazine ring, etc.).

In the y component in the general formula (Pb), the connecting main chain composed of a bonding group: [—A ⁴ —G ^O —A ³ —] is
Those having a total number of atoms of 8 or more are preferred.
Here, the number of atoms in the connecting main chain means that, for example, A ⁴ is -CO
When O— and —CONH— are represented, the oxo group (＝ O group) and the hydrogen atom are not included in the number of atoms, and the carbon atom, the ether-type oxygen atom, and the nitrogen atom constituting the connecting main chain are included in the number of atoms. It is. Therefore, -COO- and -CONH
-Is counted as 2 atoms.

Hereinafter, specific examples of the repeating unit (y component) containing a polymerizable bonding group will be shown, but the present invention is not limited thereto. In the following formula, each symbol represents the following contents.

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

The dispersion stabilizing resin (PG) containing a polymerizable double bond group in the substituent of the polymerization component can be easily synthesized by a conventionally known synthesis method. Namely, in the resin, as a method for introducing a polymerizable component (y component) containing a polymerizable double bond group, pre-specific reactive group (e.g. _{-OH, -COOH, -SO 3 H,} -NH 2 , -S
_{H, -PO 3 H 2, -NCO} , -NCS, -COCl, -
After polymerizing a monomer containing SO ₂ Cl, an epoxy group, etc.) with a monomer corresponding to the general formula (Pb) in the x component, a reactive reagent containing a polymerizable double bond group is reacted. Then, a polymerizable double bond group is introduced by a polymer reaction.

More specifically, the polymerizable double bond is prepared according to the method described in the above-mentioned reviews of the resin (PG) having a polymerizable double bond group at one end of the polymer main chain and the literature cited therein. Groups can be introduced.

As another method, a bifunctional monomer having a different polymerization reactivity in a radical polymerization reaction is used.
A method described in JP-A-60-185962, in which a polymerization reaction is carried out with a monomer corresponding to the x component to synthesize a copolymer represented by the general formula (Pb) without causing a gelling reaction, is mentioned.

In the resin represented by the general formula (Pb),
The proportion of the x component / y component is from 90/10 to 99/1 by mass, preferably from 92/8 to 98/2 by mass. Within this range, there is no danger of gelling the reaction mixture or increasing the particle size of the resulting resin particles during the polymerization granulation reaction.

The dispersion stabilizing resin (PG) used in the present invention may contain other repeating units as copolymer components together with the repeating units of the general formulas (Pa) and (Pb). Other copolymer components include those represented by the general formula (P
Any compound may be used as long as it is composed of a monomer copolymerizable with a monomer corresponding to each of the repeating units a) and (Pb). However, in order to obtain good dispersion stability of the dispersed resin particles, it is preferable to use the dispersed resin particles in an amount not exceeding 20 parts by mass in 100 parts by mass of all polymer components.

The weight average molecular weight (Mw) of the dispersion stabilizing resin (P) of the present invention is preferably 2 × 10 ⁴ to 1 × 10 ⁶ , more preferably 3 × 10 ⁴ to 2 × 10 ⁵ .

As described above, the soluble component (general formula (PI)
Is preferred to use a dispersion stabilizing resin (P) composed of a block copolymer of a component (A) and an insoluble component. In this case, the block portion of the insoluble component of the dispersion stabilizing resin (P) is sufficiently adsorbed on the insoluble resin particles. Alternatively, it is preferable to use a dispersion stabilizing resin (PG) containing a polymerizable double bond group. In this case, the resin (PG) chemically bonds to the insoluble resin particles. Thereby, the dispersion stabilizing resin (P) sufficiently adsorbed or chemically bonded to the dispersed resin particles.
It is considered that the so-called steric repulsion effect is brought about by improving the affinity of the soluble component for the dispersion medium, and the dispersibility is further improved.

To produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin (P) as described above,
Monomer (A), monomer (B), monomer (C) and macromonomer (MA) in a non-aqueous solvent with benzoyl peroxide;
Heat polymerization may be performed in the presence of a polymerization initiator such as azobisisobutyronitrile and butyllithium. In particular,
A method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin (P), a monomer (A), a monomer (B), a monomer (C) and a macromonomer (MA). A method in which the monomer (A), the monomer (B), the monomer (C) and the macromonomer (MA) are dropped together with a polymerization initiator into a solution in which the resin (P) is dissolved, or In the solution in which the stabilizing resin (P) is dissolved, a mixture of the monomer (A) and the monomer (B) and a half of the monomer (A), the monomer (C) and the macromonomer ( There is a method in which a mixture of MA) and the polymerization initiator are respectively simultaneously dropped, and any of these methods can be used for production.

The total amount of the monomer (A), the monomer (B), the monomer (C) and the macromonomer (MA) is preferably from 10 to 100 parts by mass based on 100 parts by mass of the nonaqueous solvent. And more preferably from 10 to 80 parts by mass.
The dispersion stabilizing resin (P) is composed of all the monomers 10 used above.
0 parts by mass, preferably 3 to 25 parts by mass,
More preferably, it is 5 to 20 parts by mass. The amount of the polymerization initiator is suitably from 0.1 to 10% by mass of all the monomers. Also,
The polymerization temperature is preferably about 40 to 180 ° C, more preferably 50 to 120 ° C. The reaction time is preferably 3 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination with the non-aqueous solvent used in the reaction, or unreacted products of monomers to be polymerized and granulated may be used. If it remains, it is preferable to remove it by heating it to a temperature higher than the boiling point of the polar solvent or the monomer or distilling it off under reduced pressure.

The non-aqueous dispersed resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution. Its average particle size is preferably 0.15
To 5 μm, more preferably 0.2 to 1.5 μm.
The particle size can be determined by CAPA-500 (trade name, manufactured by Horiba, Ltd.).

The mass average molecular weight (Mw) of the resin constituting the above particles (polystyrene conversion value by GPC method)
Is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 8 × 10 ^{3 to} 5 × 10 ⁵ . Further, its thermophysical properties include a glass transition point of 0 ° C. to 80 ° C. or a softening point of 35 ° C.
C. to 120 C. are preferred, and more preferably a glass transition point of 10 C. to 70 C. or a softening point of 38 C. to 90 C.

The oil-based ink of the present invention is excellent in dispersion stability, re-dispersibility and storage stability of dispersed resin particles, has good fast fixing property after image formation, and maintains sufficient strength during printing. Shows high printing durability. In other words, it shows extremely stable dispersibility, and particularly in a recording apparatus, has good dispersibility even when used repeatedly for a long time, and is easy to redisperse. I can't.

Furthermore, because of good fixability, a solid film is easily formed on the surface of the lithographic printing plate precursor by fixing the ink image by rapid processing by heating or the like after the formation of the ink image.
Thereby, even in offset printing, printing of a large number of sheets (high printing durability) becomes possible. The oil-based ink of the present invention having the above effects is made possible by the non-aqueous latex provided by the present invention.

The dispersed resin particles in the oil-based ink used in the present invention exhibit positive charge. In order to adjust the charging characteristics of the oil-based ink, a technique of a wet developer for electrophotography can be appropriately used. Specifically, “Recent development and practical application of electrophotographic development systems and toner materials”, pp. 139-148, “Basic and Application of Electrophotographic Technology”, ed.
Page 05 (Corona Publishing, 1988), Yuji Harasaki "Electrophotography"
16 (No. 2), p. 44 (1977), etc.
This is done by using D) and other additives.

Examples of the charge controlling agent include metal soaps, organic phosphoric acids or salts thereof, organic sulfonic acids or salts thereof,
Amphoteric surfactant compounds are useful. For example, as metal soaps, fatty acids having 6 to 24 carbon atoms (for example, 2-ethylhexanoic acid, 2-ethylcaproic acid, lauric acid,
Metal salts such as palmitic acid, elaidic acid, linoleic acid, ricinoleic acid, oleic acid, stearic acid, enanthic acid, naphthenic acid, ethylenediaminetetraacetic acid), resin acids, dialkyl succinic acids, alkyl phthalic acids, and alkyl salicylic acids Na, K, Li, as metals of
B, Al, Ti, Ca, Pb, Mn, Co, Zn, M
g, Ce, Ag, Cd, Zr, Cu, Fe, Ba, etc.)
(For example, US Pat. Nos. 3,411,936 and 3,90
0,412, JP-B-49-27707, JP-A-Sho 51
-37651, 52-38937, and 52-10
7837 and 53-123138).

The organic phosphoric acid or salts thereof have 3 carbon atoms.
Mono-, di- or trialkylphosphoric acid or dialkyldithiophosphoric acid or the like comprising alkyl groups (for example, British Patent Nos. 1,411,739 and 1,276,3)
63, etc.). Examples of the organic sulfonic acids and salts thereof include long-chain aliphatic sulfonic acids, long-chain alkylbenzenesulfonic acids, dialkylsulfosuccinic acids, and metal salts thereof (for example, Japanese Patent Publication No. 47-128128).
And JP-A-53-123138 and JP-A-51-47437.
No. 50-79640, and No. 53-30340).

As amphoteric surfactant compounds, phospholipids such as lecithin and kephalin (for example, JP-B-51-47046)
Metal complexes of β-diketones such as β-alanines containing an alkyl group having 8 or more carbon atoms (JP-A-50-17642 and JP-A-49-17774).
707) and copolymers containing a maleic acid half-amide component (for example, JP-B-6-19596 and JP-B6-1959).
No. 5, No. 6-23865, etc.).

These charge control agents (CD) can be used alone or in combination of two or more. The charge control agent is preferably used in an amount of 0.001 to 1.0 part by mass with respect to 1000 parts by mass of the dispersion medium as the carrier liquid.

The oil-based ink of the present invention contains dispersed resin particles composed of at least a monomer (A), a monomer (B), a monomer (C) and a macromonomer (MA), and preferably a charge control. Agent (CD).

The oil-based ink of the present invention was prepared using the above-mentioned WO 93/1.
When used in the method of forming an image by an electrostatic ink jet recording method involving concentration or coagulation disclosed in Japanese Patent No. 1866, loss of ink dots and deformation of the dot shape to be printed even at high printing speeds can be achieved. A high-definition image is formed without occurrence, and the thickness of the printed dot image is sufficiently maintained at 1 μm or more. This means that the positively charged resin particles in the oil-based ink are rapidly electrophoresed in the ink meniscus formed at the tip of the ejection electrode under an electrostatic field, and the particles are concentrated, resulting in an image signal. It is considered that the ejection is performed completely in response to the pulse voltage application.

Furthermore, the oil-based ink of the present invention may be used after being stored for a long time,
%), Shows the same performance as a fresh product immediately after ink production even when ink-jet recording is performed after storage. This is considered to be due to the fact that the charging characteristics of the oil-based ink of the present invention, in particular, the charging characteristics of the positively charged particles are stably maintained, and that the aggregation and precipitation of the particles are prevented by maintaining the above-mentioned dispersion stability.

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 oil-based ink. That is, if the electric resistance of the ink from which the dispersed particles have been removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, it is desirable to control the amount of each additive within this limit. .

The oil-based ink of the present invention preferably contains a coloring material as a coloring component together with the above-mentioned dispersed resin particles for the purpose of plate inspection of a plate after plate making.

As the coloring material, any pigments and dyes conventionally used in oil-based ink compositions or liquid developers for electrophotography can be used.

As the pigments, those generally used in the technical field of printing can be used irrespective of inorganic pigments and organic pigments. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, pyridian, cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment , Quinacridone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, and other conventionally known pigments are particularly limited. It can be used without.

As the dye, azo dyes, metal complex dyes,
Naphthol dye, anthraquinone dye, indigo dye,
Oil-soluble dyes such as carbonium dyes, quinone imine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred.

These pigments and dyes may be used alone or in an appropriate combination, but may be contained in the range of 0.05 to 20% by mass based on the whole ink. desirable.

These coloring materials may be dispersed in the non-aqueous solvent as the dispersed particles themselves in addition to the dispersed resin particles, or may be contained in the dispersed resin particles. One of the methods for adding the dye is to dye the dispersed resin material with an appropriate dye as described in JP-A-57-48738. Another method is disclosed in JP-A-53-5 / 78.
As disclosed in JP-A No. 4029 and the like, there is a method of chemically bonding a dispersing resin and a dye.
As described in, for example, No. 22555, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Next, an image forming method by the electrostatic ink jet method using the oil-based ink of the present invention will be described. Here, a method of forming an image (plate making) using a printing original plate as an ink receiving material to form a printing plate will be described as an example.

Printing masters are broadly classified into those having a lithographically printable hydrophilic surface and those having a hydrophobic surface, and any of them can be used. The former printing original plate includes those in which the support itself has a hydrophilic surface and those in which a layer having a hydrophilic surface is provided on the support.

The water-resistant support having a lithographically printable hydrophilic surface may be any as long as it provides a hydrophilic surface suitable for lithographic printing, and a support conventionally used for offset printing plates may be used as it is. it can. Specifically, bimetal plates such as aluminum plates, zinc plates, copper-aluminum plates, copper-stainless steel plates, chromium-copper plates, chromium-copper-aluminum plates, chromium-lead-iron plates, chromium-copper-stainless steel plates, etc. A substrate having a hydrophilic surface such as a trimetal plate is used. Its thickness is 0.1-3 mm, especially 0.1
１1 mm is preferred.

In the case of a support having an aluminum surface, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation treatment is performed. Is preferred. Further, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate is disclosed in JP-B-47-51.
As described in No. 25, a material obtained by subjecting an aluminum plate to anodizing treatment and then immersing the plate in an aqueous solution of an alkali metal silicate is also preferably used.

The anodizing treatment may be carried out, for example, by using an inorganic acid such as phosphoric acid, chromic acid, sulfur, boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous or non-aqueous solution of a salt thereof, alone or in combination of two or more. It is carried out by flowing a current in the combined electrolyte using the aluminum plate as an anode. Also, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is effective. The treatment with polyvinyl sulfonic acid described in West German Patent Publication No. 1,621,478 is also suitable.

According to the combination of the ink and the recording method of the present invention, even when an image is formed on a metal surface, the ink is printed in a state where the particles in the ink are sufficiently concentrated, so that the ink bleeds on the printed surface. No image bleeding occurs.

These surface treatments are performed not only to make the surface of the support hydrophilic, but also to improve the adhesion to the ink image provided thereon. A surface layer may be provided on the surface of the support in order to adjust the adhesion between the support and the ink image.

When a plastic sheet or paper is used as the support, a material provided with a hydrophilic surface layer is provided since the portion other than the ink image portion must be hydrophilic. Specifically, a known direct-drawing lithographic printing original plate or a plate material having a layer similar to the image receiving layer of the original plate can be used.

For example, as the image receiving layer, there is an image receiving layer mainly composed of a water-soluble binder, an inorganic pigment and a waterproofing agent. As the binder, PVA, modified PVA such as carboxy PVA, starch and its derivatives, CM
Water-soluble resins such as C, hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, and styrene-maleic acid copolymer are used.

Examples of the water-proofing agent include an initial condensate of aminoblast such as glyoxal, melamine formaldehyde resin, and urea formaldehyde resin; a modified polyamide resin such as a methylolated polyamide resin; a polyamide / polyamine / epichlorohydrin adduct; a polyamide epichlorohydrin resin; Polyamide polyimide resin and the like can be mentioned. Examples of the inorganic pigment include kaolin, clay, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, and alumina, and silica is preferred.

In addition, a crosslinking agent such as ammonium chloride or a silane coupling agent can be used in the image receiving layer.

On the other hand, in a printing master having an image receiving layer composed of a hydrophobic surface, after forming an image, the non-image portion is desensitized by a desensitizing treatment (that is, the non-image portion is formed on the hydrophilic surface of the printing ink repellent). Conversion) to make a printing plate.

These printing masters include a printing master having an image-receiving layer containing at least zinc oxide and a binder resin, and a hydrophobic binder formed by a desensitizing treatment (treatment liquid, light irradiation, heat treatment, etc.). A printing plate having an image receiving layer containing at least a binder resin which chemically converts the binder resin into a hydrophilic binder resin (for example, JP-A-1-226394,
Japanese Patent Publication No. 7-94191).

A lithographic printing original plate having an image receiving layer containing at least zinc oxide and a binder resin will be described.

The zinc oxide to be used is described in, for example, “Pigment Handbook”, p. 319, edited by Japan Pigment Technical Association, Seibundo Co., Ltd.
(1968), zinc oxide, zinc white,
Any of those commercially available as wet zinc white or activated zinc white may be used. That is, zinc oxide includes, as a dry method, a French method (indirect method), an American method (direct method) and a wet method, depending on the starting materials and the production method. For example, Shodo Chemical Co., Ltd., Sakai Chemical ( Co., Ltd.), Hakusui Chemical Co., Ltd., Honjo Chemical Co., Ltd., Toho Zinc Co., Ltd.,
Examples include those commercially available from various companies such as Mitsui Kinzoku Kogyo.

The content of zinc oxide in the image receiving layer was 7
It is preferably from 5 to 90% by mass, more preferably from 78 to 88% by mass. If the amount of zinc oxide is too small, hydrophilization of the surface of the image receiving layer by the desensitizing treatment becomes insufficient. On the other hand, if the amount is too large, the necessary strength of the image receiving layer cannot be secured, which is not preferable.

As described above, the binder resin provided to the image receiving layer is a hydrophobic resin constituting the image receiving layer together with zinc oxide, and has a molecular weight of a weight average molecular weight Mw.
Preferably from 10 ³ to 10 ⁶ , more preferably from 5 × 10 ³ to
It is 5 × 10 ⁵ . Further, the glass transition point of this resin is preferably 0 ° C to 120 ° C, more preferably 10 ° C to 90 ° C.
° C.

Specifically, styrene copolymers, methacrylate copolymers, acrylate copolymers, vinyl acetate copolymers, polyvinyl butyral, alkyd resins, epoxy resins, epoxy ester resins, polyester resins, polyurethane resins and the like can be mentioned. Can be These resins may be used alone or in combination of two or more.

In the image receiving layer, together with the above components,
Other components may be contained. Other components that may be included are other inorganic pigments of zinc oxide, such as kaolin, clay, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate, oxides Examples include titanium, silica, and alumina. When these other inorganic pigments are used in combination, it is desirable to use them in a range not exceeding 20 parts by mass with respect to 100 parts by mass of zinc oxide.

Further, in order to improve the desensitization of the image receiving layer, JP-A-4-201387 and JP-A-4-223196 are known.
No. 4-319494, No. 5-58071, No. 4
Resin particles such as acrylic acid resin particles containing a specific functional group described in JP-A-353495 and JP-A-5-119545 may also be contained. These resin particles are usually spherical, and preferably have an average particle size of 0.1 to 2 μm. The content of the resin particles is preferably 20% by mass or less of the components of the image receiving layer.

By using these other inorganic pigments or resin particles, desensitization (hydrophilicity) of the non-image area due to the desensitization treatment is sufficiently performed, the background stain on the printed matter is suppressed, and the image area is reduced. It is sufficiently adhered to the image receiving layer, and sufficient printing durability can be obtained without causing image defects even when the number of printed sheets increases.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength.

The binder resin is preferably cured with light and / or heat after the image receiving layer composition is applied. In order to carry out thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of preparing the conventional image receiving layer. For example, it is preferable to set the drying conditions to a high temperature and / or a long time, or to further heat after drying the coating solvent.
For example, the treatment is performed at 60 ° C to 150 ° C for 5 to 120 minutes. When a reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method of curing by light irradiation, a specific functional group in the resin may be irradiated with light by a chemically active light beam. The chemical actinic ray may be any of visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, γ ray, α ray and the like, but is preferably ultraviolet ray, more preferably a ray having a wavelength of 310 nm to 500 nm. . Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp, or the like is used. The light irradiation treatment can be sufficiently carried out by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

The thickness of the image receiving layer is from 3 to 3 in terms of the coating amount of the image receiving layer composition per m ^{2 of} the printing plate precursor (after drying).
It is preferred to be about 30 g. The image receiving layer is usually 3 to 50 vol%, preferably 10 to 40 vol%.
It is preferable to have a porosity of the order.

The image receiving layer is provided on a water-resistant support. As the water-resistant support, paper, a plastic film or a paper or a plastic film laminated with a metal foil, which has been subjected to a water-resistant treatment can be used.

The support preferably has a highly smooth surface. That is, the smoothness of the surface on the side adjacent to the image receiving layer is adjusted to a Beck smoothness of 300 (sec / 10 ml) or more, preferably 900 to 3000 (sec / 10 ml), and more preferably. 1000-300
It is preferably 0 (second / 10 ml).

By regulating the smoothness of the surface of the support adjacent to the image receiving layer to a Beck smoothness of 300 (sec / 10 ml) or more, image reproducibility and printing durability can be further improved. . Such an improvement effect is obtained even if the smoothness of the image receiving layer surface itself is the same, and the adhesion between the image portion and the image receiving layer is improved by increasing the smoothness of the support surface. it is conceivable that.

Here, the Beck smoothness can be measured by a Beck smoothness tester. A Beck smoothness tester presses a test piece at a constant pressure (1 kg / cm ² ) on a highly smooth finished circular glass plate with a hole in the center, and a fixed amount (10 ml) under reduced pressure. It measures the time required for air to pass between the glass surface and the specimen.

The highly smooth surface of such a water-resistant support means a surface on which an image receiving layer is directly applied. For example, when an under layer or an overcoat layer described later is provided on the support, , The surface of the underlayer or overcoat layer. As a result, the image receiving layer whose surface condition has been adjusted as described above is sufficiently retained without receiving the unevenness of the surface of the support, and the image quality can be further improved.

As a method for setting the smoothness within the range, various conventionally known methods can be used. Specifically, by a method of melting and bonding the substrate surface with a resin, a method such as a calendar strengthening method using a highly smooth heat roller,
A method of adjusting the Beck smoothness of the surface of the support can be used.

As a method for melting and bonding the above-mentioned resins, it is preferable that the resin is coated by an extrusion lamination method. By coating by this extrusion lamination method, a support having a desired smoothness can be produced. The extrusion laminating method is a method in which a resin is melted, formed into a film, immediately pressure-bonded to base paper, and then cooled and laminated, and various apparatuses are known. The thickness of the resin layer laminated in this manner is 10 μm from the viewpoint of production stability.
That is all. Preferably it is 10 μm to 30 μm.

As described above, an under layer is provided between the support and the image receiving layer for the purpose of improving the water resistance and interlayer adhesion, and a curl is provided on the surface of the support opposite to the image receiving layer to prevent curling. A back coat layer (back layer) can be provided, and the back coat layer has a smoothness of 150 to
It is preferably in the range of 700 (sec / 10 ml).
Accordingly, when the printing plate is supplied to the offset printing press, the printing plate is accurately set on the printing press without causing displacement or slippage.

When the smoothness of the underlayer and the backcoat layer of such a support are individually adjusted, for example, calendering is performed once after the underlayer is formed, and calendering is performed again after the backcoat layer is formed. In addition, the process of calendar processing is performed multiple times,
It is desirable to control the smoothness by a combination of adjusting the composition of the under layer and the back coat layer, for example, the proportion and particle size of the pigment, and adjusting the calendering conditions as described below.

Examples of the substrate to be used for the printing original plate include substrates such as wood pulp paper, synthetic pulp paper, mixed paper of wood pulp and synthetic pulp, non-woven fabric, plastic film, cloth, metal sheet, and composite sheet materials thereof. Can be used as it is. Also, to obtain a specific smoothness,
And in order to adjust the water resistance and other properties, the above substrate is impregnated with a coating material composed of a hydrophobic resin, a water-dispersible or water-soluble resin, a pigment, or the like used for an under layer or a back coat layer described below. You may.

In order to satisfy the printing suitability required for the lithographic printing original plate, for example, recording characteristics, water resistance, durability and the like, and to adjust the desired smoothness as described above, an under layer and a back coat layer are formed on the substrate. It is preferable to use a support provided with. Such an under layer and a back coat layer are formed by applying a coating solution containing a resin, a pigment, and the like on a support, drying and laminating the coating solution.
Various resins are appropriately selected and used as the resin used here. Specifically, examples of the hydrophobic resin include an acrylic resin, a vinyl chloride resin, a styrene resin, a urethane resin, a vinylidene chloride resin, and a vinyl acetate resin.Examples of the hydrophilic resin include polyvinyl resin. Alcohol resins, cellulose derivatives, starch and derivatives thereof, polyacrylamide resins, styrene-maleic anhydride copolymers and the like can be mentioned.

Examples of the pigment include clay, kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica and the like. These pigments are used to achieve the desired smoothness.
It is preferable to appropriately select and use the particle size. For example, since a relatively high degree of smoothness is required in the under layer, a small particle size or a large particle is cut to specifically 8 μm or less, preferably Preferably, a pigment having a particle size of about 0.5 to 5 μm is used. Further, since a lower smoothness is required in the back coat layer as compared with the under layer, a larger particle size, specifically, 0.5 to 10
A pigment having a particle size of about μm is preferably used. The pigment as described above is preferably used in a ratio of 80 to 150 parts by mass in the under layer and 80 to 200 parts by mass in the back coat layer, based on 100 parts by mass of the resin. In order to obtain excellent water resistance, it is effective for the under layer and the back coat layer to contain a water-resistant agent such as a melamine resin or a polyamide epichlorohydrin resin. The particle size can be measured by a scanning electron microscope (SEM) photograph. When the particles are not spherical, the diameter is obtained by converting the projected area into a circle.

In order to prepare a lithographic printing plate precursor, a solution containing an under layer component is coated on one side of the support, if necessary, and dried to form an under layer. If necessary, a back layer is formed on the other side. After forming a back coat layer by applying and drying a solution containing a coating layer component, a coating solution containing an image receiving layer component may be applied and dried to form an image receiving layer. Note that the image-receiving layer, the under layer, the coating amount of the backcoat layer are each 1 to 30 g / m ^2, in particular 6~20g / m ² is suitable. Preferably, the water-resistant support provided with an under layer or a back coat layer has a thickness of 90 to 1
It is in the range of 30 μm, more preferably in the range of 100 to 120 μm.

Next, a method of forming an image on the lithographic printing original plate (hereinafter also referred to as “master”) will be described. FIG. 1 shows an example of an apparatus system for performing such a method. The apparatus system shown in FIG. 1 has an ink jet recording apparatus 1 using oil-based ink.

As shown in FIG. 1, first, pattern information of an image (figure or text) to be formed on the master 2 is transmitted from an information supply source such as the computer 3 through a transmission means such as the bus 4 to the oil-based ink. Is supplied to the ink jet recording apparatus 1 that uses. The ink jet recording head 10 of the recording apparatus 1 stores oil-based ink therein, and when the master 2 passes through the recording apparatus 1, ejects minute droplets of the ink to the master 2 according to the information. Thereby, ink adheres to the master 2 in the pattern. Thus, an image is formed on the master 2 to obtain a plate-making master (plate-making printing original plate).

FIGS. 2 and 3 show examples of the configuration of an ink jet recording apparatus as in the apparatus system of FIG. FIG. 2 is a view showing a part of the head of such an ink jet recording apparatus, and FIG. 3 is a view for further explaining the structure thereof.

The ink jet recording head 10 provided in the ink jet recording apparatus comprises a head body 14 made of an insulating material such as plastic or ceramic, and meniscus regulating plates 15 and 16 as shown in FIG. In the figure, reference numeral 17 denotes an ejection electrode for applying a voltage to perform ejection. Fig. 3 with the restriction plate removed from the head
The head body will be described in detail below.

The head main body 14 is provided with a plurality of ink grooves 18 for circulating ink, perpendicular to the edge of the head main body.
Two adjacent ink grooves form one cell, and ejection parts 20, 20 'are provided at the end of the partition wall 19 at the center. In the ejection portions 20 and 20 ′, the partition walls are thinner than the other partition portions 25 and are sharpened. The tip of the discharge unit may be slightly chamfered as in 20 '. Although only two cells are shown in the figure, the cells are separated by a partition 21 and the tip 22 thereof is formed by a discharge unit 20.
It is chamfered so as to be retracted from 20 '.

Ink is supplied to the head from an I direction through an ink groove by an ink supply means (not shown) to supply ink to a discharge section. Excess ink is collected in the O direction by an ink collecting means (not shown).
As a result, fresh ink is always supplied to the ejection unit. In this state, by applying a voltage to the discharge electrode against a counter electrode (not shown) which is provided in a form opposing the discharge unit and holds the printing original on the surface, ink is discharged from the discharge unit, and An image is formed on the original.

As described above, on the lithographic printing original plate,
An image is formed by an ink-jet method using oil-based ink, and plate making is performed. When the lithographic printing plate precursor used comprises a hydrophilic surface layer, it is used as it is as a printing plate for offset printing.

On the other hand, in the case of a lithographic printing original plate accompanied by desensitization, a non-image portion is desensitized by surface treatment with a desensitizing solution to prepare a printing plate. Desensitization of zinc oxide
Conventionally, as this type of desensitizing treatment solution, a cyanide-containing treatment solution containing ferrocyanide salt, ferricyan salt as a main component, an ammine cobalt complex, phytic acid and derivatives thereof, and a cyan-free treatment containing a guanidine derivative as a main component Liquids, treatment liquids containing an inorganic or organic acid which forms a chelate with zinc ions as a main component, treatment liquids containing a water-soluble polymer, and the like are known.

For example, as a cyanide-containing treatment solution,
JP-B-44-9045, JP-B-46-39403, JP-A-52-76101, JP-A-57-107889, and JP-A-57-107889.
4-117201 and the like. Phytic acid-based compound-containing treatment solutions are disclosed in JP-A-53-83.
No. 807, No. 53-83805, No. 53-10210
No. 2, No. 53-109701, No. 53-127003
And Nos. 54-2803 and 54-44901.

Examples of the treating solution containing a metal complex compound such as a cobalt complex include JP-A-53-104301 and JP-A-53-104301.
No. 140103, No. 54-18304, Tokuhei 43-
No. 28404. As an inorganic or organic acid-containing treatment solution, JP-B-39-13702,
Nos. 40-10308, 43-28408, 40
-26124 and JP-A-51-118501.

Examples of the guanidine compound-containing treating solution include those described in JP-A-56-111695. As a processing solution containing a water-soluble polymer, Japanese Patent Application Laid-Open
-126302, 52-134501, 53-
49506, 53-59022, 53-104
No. 302, JP-B-38-9665 and 39-2226
3, No. 40-763, No. 40-2202, and JP-A-49-36402.

In any of the above desensitizing treatments,
Zinc oxide in the surface layer ionizes into zinc ions,
It is believed that these ions cause a chelation reaction with a compound forming a chelate in the desensitizing solution to form a zinc chelate, which is deposited in the surface layer and hydrophilized.

The desensitizing treatment is usually performed at room temperature (15 ° C. to 35 ° C.).
) For about 2 to 60 seconds. Using this printing plate, several thousand sheets of offset printing are possible using dampening water.

[0228]

EXAMPLES The present invention will be described in more detail with reference to Production Examples and Examples of resin particles used in the present invention, but the present invention is not limited to these.

Production Example 1 of Macromonomer (MA) A mixture of 100 g of macromonomer (MA-1) octadecyl methacrylate, 2 g of 3-mercaptopropionic acid and 200 g of toluene was added to a temperature of 70 ° C. while stirring under a nitrogen stream. Warmed.
2,2'-azobis (isobutyronitrile) (abbreviation A.
I. B. 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, and the mixture was stirred at a temperature of 100 ° C. for 10 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. The weight average molecular weight (Mw) of the polymer was 1 × 10 ⁴ (the weight average molecular weight was
G. FIG. P. The value is expressed in terms of polystyrene by the C method. same as below).

[0230]

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Production Examples 2-1 of Macromonomer (MA)
1: Macromonomer (MA-2) to (MA-11) In the same manner as in Production Example 1 except that only octadecyl methacrylate was replaced with a compound corresponding to Table 1 below in Production Example 1 of Macromonomer (MA). By reacting, macromonomers (MA-2) to (MA-11) were synthesized. The mass average molecular weight of each of the obtained macromonomers is 9 × 10 ³ to 1
× 10 ⁴ range.

[0232]

[Table 1]

Production Example 12 of Macromonomer (MA) Macromonomer (MA-12) A mixed solution of 100 g of tetradecyl methacrylate, 2 g of thioethanol and 200 g of toluene was 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. 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, 8 g of 2-carboxyethyl acrylate was added, and dicyclohexylcarbodiimide (abbreviated as D.I.
C. C. ) And 60 g of methylene chloride were added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred as it was 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 give a yield of 60 g and a Mw of 8 ×.
To obtain a 10 ³ polymer.

[0235]

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Production Examples of Macromonomer (MA) 13-1
5: Macromonomer (MA-13) to (MA-15) In Production Example 12 of macromonomer (MA), methacrylate monomer (corresponding to tetradecyl methacrylate) and unsaturated carboxylic acid (corresponding to 2-carboxyethyl acrylate) were used. Except that each was replaced, the same procedure as in Production Example 12 was carried out to produce each of the macromonomers shown in Table 2 below. 60
The weight average molecular weight of each macromonomer obtained at で 70 g ranged from 7 × 10 ^{3 to} 9 × 10 ³ .

[0237]

[Table 2]

Preparation Example 16 of Macromonomer (MA) Macromonomer (MA-16) A mixed solution of 100 g of 2,3-dihexanoyloxypropyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated at a temperature of 7 under a nitrogen stream.
Warmed to 5 ° C. 5.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: A.C.V.) was added and reacted for 5 hours. 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
g, 1.0 g of 2,2'-methylenebis (6-t-butyl-p-cresol) and 100 g of toluene were stirred at a temperature of 100 DEG 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 weight average molecular weight was 7 × 10 ³ .

[0240]

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Production Example 1 of Resin Particles (L)
-1) A mixture of 8 g of the dispersion stabilizing resin (P-1) having the following structure and 280 g of Isopar G was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. Methyl methacrylate 15
g, 25.8 g of methyl acrylate, 4 g of macromonomer (MA-1), 6 g of 2- (N, N-dimethylamino) ethyl methacrylate, and 2,2-azobisisovaleronitrile (abbreviation: AIVN) ), 1.5 g of a mixture and a mixture of 15 g of methyl methacrylate, 30.2 g of methyl acrylate, 4 g of 3-sulfopropyl methacrylate and 10 g of ethanol were simultaneously added dropwise for 1 hour, followed by stirring for 2 hours.

Next, A.I. I. V. N. Was added, and the mixture was heated to a temperature of 75 ° C. and stirred for 4 hours. I. B.
N. Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 4 hours. Then, the temperature was raised to 100 ° C.
After stirring under Hg for 2 hours, ethanol and unreacted monomers were distilled off. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was obtained at a conversion of 99% and an average particle size of 0.1%.
It was a 45 μm latex. Particle size is CAPA-50
0 (manufactured by Horiba, Ltd.). A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm,
(Rotation time 1 hour) to collect the sedimented resin particles
After drying, the weight average molecular weight (Mw) and glass transition point (Tg) of the resin particles were measured.
⁵ (polystyrene equivalent value by GPC; the same applies hereinafter), and Tg was 41 ° C.

[0243]

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Production Example 2 of Resin Particles (L): Resin Particles (L)
-2) A mixture of 12 g of a dispersion stabilizing resin (P-2) having the following structure and 283 g of Isopar G was heated to a temperature of 70 ° C while stirring under a nitrogen stream. Methyl methacrylate 20
g, ethyl acrylate 26 g, macromonomer (MA
-14) 3 g, 2- (N, N-diethylamino) ethyl methacrylate 8 g and A.I. I. V. N. , 1.5 g of a mixture and a mixture of 15 g of methyl methacrylate, 23.6 g of methyl acrylate, 4.4 g of 3-sulfopropyl acrylate and 10 g of ethanol were simultaneously added dropwise for 1 hour, and the mixture was stirred for 2 hours. Next, A.
I. V. N. And heated to a temperature of 75 ° C.
Stir for an hour. I. B. N. Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Then set the temperature to 1
The temperature was raised to 00 ° C., and the mixture was stirred for 2 hours under a reduced pressure of 200 mmHg to distill off ethanol and unreacted monomers. After cooling 2
After passing through a 00 mesh nylon cloth, the obtained white dispersion was a latex having a conversion of 99% and an average particle size of 0.42 μm. Mw of the resin particles was 3 × 10 ⁵ and Tg was 41 ° C.

[0245]

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Production Examples 3-5 of Resin Particles (L): Resin Particles (L-3)-(L-5) In Production Example 1 of resin particles (L), 8 g of dispersion stabilizing resin (P-1) was added. Production Example 1 above except that 6 g of 2 (N, N-dimethylamino) ethyl methacrylate was replaced by 12 g of a dispersion stabilizing resin (P-3) having the following structure and 6 g of each monomer (B) shown in Table A below. Each particle was produced in the same manner as described above. The average particle size of each of the obtained particles is 0.40 to
The latex was in the range of 0.45 μm. Mw of the resin particles was 1 × 10 ^{5 to} 3 × 10 ⁵ , and Tg was in the range of 40 to 50 ° C.

[0247]

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[0248]

[Table 3]

Production Example 6 of Resin Particle (L): Resin Particle (L)
-6) A mixture of 9 g of a dispersion stabilizing resin (P-4) having the following structure and 280 g of Isopar G was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. In addition, methyl methacrylate 15
g, methyl acrylate 22 g, macromonomer (MA
-6) 3 g, 4- (N, N-dimethylamino) methylstyrene 8 g and A.I. I. B. N. , 1.5 g of a mixture and 10 g of methyl methacrylate, methyl acrylate 3
A mixture of 5.4 g, 6.6 g of 4-sulfomethylstyrene and 15 g of ethanol was simultaneously added dropwise for 1 hour, and the mixture was stirred for 2 hours. Next, A. I. B. N. Was added and stirred for 3 hours. I. B. N.
Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Next, the temperature was raised to 100 ° C., and the degree of decompression was 200 mmH.
Then, the mixture was stirred for 2 hours under g and ethanol and unreacted monomers were distilled off. After cooling, pass through a 200 mesh nylon cloth,
The resulting white dispersion had a conversion of 98% and an average particle size of 0.48.
μm latex. Mw for resin particles is 9 × 1
O ⁴ and Tg were 42 ° C.

[0250]

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Production Examples 7-14 of Resin Particles (L): Resin Particles (L-7) to (L-14) In Production Example 6 of resin particles (L), instead of macromonomer (MA-6), Except for using the macromonomer (MA) shown in Table B below, each particle was produced in the same manner as in Production Example 6 above. The average particle diameter of each of the obtained particles is 0.40 to 0.45 μm.
m in the range of m. Mw for resin particles is 8
× 10 ^{4 to} 2 × 10 ⁵ and Tg were in the respective ranges of 38 to 42 ° C.

[0252]

[Table 4]

Production Examples 15-20 of Resin Particles (L): Resin Particles (L-15)-(L-20) In Production Example 6 of resin particles (L), instead of 6.6 g of 4-sulfomethylstyrene, 0.028 mol of each monomer (C) in Table-C below (monomer (B) / monomer (C))
= 1.8 mol ratio), except that particles were produced in the same manner as in Production Example 6 above. The average particle diameter of each of the obtained particles was a latex in the range of 0.40 to 0.50 μm.
Mw of the resin particles is 9 × 10 ⁴ to 2 × 10 ⁵ , and Tg is 40
４８48 ° C.

[0254]

[Table 5]

Production Example 21 of Resin Particles (L): Resin Particles (L-21) A mixture of 8 g of a dispersion stabilizing resin (P-5) having the following structure and 230 g of Isopar G was stirred at a temperature of 75 ° C. under a nitrogen stream. Heated. To this, 42 g of vinyl acetate, 2-
(N, N-dimethylamino) ethyl crotonate 7 g,
5 g of macromonomer (MA-15), and I. B.
N. , 1.5 g of a mixture and 45 g of vinyl acetate, 6 g of 3-sulfopropylcrotonate and 10 g of ethanol were simultaneously added dropwise over 30 minutes each.
Stir for 5 hours. Next, A. I. B. N. Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. I.
B. N. Was added, and the mixture was heated to a temperature of 85 ° C. and stirred for 3 hours. Next, the temperature was raised to 100 ° C.,
The mixture was stirred under mmHg for 2 hours to distill off ethanol and unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 90% and an average particle size of 0.45 μm. Mw of the obtained resin particles was 8 × 10 ⁴ , and Tg was 45 ° C.

[0256]

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Production Examples 22 to 26 of Resin Particles (L): Resin Particles (L-22) to (L-26) In Production Example 6 of resin particles (L), 9 g of resin (P-4) for dispersion stabilization was prepared. Instead, 10 g of a dispersion stabilizing resin (P-6) having the following structure and 4- (N, N-dimethylamino)
Each particle was produced in the same manner as in Production Example 6 except that 0.04 mol of each compound shown in Table D below was used instead of 8 g of methylstyrene. The average particle size of each of the obtained grains is 0.40.
Latex in the range of ０．５0.50 μm. Mw of resin particles is 1 × 10 ^{5 to} 3 × 10 ⁵ , and Tg is 40 to 50 ° C.
Of each range.

[0258]

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[0259]

[Table 6]

Production Example of Comparative Resin Particles 1: Resin Particles (L
L-1) 8 g of dispersion stabilizing resin (P-1) and Isopar G 28
While stirring 0 g of the mixture under a nitrogen stream, the mixture was heated to a temperature of 70 ° C. 30 g of methyl methacrylate, 60 g of methyl acrylate, 2- (N, N-dimethylamino)
6 g of ethyl methacrylate, macromonomer (MA-
1) 4 g; I. V. N. , 1.5 g of the mixture was added dropwise over 1 hour, and the mixture was stirred for 2 hours. Next, A.
I. V. N. Was added and stirred at a temperature of 75 ° C. for 3 hours. I. B. N. 0.8 g and the temperature is 80
C. and stirred for 3 hours. Then, the temperature was increased to 100 ° C., and the mixture was stirred for 2 hours under a reduced pressure of 200 mmHg to distill off unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having a conversion of 99% and an average particle size of 0.42 μm. M of resin particles
w was 2 × 10 ⁵ and Tg was 38 ° C.

Production Example 2 of Comparative Resin Particles: Resin Particles (L
L-2) Dispersion stabilizing resin (P-1) 10 g and Isopar G 2
85 g of the mixture was stirred at a temperature of 70 ° C. under a nitrogen stream.
Was heated. 30 g of methyl methacrylate, 62 g of methyl acrylate, 4 g of 3-sulfopropyl methacrylate, 4 g of macromonomer (MA-1), 10 g of ethanol and I. V. N. , 1.5 g of the mixture in 1
The mixture was added dropwise over time, and the mixture was stirred for 2 hours. Next, A. I.
V. N. Was added and stirred at a temperature of 75 ° C. for 3 hours.
Further, A. I. B. N. Was added and the temperature was raised to 80 ° C., followed by stirring for 3 hours. Next, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours under a reduced pressure of 200 mmHg to distill off ethanol and unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth.
The latex was 9% and had an average particle size of 0.48 μm. The Mw of the resin particles was 2 × 10 ⁵ , and the Tg was 43 ° C.

Example 1 <Preparation of a lithographic printing plate precursor> A composition having the following content was added to a paint shaker (Toyo Seiki Co., Ltd.) together with glass beads.
And dispersed for 60 minutes, and then the glass beads were separated by filtration to obtain a dispersion.

Gelatin 7.5 g Alkoxysilane-modified polyvinyl alcohol R1130 2.5 g (manufactured by Kuraray Co., Ltd.) Silica: Thylsia 310 (manufactured by Fuji Silysia Chemical Ltd.) 8 g Colloidal silica 20% solution: Snowtec C 38 g (manufactured by Nissan Chemical Industries, Ltd.)-Fluorinated alkyl ester FC430 (manufactured by 3M) 0.8 g-Hardening compound CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂ 0.24g ・ Water 54g

Using the support of ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing, the above composition was applied thereon using a wire bar. The resultant was dried at 100 ° C. for 10 minutes to form an image receiving layer having a coating amount of 8 g / m ² , thereby obtaining a lithographic printing original plate. The surface smoothness of the obtained image-receiving layer was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air volume of 10 ml and its smoothness (sec / 10 m).
1) was measured and found to be 250 (sec / 10 ml).
Further, 2 μl of distilled water was placed on the surface of the image receiving layer, and
After 2 seconds, the surface contact angle (degree) was measured using a surface contact meter CA-D (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the surface of the image receiving layer with water was 0 degree.

<Preparation of Oil Ink (IK-1)> 10 g of polydodecyl methacrylate and 10 g of alkali blue
And 30 g of Isopar G was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) together with the glass beads and dispersed for 4 hours, and the glass beads were filtered off to obtain a fine blue dispersion. 50 g (as solid content) of the resin particles (L-1) produced in Production Example 1 of the resin particles (L), 18 g of the alkali blue dispersion, and 0.18 g of zirconium naphthenate are diluted to 1 liter of Isopar E. Thus, a blue oil-based ink was prepared.

Comparative Example A Example 1 was carried out in the same manner as in Example 1, except that the oil-based ink (IKR-1) was replaced with the oil-based ink (IKR-1) described below. <Preparation of Comparative Oil-Based Ink (IKR-1)> In preparing the oil-based ink (IK-1), 50 g (as a solid content) of comparative resin particles (LL-1) were used instead of the resin particles (L-1). Except for using, it was prepared in the same manner as the ink (IK-1).

Comparative Example B The procedure of Example 1 was repeated, except that the oil-based ink (IKR-2) having the following content was used in place of the oil-based ink (IK-1). <Preparation of Comparative Oil-Based Ink (IKR-2)> In preparing the oil-based ink (IK-1), 50 g (as a solid content) of comparative resin particles (LL-2) were used instead of the resin particles (L-1). Except for using, it was prepared in the same manner as the ink (IK-1).

The charging characteristics, ejection properties,
The shape of print dots, image reproducibility, printing durability, etc. were examined, and the results are shown in Table-E.

[0269]

[Table 7]

The evaluation items described in Table-E were performed in accordance with the following contents. Note 1) Charging characteristics-AC electric conductivity AC electric conductivity (pS / cm) was measured as the amount of charge of the ink. The AC electrical conductivity of the ink was measured with an LCR meter (AG-4311, manufactured by Ando Electric Co., Ltd.). At the time of measurement, a liquid electrode placed in a self-made aluminum shield box was filled with 2.3 ml of the ink to be measured via a test lead (AG-4912, manufactured by Ando Electric Co., Ltd.) using an LCR meter. (LP- manufactured by Kawaguchi Electric Co., Ltd.)
05, electrode constant 198), conductance was measured at an applied voltage of 5 V and a measurement frequency of 1 kHz, and the value was converted to an electric conductivity by dividing the value by the electrode constant. In the measurement, the measurement parameters of the LCR meter were set to capacitance, and the circuit mode was set to parallel mode.

Particle charge ratio Indicates the ratio of the amount of charge of the dispersed particles in the ink.

[0272]

(Equation 1)

Here, the charge amount of the supernatant is determined by the centrifugal separation of the ink (condition: 1 × 10 ⁴ rpm, 1 hour), and the amount of the supernatant liquid obtained by sedimenting the ink. Indicates AC electrical conductivity.

Further, the conditions I and II show changes in the time-lapse state after the ink production, and the condition I means that the ink obtained by mixing all the components was allowed to stand naturally for one week (normal temperature, normal humidity). )
(Fresh product), while condition II is
The fresh product was stored under high-temperature and high-humidity (40 ° C., 85% RH) conditions for 2 weeks and was forcibly aged (aged product).

Note 2) Dischargeability Dischargeability was measured by an apparatus using an injection needle as shown in FIG. The injection needle is made of stainless steel and has an inner diameter of 36.
0 μm, an outer diameter of 615 μm, a cutting angle at the tip of 19 °, a radius of curvature of 13 μm, and an ink tank 36 at the tip of the needle.
Is always supplied from the inside of the needle by the liquid sending pump 35, and the excess ink is naturally transmitted to the needle surface and collected in the waste liquid tank 37. The ink flow rate at this time is 0.75
ml / min. This injection needle is arranged at a distance of 300 μm from the surface of the plate material as the recording medium 32 mounted on the drum-shaped counter electrode 31, and a power supply 33 supplies a bias voltage of 700 V, a discharge voltage of 800 V, and a pulse voltage of 100 μSec width of 5 μm. Printing was performed by superimposing and applying at a frequency of 0.0 kHz. The polarity of the bias and the pulse voltage was determined so that the ink was repelled from the injection needle. The ejection rate was calculated from the number of dots actually printed with respect to the number of applied pulses (%). Conditions I and II are the same as in Note 1).

Note 3) Shape and thickness of print dot In the above evaluation items of dischargeability, the film thickness of the print dot of the sample subjected to the discharge test was measured from a scanning electron microscope (SEM) photograph. The larger the film thickness is, the more concentrated the particles in the ink are ejected. -Shape Similarly, the presence or absence of dot bleeding, distortion, or the like was examined using the above-mentioned sample by optical microscope and SEM photograph observation.

Note 4) Image reproducibility Using a lithographic printing plate prepared as described above, a servoproter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing output from a personal computer, was modified and shown in FIG. 2 in the Ben plotter section. The ink ejection head was mounted, and printing was performed on the lithographic printing original plate placed on the counter electrode spaced at a distance of 500 μm using the above oil-based ink to make a plate. At this time, printing was performed at a bias voltage of 650 V, an ejection voltage of 700 V,
The test was performed under the condition that a pulse voltage having a width of 0 μsec and a frequency of 2.0 kHz were used. Next, RICOFUUSER model 5
Using 92 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image was adjusted to 95 ° C. and heated for 20 seconds to sufficiently fix the image area. A copy image of the obtained plate (ie, printing plate) was visually observed at a magnification of 200 times with an optical microscope.

Note 5) Printing durability Using a printing plate obtained according to the method of Note 4), using a solution obtained by diluting SLM-OD (manufactured by Mitsubishi Paper Mills) 30 times with water as immersion water. Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) was used as a printing machine, and printing was performed using black ink for offset printing. The number of prints on which a clear image with no background stains and no missing fine lines or characters is obtained is represented as printing durability.

As shown in Table-E, Example 1 and Comparative Example A
Showed that the chargeability was good. In particular, Example 1
The overall charge and the charge fraction of the particles were excellent. On the other hand, in Comparative Example B, the amount of charge generation was extremely small, and the charge fraction of the particles was also low. Further, the change in charge was large with the lapse of time, and in particular, the charge fraction of the particles was significantly reduced.

Next, from the results of the ejection properties and the shape of the dots on the printed plate material, those showing good performance in both the fresh product (condition I) and the aging product (condition II) are the same as those of Example 1 and Comparative Example. A. Comparative Example B had an extremely thin film thickness of 0.1 μm or less, and blurred dot shapes occurred. Only the image of Example 1 showed good performance in both the fresh product and the aged product. Comparative Example A is an aged product, in which a slight drop was generated at the front end of the image. This is considered to be caused by a slight delay in the ejection of the ink at the start of the plate making drawing.

Further, when printing was performed using this printing plate, only Example 1 had a printing durability of 10,000 sheets or more. In Comparative Example A, in the aged product (II), there was a slight loss at the leading end of the image portion from the start of printing, and the formed image portion had about 8,000 sheets even if the printing durability was high, and the image disappeared. This is probably because the dot film thickness was insufficient.

From the above results, the ink of the present invention has a large charge amount of the whole ink and a very high charge fraction of 90% or more. As a result, in the ink discharge of the electrostatic ink jet method, the ink meniscus is stably formed on the discharge electrode, and the charged particles in the ink are also electrophoresed rapidly under the voltage suppression, and the particles are concentrated. Is printed on a printing original plate which is an ink receiving material. Therefore, the print dots on the plate material have a thickness as large as 2.0 μm or more, and the dots also have circular bleeding, and no generation of distortion or the like is observed. Furthermore, when the printing plate is actually printed, the printing durability shows good performance of 10,000 sheets or more because the image portion has a sufficient thickness. From the above, only the oil-based ink of the present invention showed stable and good performance over time.

Examples 2 to 6 In Example 1, instead of 50 g of the resin particles (L-1) in the oil-based ink (IK-1), 50 g (as solid content) of each resin particle shown in Table F below was used. Otherwise, each oil-based ink was prepared in the same manner as in the oil-based ink (IK-1) and evaluated in the same manner as in Example 1. Each ink showed the same good results as in Example 1. As for the printing durability, a result of 10,000 sheets or more was obtained.

[0284]

[Table 8]

Example 7 <Preparation of a lithographic printing plate precursor> A composition having the following contents was put together with glass beads in a paint shaker and dispersed for 80 minutes. Then, the glass beads were separated by filtration to obtain a dispersion.

• Silica: 40 g of Sylysia 445 (manufactured by Fuji Silysia Chemical Ltd.) • 200 g of colloidal silica: 200 g of Snowtec C (manufactured by Nissan Chemical Industries, Ltd.) • 40 g of clay 50% dispersion • polyvinyl alcohol: PVA -117, 10% solution 80 g (manufactured by Kuraray Co., Ltd.)-Gelatin 4.0 g-Melamine resin 2.0 g-Ammonium chloride 0.2 g-Water 50 g

Using a support of ELP-1X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing plate for light printing, the above composition was coated thereon with a wire bar. Then, the resultant was heated at 110 ° C. for 10 minutes to form an image receiving layer having a coating amount of 6 g / m ² , thereby obtaining a lithographic printing original plate. The surface smoothness of the obtained image receiving layer was 300 (sec / 10 ml) in Beck's smoothness, and the contact angle with water on the surface was 0 degree. This printing plate was used in Example 1
The plate was made in the same manner as described above. However, instead of the oil-based ink (IK-1) used in Example 1, the following oil-based ink (IK-7) was used.

<Preparation of oil-based ink (IK-7)> 10 g of the dispersion stabilizing resin (P-3), Microlich Blue 4G
10 g (manufactured by Ciba-Geigy) and Isopar G 80
g into a paint shaker with glass beads,
The mixture was dispersed for 3 hours, and the glass beads were separated by filtration to obtain a fine blue dispersion. 50 g (as a solid content) of the resin particles (L-2) produced in Production Example 2 of the resin particles (L), 3 g (as a solid content) of the blue dispersion and 0.20 g of cobalt octenoate were added to 1 liter of Isopar E. A blue oil-based ink was prepared by dilution.

The properties of the obtained ink were measured in the same manner as in Example 1, and the results as shown in Table G below were obtained. The chargeability, dischargeability, and dot shape were good even with the lapse of time.

[0290]

[Table 9]

Next, printing was performed in the same manner as in Example 1. The obtained printed matter has clear image quality with no stain on the non-image area, similarly to the printed matter of Example 1, and has a printing durability of 3
It was a good one with over 1,000 sheets.

Next, an ink ejection test was carried out using the ejection device of Example 1 (FIG. 4). As a result, stable ink ejection was obtained even after 500 hours. The ink stored at room temperature for 6 months showed no generation of aggregates, and stable ink ejection was obtained even when the same ejection test was performed. Further, when printing was actually performed using the printing plate under these conditions, 3,000 or more printed matters having clear images without background smear were obtained.

Further, the redispersibility of the ink was evaluated under forced conditions. That is, after the ink used in the above-described ejection experiment was filled with ink, removed, left at 35 ° C. for 3 days, the ejection head was immersed in Isopar G for 30 minutes, and then lightly stirred, the ink (IK-7) became Everything was removed from inside the slit. That is, the ink of (IK-7) which had adhered to the tip of the slit of the ejection head in a non-fluid state by being left undisturbed was easily redispersed by solvation with the dispersion medium. As described above, the ink of the present invention is excellent in chargeability, enables fine drawing, and exhibits high printing durability as a printing plate. Further, the dispersion stability and redispersibility of the particles are excellent.

Examples 8 to 25 Plates were prepared in the same manner as in Example 7, except that the oil-based ink (IK-7) was replaced with the oil-based ink shown in Table H below. The oil-based ink used was the same as the oil-based ink (IK-7) in Example 7 except that 50 g (as a solid content) of the resin particles shown in Table H below were used instead of the resin particles (L-2) used. It was created similarly.

[0295]

[Table 10]

When the characteristics of the ink were evaluated in the same manner as in Example 1, the AC electric conductivity of the ink was 480 for each ink.
５530 (pS / cm), and the charged fraction of particles is 90９５95.
% Range. Plate making was performed in the same manner as in Example 7 using the lithographic printing original plate used in Example 7. Fresh product (I)
In addition, both the aged product (II) and the aged product exhibited the same performance as that of Example 7 and were excellent. When printing was performed as a printing plate, all plates exhibited printing durability of 3,000 or more. When the ink continuous ejection test was performed in the same manner as in Example 7, each of the aged inks was stable for 500 hours or more. Further, in a forced test of ink redispersibility, performance equivalent to that of Example 7 was shown.

Example 26 <Preparation of Water-Resistant Support> 100 g / m ² weighed as substrate
Using a high-quality paper, a coating for underlayer having the following composition was applied to one surface of the substrate using a wire bar to provide an underlayer with a dry coating amount of 10 g / m ² . The smoothness of the under layer surface was 150 seconds / 10 ml, and the smoothness was adjusted to 1500 (second / 10 ml) by calendering.

<Coating for Under Layer>-10 parts by mass of silica gel-92 parts by mass of SBR latex (50% by mass aqueous dispersion, Tg: 25 ° C)-110 parts by mass of clay (45% by mass aqueous dispersion)-Melamine (80 5% by mass ・ Water 191 parts by mass

Further, a coating material for a back coat having the following composition was applied to the other surface of the substrate using a wire bar to provide a back coat layer having a dry coating amount of 12 g / m ² . Calendar processing was performed by setting calendar conditions so that the smoothness was about 50 (seconds / 10 ml).

<Coating for Back Coat Layer> ・ 200 parts of kaolin (50% aqueous dispersion) ・ 60 parts of aqueous polyvinyl alcohol solution (10%) ・ 100 parts of SBR latex (solid content 49%, Tg: 0 ° C.) 100 parts ・ melamine resin Initial condensate 5 parts (solid content 80%, Sumiretz Resin SR-613)

<Preparation of lithographic printing plate precursor> Zinc oxide 100
g, 16 g of binder resin (B-1) having the following structure, 2 g of binder resin (B-2), 0.15 g of benzoic acid, and 1 part of toluene
55 g of the mixture was dispersed at a rotation speed of 6 × 10 ³ rpm for 8 minutes using a wet disperser homogenizer (manufactured by Nippon Seiki Co., Ltd.).

[0302]

Embedded image

This dispersion was coated on the above-mentioned water-resistant support using a wire bar so that the coating amount was 10 g / m ² .
By coating and drying, a lithographic printing original plate having a surface smoothness of 250 (seconds / 10 ml) was prepared. Surface contact angle with water is 10
It was twice.

<Preparation of oil-based ink (IK-26)> 10 g of dispersion stabilizing resin (P-2), black pigment (Microlith Bl)
ack CT, Ciba-Geigy) 10 g and Isopar E,
113 g was placed in a paint shaker together with the glass beads and dispersed for 6 hours, and the glass beads were separated by filtration to obtain a black dispersion. 60 g (as a solid content) of the resin particles (L-26) produced in Production Example 26 of the resin particles (L), 4 g (as a solid content) of the black dispersion, and 0.1 g of zirconium behenate.
18 g was diluted with hexamethyldisiloxane to a total volume of 1 liter to prepare a black oil-based ink (IK-26). The AC conductivity of the obtained ink is 500 (pS
/ Cm), and the charged fraction of the particles was 90%.

The printing original plate and oil-based ink (IK-2
A plate was made in the same manner as in Example 1, except that 6) was used, to obtain a plate having a clear image with no loss of fine lines and characters. The dot thickness was 2.5 μm, and a good one with no bleeding or distortion was used.

Next, a desensitizing solution (ELP-E2, manufactured by Fuji Photo Film Co., Ltd.) was applied to a fully automatic printing machine (AM-28).
50, manufactured by Am Co., Ltd.), and a solution obtained by diluting a desensitizing solution (ELP-E2) four times with distilled water as a dampening solution was put into a dampening solution tray, Printing was performed using black ink for offset printing. as a result,
More than 3,000 printed images with clear images without background staining were obtained.

[0307]

By using the oil-based ink of the present invention, it is possible to form an image excellent in ink ejection stability, clear image forming property and image strength, and to obtain a clear image in an electrostatic ink jet recording system. A printing plate capable of printing a large number of prints can be provided. Further, according to the oil-based ink for an electrostatic ink jet of the present invention, the redispersibility of the dispersed particles and the storage stability are excellent, the ink is not clogged in the ink supply path, and the ejection of the ink is stabilized.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system to which the oil-based ink of the present invention can be applied.

FIG. 2 is a diagram showing a part of a head of an ink jet recording apparatus to which the oil-based ink of the present invention can be applied.

FIG. 3 is a diagram in which a meniscus regulating plate is removed from the head shown in FIG. 2;

FIG. 4 is a view showing a discharge test apparatus used in the examples.

[Explanation of symbols]

 1 Inkjet recording apparatus 2 Lithographic printing master (master) 3 Computer 4 Bus 10 Inkjet recording head 13 Inkjet recording head 14 Head body 15, 16 Meniscus regulating plate 17 Ejection electrode 18 Ink groove 19, 21 Partition 20, 20 'Ejection Part 22 Tip part 31 Drum-shaped counter electrode 32 Recording medium 33 Power supply 34 Recording head 35 Liquid feed pump 36 Ink tank 37 Waste liquid tank

Claims (2)

[Claims] 1. An oil ink for electrostatic inkjet comprising at least charged resin particles dispersed in a non-aqueous carrier liquid having an electric resistance of not less than 10 ⁹ Ω · cm and a dielectric constant of not more than 3.5. A resin particle which is soluble in a non-aqueous solvent and which contains at least one monofunctional monomer (A) which is insoluble by polymerization, containing an amino group represented by the general formula (I). At least one monofunctional monomer (B) copolymerizable with the monomer (A), containing -SO ₃ H and / or -SO ₂ H groups and copolymerizable with the monomer (A) At least one of the following monofunctional monomers (C), and only one terminal of the main chain of a polymer containing a repeating unit corresponding to the monomer represented by the following general formula (II): is weight-average molecular weight 2 × 10 ⁴ or less made by combining a polymerizable double bond group represented in At least one functional macromonomer (MA), and the following general formula (P
A copolymer resin particle obtained by polymerizing and granulating a solution containing at least one kind of the dispersion stabilizing resin (P) containing at least the component represented by I), for an electrostatic ink jet. Oil-based ink. Embedded image In the general formula (I), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or R ¹ and R ² are bonded together with a nitrogen atom. A ring may be formed. Embedded image In the general formula (II): U ⁰ is -COO-, -OCO-,-
(CH ₂ ) _r COO-,-(CH ₂ ) _r OCO-, -O-,-
SO _2- , -CONHCOO-, -CONHCONH
^{-, - CON (D 11)} -, - SO 2 N (D 11) -, or a phenylene group (wherein D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, r is 1 4 indicates an integer). a ¹ and a 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 having 1 to 7 carbon atoms, —COO-D ¹² , or — It represents a COO-D ¹² (wherein D ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). D ⁰
Represents a hydrocarbon group having 8 to 22 carbon atoms or a substituent represented by the following general formula (IIa) having a total of 8 or more atoms (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom). Formula ^{(IIa) - (A 1 -B} 1) m - (A 2 -B 2) in _n -D ²¹ formula (IIa), D ²¹ 1 to 22 hydrogen atoms or carbon atoms
Represents a hydrocarbon group. 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) -, - C
ON (D ²²⁾ - or -N represents a (D ²²⁾ CO- (wherein D ²² has the same meaning as above D ^21). m and n may be the same or different, and each represents an integer of 0 to 4. However, m and n do not become 0 at the same time.
A ¹ and A ² may be the same or different from each other, and each has a group represented by the following general formula (IIb) and a carbon number of 1 to
Represents at least one group selected from 18 hydrocarbon groups. Embedded image In the general formula (IIb), B ³ and B ⁴ may be the same or different from each other, have the same meaning as above B ^1, B ^2, A ⁴
Represents a hydrocarbon group having 1 to 18 carbon atoms, D ²³ is the D ²¹
Is synonymous with p represents an integer of 0 to 4. Embedded image In the general formula (IIc), U ¹ is -COO-, -CONHCO
O-, -CONHCONH-, -CONH- or a phenylene group. a ¹¹ and a ¹² may be the same or different and have the same meaning as a ¹ and a ² in the formula (II). Embedded image In the general formula (PI), A ¹ is -COO-, -OCO-,-
(CH ₂ ) _a COO-,-(CH ₂ ) _a OCO-, -O-, or (Where E is a mere bond, -O-, -OCO- or -C
OO-). a represents an integer of 1 to 12. L
Represents an alkyl group having 8 to 32 carbon atoms or an alkyl group having 8 to 32 carbon atoms.
Represents an alkenyl group. p ¹ and p ² may be the same or different, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO-D ¹ ,
Or an -COO-D ¹ via a hydrocarbon group (wherein by D ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). 2. The dispersion stabilizing resin (P) is contained in one end of the polymer main chain or in a substituent of a polymer copolymer component.
3. The electrostatic oil-based ink according to claim 1, wherein the oil-based ink is formed by bonding a polymerizable double bond group represented by the following general formula (PII). Embedded image In the general formula (PII), A ² represents —COO—, —OCO—,
_{(CH 2) b COO -,} - (CH 2) b OCO -, - O -, -
SO _2- , -CONHCOO-, -CONHCONH
^{-, - CON (E 1)} -, - SO 2 N (E 1) - or a phenylene group (E ^1, where represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, b is 1 to 4 Is an integer). q ¹ and q ² may be the same or different from each other, and have the same meanings as p ¹ and p ^{2 in} formula (PI).