JPH10316917A - Oil-based ink for ink jet process printing plate and method for making ink jet process printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink which an provide ink jet recording stably and repeatedly and is improved in plate wear, redispersibility and storage stability by dispersing resin particles having a specified composition in a nonaqueous carrier liquid. SOLUTION: A nonaqueous carrier liquid having an electric resistance of 10<9> Ωor above and a permittivity of 3.5 or below is used. Particles of a polymer obtained by polymerizing a solution containing a monofunctional monomer being soluble in a nonaqueous solvent miscible with the liquid and becoming insoluble therein when polymerized, a monomer copolymerizable therewith and represented by formula I [wherein E<1> is an 8C or higher aliphatic group or the formula: -(A<1> -B<1> )n -(A<2> -B<2> )n -R<21> ; (wherein R<21> is H or a 1-18C aliphatic group; B<1> and R<2> are each -O-, -S- or the like; A<1> and A<2> are each a (substituted) group of formula III or the like; and m and n are each 0-4)] and having the total number of carbon atoms of 8 or above (excluding H bonded to carbon or nitrogen) and a dispersion stabilizing resin which is a polymer comprising repeating units of formula III (wherein X<1> is -COO or the like; Y<1> is a 10-32C aliphatic group; and b<1> and b<2> are each 0-4), in which part of the main chain of the polymer is crosslinked and which is soluble in the nonaqueous solvent are dispersed in the liquid.

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 used for an ink-jet type plate-making printing plate and a method for producing a plate-making printing plate using the same. More specifically, the present invention relates to an oil-based ink having excellent image reproducibility and printability. The present invention relates to a method of making a printing plate using the same.

[0002]

2. Description of the Related Art With the recent development of office equipment and the development of OA, in the field of light printing, a direct-drawing lithographic printing plate precursor having a hydrophilic surface image-receiving layer on a water-resistant support is produced by various methods. Plate making, that is, an offset lithographic printing method for forming a printing plate by performing image formation has become widespread.

[0003] A conventional plate material for direct drawing type lithographic printing is obtained by forming an image receiving layer (including an inorganic pigment, a water-soluble resin and a water-proofing agent) on a support made of water-resistant paper or a plastic film. Or an image receiving layer).
Using a lipophilic ink on such a direct drawing type lithographic printing plate, a lipophilic image is formed by a typewriter or handwriting, or a lipophilic image is formed by thermally melting and transferring an image from an ink ribbon with a thermal transfer printer. A method of forming a printing plate by forming a printing plate is known.

However, the printing plate prepared by such a method has insufficient mechanical strength of the image portion, and the image portion is easily missing when printed.

[0005] On the other hand, ink jet recording is a recording method capable of high-speed printing with low noise, and is a recording method that is rapidly spreading recently.

As such an ink jet recording system, there is a so-called electric field control system in which ink is ejected by using an electrostatic attraction, and a so-called drop-on system in which ink is ejected by using the vibration pressure of a piezo element. Various ink jet recording methods, such as a demand type (pressure pulse method) and a so-called bubble (thermal) jet method, in which ink is ejected using pressure generated by forming and growing bubbles by high heat, have been proposed. With these methods, extremely high-precision images can be obtained.

[0007] In these ink jet recording systems, an aqueous ink using water as a main solvent and an oil-based ink using an organic solvent as a main solvent are generally used.

In addition, plate making of the above-mentioned direct drawing type lithographic printing plate precursor is also performed by an ink jet printer using an ink jet recording system, and at this time, an aqueous ink using water as a dispersion medium is also used. However,
The water-based ink has a problem that an image on a plate material is blurred and a drawing speed is reduced due to slow drying.
In order to reduce such a problem, a method using an oil-based ink using a non-aqueous solvent as a dispersion medium is disclosed in Japanese Patent Application Laid-Open No. Sho 54-11720.
No. 3.

However, even in this method, bleeding is observed in the actual image quality of the plate making, bleeding occurs when further printing is performed, and the number of prints is limited to several hundred at most, which is insufficient. In addition, such an ink has a problem that nozzles for ejecting minute ink droplets that enable high-resolution plate-making images are easily clogged.

In general, in an ink jet recording system, ink is ejected from a nozzle after passing through a filter. Therefore, clogging of a nozzle or clogging of a filter may occur, or fluidity of ink may change with time. Abnormal ink ejection is likely to occur due to various factors.

[0011] The abnormal discharge of the ink occurs not only in the aqueous ink composition but also in the oil-based ink composition. There have been various proposals to improve such ink ejection abnormalities.For example, in order to prevent ink ejection abnormalities when using an oil-based ink composition, an electric field control type inkjet recording method is described. JP-A-49-50935
As described in Japanese Patent Application Laid-Open Publication No. H05-163, there has been proposed to control the viscosity and specific resistance of the ink composition.
As described in Japanese Patent No. 29808/29, a proposal has been made to control the relative dielectric constant and specific resistance of a solvent used in an ink composition.

As an attempt to prevent clogging of nozzles with oily ink for general ink jet printers, for example, a method of improving the dispersion stability of pigment particles (JP-A-4-25573, JP-A-5-25413). And Japanese Patent Application Laid-Open No. 5-65443), a method of including a specific compound as an ink composition (Japanese Patent Laid-Open No. 3-796).
No. 77, 3-64377, 4-2023
No. 86, No. 7-109431, etc.).

However, when any of them is used for forming an image on a lithographic printing plate, none of them can satisfy the printing durability due to insufficient strength of the image at the time of printing.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for stably performing ink jet recording even when used repeatedly.
An object of the present invention is to provide a method of manufacturing an ink-jet type plate-making printing plate capable of producing a planographic printing plate having excellent printing durability. Also,
Another object of the present invention is to provide a method for producing an ink-jet type plate making plate capable of printing a large number of prints with clear images.

Another object of the present invention is to provide an oil-based ink for an ink-jet type plate-making printing plate having excellent redispersibility, storage stability and printing durability. Another object of the present invention is to provide an oil-based ink for an ink-jet type plate-making printing plate, in which the nozzle and the ink supply path are not clogged and the ejection of the ink is stable.

[0016]

The above object is achieved by the following constitutions (1) to (7). (1) An oil-based ink in which at least resin particles are dispersed in a non-aqueous carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less is placed on a lithographic printing original plate having a lithographically printable hydrophilic surface. In a prepress printing plate oil-based ink for forming an image by an ink-jet method in which a droplet is ejected from a nozzle, the dispersed resin particles are (i) a non-aqueous carrier liquid which is at least miscible with the non-aqueous carrier liquid. At least one monofunctional monomer (A) that is soluble in a water solvent and becomes insoluble by polymerization; (ii) the following general formula (I) copolymerizable with the monomer (A): And (iii) a polymer containing a repeating unit represented by the following general formula (II), and a part of the polymer main chain is cross-linked; At least the dispersion stabilizing resin (P) soluble in the non-aqueous solvent Ink jet plate making printing plate oil ink is a polymer obtained by solution polymerization reactions containing species.

[0017]

Embedded image

In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms or a total of 8 or more atoms (excluding a hydrogen atom bonded to carbon or nitrogen) in the following general formula (III). Represents the substituent shown.

Formula (III)-(A ¹ -B ¹ ) _m- (A ² -B ² ) _n -R ²¹

In the formula (III), R ²¹ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ¹ and B ² may be the same or different from each other, and are each -O-, -S-,-
_{CO -, - CO 2 -,} - OCO -, - SO 2 -, - N (R
^{22) -, - CON (R} 22) -, - N (R 22) CO -, -
_{^{N (R 22) SO 2 -}} , - SO 2 N (R 22) -, - NHCO
₂ - or an -NHCONH- (wherein R ²² is as defined in the above R ^21). A ¹ and A ² may be the same or different from each other, and each may be substituted, at least selected from a group represented by the following general formula (IIIa) and a hydrocarbon group having 1 to 18 carbon atoms. One group (however,
The case of two or more represents a bond of the group of the formula (IIIa) and / or the hydrocarbon group).

[0021]

Embedded image

In the formula (IIIa), B ³ and B ⁴ may be the same or different from each other, and have the same contents as B ¹ and B ² above, and A ⁴ has 1 to 18 carbon atoms which may be substituted. It represents a hydrocarbon group, and R ²³ has the same contents as R ²¹ described above. m, n and p may be the same or different from each other;
Represents an integer of from 4 to 4. However, there is no possibility that m + n + p = 0.

In the formula (I), U ¹ is -COO-, -CON
^{H -, - CON (R 11} ) - [wherein, R ¹¹ represents a substituent represented by the aliphatic group or the general formula (III)], -OC
O -, - CONHCOO -, - CH 2 COO -, - (C
H ₂ ) _k OCO—, where k represents an integer of 1 to 4, and —O—, —C ₆ H ₄ —, or —C ₆ H ₄ —COO—. 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, an alkyl group, —COO—R ¹² or —CH ₂ COO—R ¹² (where R ¹² is an aliphatic group) Represents a group).

[0024]

Embedded image

In the formula (II), X ¹ is -COO-, -OCO
_{-, - CH 2 OCO -,} - CH 2 COO -, - O- or -SO ₂ - represents a. Y ¹ represents an aliphatic group having 10 to 32 carbon atoms. b ¹ and b ² may be the same or different and have the same meaning as a ¹ and a ² in the formula (I).

(2) Smell of the dispersion stabilizing resin (P)
At one end of at least one polymer backbone, -PO_Three
H_Two, -SO_ThreeH, -COOH, -P (= O) (OH) R¹
[Where R ¹Is a hydrocarbon group, or -OR^Two(R^TwoIs hydrocarbon
OH, formyl group, -CON
R^ThreeR^Four, -SO_TwoNR^ThreeR^Four[Where R^ThreeAnd R^FourIs each
Each independently represents a hydrogen atom or a hydrocarbon group], a cyclic acid
At least one selected from an anhydride-containing group and an amino group
The inkjet according to the above (1), which contains two polar groups.
Oil-based ink for formula plate printing.

(3) On a lithographic printing original plate having a lithographically printable hydrophilic surface, at least resin particles are dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less. A method for producing a plate-making printing plate for forming an image by an inkjet method in which an oil-based ink is ejected from a nozzle in the form of droplets, wherein the method for producing an ink-jet type plate-making printing plate using the oil-based ink according to the above (1) or (2). .

(4) The method for producing an ink-jet type plate-making printing plate as described in (3) above, wherein the oil-based ink is discharged from a nozzle using an electrostatic field.

(5) The lithographic printing plate precursor has an image-receiving layer capable of lithographic printing and having at least a hydrophilic surface on a water-resistant support, and the water-resistant support is at least immediately below the image-receiving layer. (3) or (4), wherein the specific resistance of the portion is 10 ¹⁰ Ω · cm or less.

(6) The method for producing an ink-jet type plate-making printing plate as described in (5) above, wherein the specific resistance of the whole water-resistant support is 10 ¹⁰ Ω · cm or less.

(7) Production of an ink-jet type plate-making printing plate according to any one of the above (3) to (6), wherein the resin particles dispersed in the oil-based ink are charged to a positive charge or a negative charge. Method.

The present invention is characterized in that an oil-based ink is ejected on a lithographic printing plate precursor by an ink-jet method to form an image, and the oil-based ink used is excellent in dispersion stability, re-dispersibility and storage stability. The obtained printing plate can print a large number of clear images.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The oil-based ink used in the present invention will be described below. Electric resistance 10 ⁹ used in the present invention
As a non-aqueous carrier liquid having a Ωcm or more and a dielectric constant of 3.5 or less, preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen-substituted product of these hydrocarbons There is. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; a product of Exxon) Name), Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits)
Etc. can be used alone or in combination. In addition,
The upper limit of the electrical resistance of such a non-aqueous carrier liquid is 10 ¹⁶ Ωcm
And the lower limit of the dielectric constant is about 1.80.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are obtained by mixing a non-aqueous solvent with a part of the polymer chain crosslinked in a non-aqueous solvent. A monomer (B) containing at least one monofunctional monomer (A) and a specific substituent in the presence of a dispersion-stabilizing resin (P) soluble in a solvent;
Are polymerized and granulated by polymerizing at least one of the above.

Here, as the non-aqueous solvent, basically,
As long as it is miscible with the carrier liquid of the oil-based ink, it can be used.

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. 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.

Solvents that can be used by mixing with these organic solvents include alcohols (eg, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol monomethyl ether, fluorinated alcohol, etc.) and ketones (eg, methyl ethyl ketone, Cyclohexanone, etc.), carboxylic esters (eg, ethyl benzoate, 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, etc.).

It is desirable that the non-aqueous solvent used by mixing these is distilled off under heating or reduced pressure after polymerization granulation. However, even if the non-aqueous solvent is brought into an oil-based ink as a latex particle dispersion, the resistance of the ink is reduced. Is within the range that can satisfy the condition of 10 ⁹ Ωcm or more.

Usually, as the non-aqueous solvent used in the step of producing the resin dispersion, it is preferable to use the same solvent as the carrier liquid. As described above, linear or branched aliphatic hydrocarbons and alicyclic solvents are used. Examples thereof include hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and the like.

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

[0041]

Embedded image

In the general formula (IV), T ¹ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-CONHCOO-, -CONHOCO-, -SO
^{_{2 -, - CON (W 1}} ) -, - SO 2 N (W 1) -. Or a phenylene group (hereinafter, phenylene group is described as "-Ph-" Incidentally, phenylene 1,2, 1, , 3- and 1,4-phenylene groups). Here, W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, -Cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group,
2-methoxyethyl group, 3-methoxypropyl group, etc.).

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

D ¹ and d ² may be the same or different, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom, an ethyl group, a bromine atom, etc.) or an alkyl group having 1 to 3 carbon atoms (eg, methyl Group, ethyl group, propyl group, etc.), -COO-Z ¹ or -CH ₂ COO-Z ¹ [where Z ¹ is a hydrogen atom or a carbon atom 1 which may be substituted.
0 or less hydrocarbon group (for example, represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group)].

Specific monofunctional monomers (A) include:
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.);
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
C1-C4 alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (for example, methyl, ethyl, propyl,
Butyl group, 2-chloroethyl group, 2-bromoethyl group,
2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2- (N , N
-Dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl Group,
2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); styrene derivatives (for example, styrene, Vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene , Vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; acrylonitrile Ril; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook -Basic-" edited by The Society of Polymer Science, p.175-184, Baifukan (1986) Compounds described in, for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline,
Vinylthiazole, N-vinylmorpholine, etc.). Two or more monomers (A) may be used in combination.

Next, in the present invention, the monomer (B) containing the specific substituent represented by the general formula (I) which is used together with the monomer (A) will be further described.

The case where E ¹ in the monomer (B) represented by the general formula (I) represents an aliphatic group having 8 or more carbon atoms will be described in detail.

E ¹ preferably represents an optionally substituted alkyl group having 10 or more carbon atoms or an alkenyl group having 10 or more carbon atoms. For example, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, docosanyl, eicosanyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, A docosenyl group, a linoleyl group, an oleyl group and the like. Examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom), a hydroxyl group, a cyano group, and an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group).

U¹ Is preferably -COO-, -CONH
-, -CON (R¹¹)-[Where R ¹¹Is preferably charcoal
Aliphatic groups having a prime number of 1 to 18 (for example,
A alkyl group, an alkenyl group or an aralkyl group).
Shown), -OCO-, -CH _TwoOCO- or -O-
Represent. More preferably, -COO-, -CONH- or
Is -CON (R¹¹)-.

A ¹ and a ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, alkyl group, -COO-R ¹³ or -CH ₂ COO-R ¹³ (wherein, R ¹³ preferably represents an aliphatic group of 1 to 32 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group , Hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl Table group, octadecenyl group and the like, these aliphatic groups may have the same substituents as represented by the E ¹⁾ You. More preferably, a ¹ and a ² each represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.),-
COO-R ¹³ or -CH ₂ COO-R ¹³ (wherein, R
¹³ more preferably 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 , A heptenyl group, an octenyl group, a decenyl group and the like. These alkyl groups and alkenyl groups may have a substituent.

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

[0052] In the monomer represented by the general formula (I) (B), E ¹ is 8 or more total atoms (provided that the carbon, excluding hydrogen atom attached to the nitrogen) said - in general formula (III) The case where the substituent is represented will be described in detail.

A ¹ and A ² are at least one group selected from the group represented by the general formula (IIIa) and the hydrocarbon group having 1 to 18 carbon atoms (however, when two or more groups, Represents a bond of a group of formula (IIIa) and / or a hydrocarbon group). More specifically, these are-
C (R ²⁴ ) (R ²⁵ )-[R ²⁴ and R ²⁵ represent a hydrogen atom, an alkyl group, a halogen atom, etc.],-(CH ＝ CH)-, a cyclohexylene group [hereinafter, a cyclohexylene group is represented by “- C
₆ H ₁₀ - expressed in "" - C ₆ H ₁₀ - "is 1,2-cyclohexylene group, 1,3-cyclohexylene group, include 1,4-cyclohexylene group], the general formula (IIIa ) And any combination of atomic groups such as the groups shown in (1) and (2).

E¹Is represented by the general formula (III) having a total number of atoms of 8 or more.
When a substituent represented by the formula (I) is represented by the following formula:¹
-(A¹-B¹)_m-(A^Two-B^Two)_n-R^{twenty one}], U¹
To R _{twenty one}(Ie, U¹, A¹, B¹, A^Two, B^Two,
R^{twenty one})) Constitutes the connecting main chain
It is preferable that the total number of atoms to be performed is 8 or more.

Here, the number of atoms constituting the “linking main chain” means, for example, when U ¹ represents —COO— or —CONH—, an oxo group (＝ O group) or a hydrogen atom included not the carbon atoms constituting the linking main chain, ether oxygen atom, nitrogen atom (different from the total number of atoms that is defined by E ¹⁾ which is meant to be included in the number of atoms. Therefore, -COO- and -CONH- are counted as 2 atoms. Similarly, when R 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.

Note that U¹Is -CON (R¹¹)-
And R¹¹Is a substituent represented by the general formula (III),
[-(A¹-B¹)_m-(A^Two-B^Two)_n-R^{twenty one}]
Of E ^TwoIs also included in the aforementioned “linking main chain”.
I will. Furthermore, A¹, A^TwoIs represented by the above general formula (IIIa)
[-B^Three-(A^Four-B^Four)_p-R^Two
Three] Are also included in the aforementioned "linking main chain."

In the above-mentioned monomer (B) represented by the general formula (I), when E ¹ represents a substituent represented by the aforementioned general formula (III), specific examples include the following compounds Can be mentioned.

In the following formulas (1) to (19), each symbol represents the following. _{r 1: -H, -CH 3,} -Cl or -CN, r _2: -
H or —CH ₃ l: an integer of 2 to 10, p: an integer of 2 to 6, q: an integer of 2 to 4, m: an integer of 1 to 12, n: an integer of 4 to 18,

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A) and the monomer (B). It is important that the resin synthesized from these monomers is a non-aqueous solvent. Insoluble in the resin, whereby a desired dispersion resin can be obtained.

More specifically, the monomer (A) to be insolubilized
To the monomer (B) represented by the general formula (I) in 0.1.
It is preferably used in an amount of 1 to 15% by weight, more preferably 0.1 to 15% by weight.
It is preferable to use 2 to 10% by weight.

The molecular weight (Mw) of the dispersion resin of the present invention
Is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 8 × 10 ^{3 to} 5 × 10 ⁵ . Further, the dispersion resin of the present invention has a glass transition point of 15 to
A range of 80 ° C. or a softening point of 38 to 120 ° C. is preferable,
In particular, the glass transition point is 20 to 60 ° C or the softening point is 40 to 9
A range of 0 ° C. is preferred.

Within the above ranges, the dispersion stability, re-dispersion stability and storage stability of the dispersed resin particles of the oil-based ink of the present invention are excellent, and the quick fixability after image formation is good. Even when printing, it is retained without causing image loss,
Shows high printing durability.

The dispersion stabilizing resin (P) of the present invention, which is used for forming a stable resin dispersion from the solvent-insoluble polymer produced by polymerizing the monomer in a non-aqueous solvent, will be described.

The dispersion stabilizing resin (P) of the present invention is a polymer containing at least one repeating unit represented by the above general formula (II), wherein a part of the polymer main chain is crosslinked. The resin is soluble in the non-aqueous solvent.

In the repeating units represented by the general formula (II), the aliphatic group and the hydrocarbon group may be substituted.

In the general formula (II), X¹ Is preferably
Is -COO-, -OCO-, -CH _TwoOCO-, -C
H_TwoCOO- or -O-, more preferably-
COO-, -CH_TwoRepresents COO- or -O-.

Y¹ Is preferably substituted with 10 to 22
Alkyl, alkenyl or aralkyl groups
Represents Examples of the substituent include a halogen atom (eg,
For example, fluorine atom, chlorine atom, bromine atom), -O-Z^Two,
-COO-Z^Two, -OCO-Z ^Two(Where Z^TwoIs carbon number 6
~ 22 represents an alkyl group, for example, hexyl group, octyl
Tyl, decyl, dodecyl, hexadecyl, octyl
And a tadecyl group). More preferred
Is Y¹Is an alkyl group having 10 to 22 carbon atoms or
Represents a phenyl group. For example, decyl, dodecyl, tri
Decyl, tetradecyl, hexadecyl, octade
A sil group, a docosanyl group, an eicosanyl group, a decenyl group,
Dodecenyl group, tetradecenyl group, hexadecenyl group,
And octadecenyl group.

B ¹ and b ² may be the same or different from each other, and have the same meaning as a ¹ and a ² in the formula (I);
Preferably each a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z ¹ or -COO-Z ¹ via a hydrocarbon group having 1 to 8 carbon atoms [wherein Z ¹
Represents a hydrocarbon group having 1 to 22 carbon atoms].

Specifically, a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, —COO—Z ³ or —CH ₂ COO— Z ³ (where Z ³ represents an aliphatic group having 1 to 22 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, Tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, pentenyl group,
Hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, and these alkyl group, alkenyl group have the same substituents as represented by the Y ¹ May be used).

More preferably, b ¹ and b ² are each
Hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), - COO-Z ⁴ or -CH ₂ COO-Z ⁴ (where, Z ⁴ is from 1 to 12 carbon atoms Represents an alkyl group or an alkenyl group, 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, octenyl group, And a decenyl group and the like. These alkyl groups and alkenyl groups may have the same substituents as those described for Y ¹ above.

The dispersion stable resin (P) of the present invention comprises a monomer corresponding to the repeating unit represented by the general formula (II) and another monomer copolymerizable with the monomer. A polymer containing a copolymer component obtained by copolymerization and having a part of the polymer main chain crosslinked.

The other copolymerizable monomer may be any as long as it contains 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 of 6 or less; vinyl esters or acrylic esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. . More specifically, a compound having the same content as the above-mentioned monomer (A) to be insolubilized may be used.

In the polymer component of the dispersion stabilizing resin (P), the component of the repeating unit represented by the general formula (II) accounts for at least 60% by weight, preferably 70% by weight or more, of the polymer component. More preferably, it is at least 80% by weight.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of the monomer, a method of performing polymerization in the presence of a polyfunctional monomer, and a method of including a functional group capable of promoting a cross-linking reaction in a polymer and performing cross-linking by a polymer reaction.

The dispersion stabilizing resin (P) of the present invention has a simple production method (for example, the reaction requires a long time, the reaction is not quantitative, or impurities are mixed in by using a reaction accelerator, etc.). ), The crosslinking reaction by polymerization is effective.

The crosslinking reaction by polymerization refers to a polymerization reaction for producing a dispersion stabilizing resin (P), wherein a monomer having two or more polymerizable functional groups is preferably represented by the formula (II)
Is a method of crosslinking between polymer chains by polymerizing with a monomer corresponding to the repeating unit represented by

As the polymerizable functional group, specifically, CH ₂ ＝
_{CH-, CH 2 = CH-CH} 2 -, CH 2 = CH-CO-
_{O-, CH 2 = C (CH} 3) -CO-O-, CH 3 -CH =
_{CH-CO-O-, CH 2} = CH-CONH-, CH 2 =
_{C (CH 3) -CONH-, CH} 2 = C (CH 3) -CON
_{HCOO-, CH 2 = C (CH} 3) -CONHCONH
—, CH ₃ —CH ＝ CH—CONH—, CH ₂ ＣＨCH—O
_{-CO-, CH 2 = C (CH} 3) -O-CO-, CH 2 = C
_{H-CH 2 -O-CO-,} CH 2 = CH-NHCO-, C
H ₂ ＣＨCH—CH ₂ —NHCO—, CH ₂ ＣＨCH—SO
_{2 -, CH 2 = CH-} CO-, CH 2 = CH-O-, CH 2
= CH-S-, etc., and the monomer having two or more polymerizable functional groups is a monomer having two or more of the same or different polymerizable functional groups. Any monomer may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene; Alcohol (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400,
# 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaeristol, etc.) or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol and the like) Derivatives) methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers; dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Vinyl esters, allyl esters, vinyl amides or allyl amides of maleic acid, phthalic acid, itaconic acid and the like; polyamines (for example, ethylenediamine,
Condensates of 1,3-propylenediamine, 1,4-butylenediamine, etc.) with carboxylic acids having a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allylic acid, etc.).

Further, as the monomer having a different polymerizable functional group, for example, a carboxylic acid having a vinyl group [eg, methacrylic acid, acrylic acid, methacryloyl acetic acid,
Reactants of acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride and alcohol or amine (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonyl Ester derivatives or amide derivatives containing a vinyl group such as benzoic acid, allylaminocarbonylpropionic acid, etc.) (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate) , Vinyl methacryloyl acetate, vinyl methacryloyl propionate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyloxycarbonylmethyl methacrylate Ester, acrylic acid vinyl oxycarbonyl methyloxycarbonyl ethylene esters, N
-Allyl acrylamide, N-acryl methacrylamide, N-allylitaconamide, methacryloylpropionic allylamide, etc.); or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol,
2-aminobutanol) and a condensate of a carboxylic acid containing a vinyl group.

The monomer having two or more polymerizable functional groups used in the present invention is polymerized using not more than 10% by weight, preferably not more than 8% by weight of all the monomers, and the non-aqueous solvent of the present invention is used. To form a soluble resin.

In the present invention, the dispersion stabilizing resin (P)
Has a specific polar group bonded to at least one end of the polymer main chain [hereinafter referred to as a dispersion stabilizing resin (P
A) or resin (PA)].

Specific polar groups include -PO ₃ H ₂ , -S
O ₃ H, —COOH, —P (＝ O) (OH) R ¹ [where,
R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)], —OH, formyl group, —CONR ³ R ⁴ ,
—SO ₂ NR ³ R ⁴ (where R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), at least one type of polar group selected from a cyclic acid anhydride-containing group and an amino group No.

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

The above -CONR ³ R ⁴ and -SO ₂ NR ³ R
^{In the} polar group represented by ⁴ , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group (preferably having 1 carbon atom).
To 8 optionally substituted hydrocarbon groups). R ³ , R ⁴
Specific examples of the hydrocarbon group represented by R ¹ and R ²
And the same as the hydrocarbon group represented by

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Things.

Examples of the aliphatic dicarboxylic anhydride include:
Succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylic anhydride, 2 , 3-bicyclo [2.2.2] octanedicarboxylic anhydride, and the like.

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Objects and the like.

Examples of the aliphatic dicarboxylic anhydride include:
Succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2-dicarboxylic anhydride,
Examples thereof include 2,3-bicyclo [2.2.2] octanedicarboxylic anhydride. These aliphatic dicarboxylic acids include, for example, a halogen atom such as a chlorine atom and a bromine atom, a methyl group, an ethyl group, and a butyl group. Or an alkyl group such as a hexyl group.

Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylic anhydride, thiophene-dicarboxylic anhydride and the like. Examples of the acid anhydride include a halogen atom such as a chlorine atom and a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a hydroxyl group, a cyano group, a nitro group and an alkoxycarbonyl group (as an alkoxy group) ,
For example, it may be substituted with a methoxy group, an ethoxy group and the like.

In the polar group of the present invention, the amino group is
Represents NH ₂ , —NHR ⁵ or —N (R ⁵ ) (R ⁶ ).
R ⁵ and R ⁶ each represent a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and specifically, the same as the hydrocarbon group represented by R ^1. Content.

In the dispersion stabilizing resin (PA), at least one of the above-mentioned specific polar groups may be directly bonded to one end of the polymer main chain, or may be bonded via a linking group.

Examples of the linking group for linking the main chain portion and a specific polar group-containing component include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, Sulfur atom, nitrogen atom, silicon atom, etc.) and any combination of heteroatom-heteroatom bond atomic groups.

More specific linking groups include -C (R ⁷ )
(R ⁸ )-[where R ⁷ and R ⁸ are each independently a hydrogen atom,
A halogen atom (such as a fluorine atom, a chlorine atom, or a bromine atom) represents a cyano group, a hydroxyl group, or an alkyl group (such as a methyl group, an ethyl group, or a propyl group). ],-(CH = CH)
_{-, - C 6 H 10 -} , ( wherein, -C ₆ H ₁₀ - 1, 2
-Represents 1,3-, 1,4-cyclohexylene. The same applies hereinafter), -Ph-, -O-, -S-, -CO-, -NR
^{9 -, - COO -, -} SO 2 -, - CONR 9 -, - SO 2
^{NR 9 -, - NHCOO -,} - NHCONH -, - Si
(R ⁹ ) (R ¹⁰ ) —where R ⁹ and R ¹⁰ are each independently
A hydrogen atom, a hydrocarbon group having the same content as that of R ¹ in the polar group]] or a single linking group selected from atomic groups or a combination of any two or more atomic groups. No.

The weight average molecular weight of the dispersion stabilizing resin (P) of the present invention is preferably in the range of 1 × 10 ⁴ to 1 × 10 ⁶ , more preferably in the range of 2.5 × 10 ⁴ to 2 × 10 ^5. . When the weight average molecular weight is less than 1 × 10 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example,
Larger than 0.8 μm) and the particle size distribution broadens.
If it exceeds 1 × 10 ⁶ , the average particle size of the resin particles obtained by polymerization granulation becomes too large, and
It may be difficult to make the average particle size uniform in the preferable range of 0.80 μm.

The dispersion stabilizing resin (P) used in the present invention
Is soluble in an organic solvent, and more specifically, it is sufficient that at least 5 parts by weight or more of the resin for dispersion stabilization is dissolved at 25 ° C. with respect to 100 parts by weight of a toluene solvent.

The dispersion stabilizing resin (P) used in the present invention
Specifically, a polymerization initiator (for example, a monomer corresponding to the repeating unit represented by the general formula (II), which is a known method, and the above-described polyfunctional monomer are allowed to coexist at least. , Azobis compounds, peroxides, etc.) are simple and preferred. The polymerization initiator used here is added in an amount of 0.1 to 100 parts by weight of all monomers.
It is 5 to 15% by weight, preferably 1 to 10% by weight.

In a preferred embodiment, the dispersion stabilizing resin (PA) of the present invention having a specific polar group bonded to only one end of at least one polymer main chain is prepared by a conventionally known anionic or cationic polymerization. A method of reacting various reagents with the terminal of the obtained living polymer (method by ionic polymerization method), a method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific polar group in the molecule (radical polymerization) Polymerization method), or a method of converting a polymer having a reactive group into a specific polarity of the present invention by a polymer reaction at the terminal obtained by the ionic polymerization method or the radical polymerization method as described above. It can be easily manufactured.

More specifically, P. Dreyfuss, RPQuirk, Enc
ycl. Poly. Sci. Eng., 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Chemistry and Industry" 60 , 57 (1986) ) Etc. and the methods described in the references cited therein.

The weight average molecular weight of the dispersion stabilizing resin (PA) of the present invention is preferably in the range of 1 × 10 ^{4 to} 5 × 10 ⁵ ,
More preferably, it is in the range of 2.5 × 10 ⁴ to 2 × 10 ⁵ . When the weight average molecular weight is less than 1 × 10 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example,
Larger than 0.8 μm) and the particle size distribution broadens.
If it exceeds 1 × 10 ⁵ , the average particle size of the resin particles obtained by polymerization granulation is too large, and
It may be difficult to make the average particle size uniform within the preferable range of 0.8 μm.

The dispersion stabilizing resin (P) used in the present invention
A) is specifically formed by polymerizing a mixture of a monomer corresponding to the repeating unit represented by the general formula (II), the above-mentioned polyfunctional monomer, and the above-mentioned chain transfer agent having a specific polar group. A method of polymerizing with an initiator (for example, an azobis compound, a peroxide, or the like), a method of polymerizing with a polymerization initiator containing the polar group without using the chain transfer agent, or a method of chain transfer agent And a method using a compound containing the polar group as a polymerization initiator, and further, in the above three methods, as a substituent of a chain transfer agent or a polymerization initiator, an amino group, a halogen atom, an epoxy group, After the polymerization reaction using a compound containing an acid halide group or the like, it can be produced by a method of introducing the polar group by reacting with a functional group by a polymer reaction.

As the chain transfer agent to be used, for example, the above-mentioned polar group or a mercapto compound containing a substituent capable of being derived from the above-mentioned polar 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, 3-mercaptopropanesulfonic acid, 4
-Mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1
-Mercapto-2-propanol, 3-mercapto-2
-Butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol and the like, or an iodoalkyl compound containing the polar group or a substituent capable of being derived from the polar group (for example, iodine Acetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Examples of the polar group or a polymerization initiator containing a substituent which can be derived from the polar group include:
4,4'-azobis (4-cyanovaleric acid), 4,4'-
Azobis (4-cyanovaleric chloride), 2,2'-
Azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-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-amidinopropane) and the like.

The amount of the chain transfer agent or polymerization initiator to be used is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 1 part by weight, based on 100 parts by weight of all monomers.
0 parts by weight.

To produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin (P) as described above,
The monomer (A) and the monomer (B) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutylnitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin (P), the monomer (A) and the monomer (B), a solution in which the dispersion stabilizing resin (P) is dissolved In the method, the monomer (A) and the monomer (B) are dropped together with the polymerization initiator, or the total amount of the dispersion stabilizing resin (P) and the monomer (A) and the monomer (B) are added. A) a method of optionally adding the remaining monomer (A) and monomer (B) together with a polymerization initiator to a mixed solution containing a part of There is a method of arbitrarily adding a mixed solution of (P), the monomer (A) and the monomer (B) together with a polymerization initiator, and any of these methods can be used for production.

The total amount of the monomers (A) and (B) is preferably from 10 to 100 parts by weight of the non-aqueous solvent.
It is 100 parts by weight, more preferably 10 to 80 parts by weight.

The dispersion stabilizing resin (P) is preferably 1 to 50 parts by weight, more preferably 5 to 3 parts by weight, based on 100 parts by weight of all the monomers (A) and (B) used above.
0 parts by weight.

The amount of the polymerization initiator is 0.1 to 10 of the total monomers.
% By weight is appropriate. The polymerization temperature is preferably 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 in the non-aqueous solvent used in the reaction, or when the monomer (A) and the monomer (A) to be polymerized and granulated are used. When the unreacted product of the monomer (B) remains,
It is preferable to remove the solvent or the monomer by heating to a boiling point or higher, or to remove the solvent or the monomer by distillation under reduced pressure.

As described above, the non-aqueous dispersion resin particles produced according to the present invention exist as fine particles having a uniform particle size distribution. The average particle size is 0.10 to 0.8
μm, and preferably 0.15 to 0.5 μm.
The particle size can be determined using CAPA-500 (trade name, manufactured by Horiba, Ltd.) or the like. At the same time, it shows extremely stable dispersibility, and especially in a recording device, has good dispersibility even when used repeatedly for a long time, and is easy to re-disperse. Is not recognized at all.

Further, after the ink image is formed, it is quickly processed by heating or the like, and a strong film is easily formed on the surface of the support for a lithographic printing plate, and good fixability is exhibited. This makes it possible to print a large number of sheets (high printing durability) even in offset printing.

The oil-based ink of the present invention having the above effects is made possible by the insoluble latex of the present invention.

The insoluble resin particles of the present invention are polymerized and granulated using the monomer (B) having a specific substituent and the dispersion stabilizing resin (P) of the present invention to obtain a monodisperse particle. And redispersibility is improved.

That is, the monomer (B) copolymerizes with the monomer (A) which is insolubilized during polymerization granulation, but the monomer (B)
The specific substituted portion contained therein forms particles by non-aqueous dispersion polymerization, so that it is designed to have good affinity with non-aqueous solvents, so that it can sneak into the particle structure. Better solvation with the dispersing medium than on the particles, so it is oriented at the interface (surface) of the particle structure, resulting in improved affinity of the particle surface with the dispersing medium and prevention of aggregation between particles It is presumed that the effect of performing the treatment is significantly enhanced.

At the same time, the dispersed resin particles of the present invention
The dispersion stabilizing resin (P) interacts with the insoluble resin particles and is adsorbed on the insoluble resin particles. Since the dispersion stabilizing resin (P) adsorbed on the resin particles is soluble in a non-aqueous solvent, a so-called steric repulsion effect known as dispersion stabilization of a non-aqueous latex is brought about. At the same time, since the dispersion stabilizing resin (P) is a soluble resin containing a crosslinked structure, the affinity for the nonaqueous solvent is significantly improved, and the adsorbed dispersion stabilizing resin (P) has a crosslinked structure. Therefore, it is presumed that it exists near the particle interface, thereby improving the amphiphilicity near the particle interface.

From these facts, it is considered that aggregation and precipitation of insoluble particles are suppressed, and redispersibility is remarkably improved.

As described above, when the dispersion stabilizing resin (P) of the present invention is used, the dispersion stability is improved, and when the resin (PA) is further used, even if the amount used is reduced, the dispersion stability is improved. The effect is obtained. On the other hand, in the case of the resin (PA), dispersion stabilization can be achieved with a small amount of use, and the dispersion stabilizing resin (P) that does not adsorb to particles is reduced. These are concentrated in the ink when the oil-based ink is repeatedly used for a long time, and the concern that various problems are caused is improved.

The oil-based ink used in the present invention preferably contains a coloring material as a coloring component together with the above-described dispersed resin particles, for example, for 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, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo-based pigment, phthalocyanine-based Pigments, 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. Can be used without.

As the dyes, 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 0.01 to 5% by weight based on the whole ink. desirable.

These coloring materials may be dispersed in the non-aqueous solvent as the coloring materials themselves as dispersed particles separately from the dispersed resin particles, or may be contained in the dispersed resin particles. In the case of containing, pigments and the like are generally coated with the resin material of the dispersed resin particles to obtain resin-coated particles, and dyes and the like are formed by coloring the surface of the dispersed resin particles into colored particles. General.

One of the methods is described in JP-A-57-487.
No. 38, etc., there is a method of dyeing a dispersed resin material with a preferable dye. As another method, there is a method disclosed in JP-A-53-54029 or the like in which a dispersing resin material and a dye are chemically bonded, or described in JP-B-44-22955. When producing by a polymerization granulation method, there is a method in which a monomer containing a dye is used in advance to obtain a dye-containing copolymer.

The dispersed resin particles and the colored particles (or coloring material particles) in the oil-based ink of the present invention are preferably positively or negatively charged electro-detectable particles.

In order to impart an electric detecting property to these particles, it can be achieved by appropriately utilizing a technique of a wet type electrophotographic developer. Specifically, the above-mentioned “Recent development and practical use of electrophotographic development systems and toner materials”, pp. 139-148,
The Society of Electrophotography, "Basics and Application of Electrophotographic Technology" 497-
505 (Corona Co., 1988), Yuji Harasaki "Electrophotography" 16 (No. 2), page 44 (1977), and the like, using an electric test material and other additives.

More specifically, for example, British Patent No. 8934
No. 29, No. 934038, U.S. Pat. No. 112239
No. 7, No. 3900412, No. 460989,
JP-B-4-51023, JP-A-6-19595, JP-A-6-19596, JP-A-6-23865, JP-A-60-185963, JP-A-2-1396
No. 5, etc.

The charge controlling agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1000 parts by weight of the dispersion medium as the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electrical resistance of the oil-based ink. That is, if the electric resistance of the ink from which the dispersed particles are removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, it is necessary to control the amount of each additive within this limit. It is.

The water-resistant support having a hydrophilic surface capable of being printed on a plate used in the present invention may be any one which provides a hydrophilic surface suitable for plate printing. The body can be used as is.

Preferably, the surface of the image receiving surface for receiving the ink image is a hydrophilic surface having a contact angle with water of preferably 5 degrees or less, more preferably 0 degrees. A printed material free from ink stains on the non-image area is obtained.

The surface smoothness of the image receiving layer is preferably 50 (sec / 10 cc) or more, more preferably 80 (sec / 10 cc) or more in Beck smoothness. Here, the Beck smoothness can be measured by a Beck smoothness tester. A Beck smoothness tester is used to press 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 constant amount (10 cc) under reduced pressure. The time required for the air to pass between the glass surface and the test piece is measured. When the Bekk smoothness is 50 or more, it is preferable because the loss and blurring of the ink image formed by the size of the unevenness of the image receiving layer are suppressed.

In a preferred embodiment, on the basis of water resistance,
A water-resistant support (also referred to as a lithographic printing plate) provided with an image receiving layer having a hydrophilic surface capable of lithographic printing.

Examples of the water-resistant support include a plastic sheet, printing-resistant paper, an aluminum plate, a zinc plate, and a copper plate.
Bimetal plates such as aluminum plate, copper-stainless plate, chrome-copper plate, chrome-copper-aluminum plate, chrome-
A trimetal plate such as a lead-iron plate, a chromium-copper-stainless plate, or the like, having a thickness of 0.1 to 3 mm, preferably 0.1 to 1 mm is preferable. In addition, paper having a thickness of 80 μm to 200 μm and subjected to a water-resistant treatment, plastic film or paper laminated with a metal foil, or a plastic film may be used.

The water-resistant support preferably has conductivity, and at least the portion immediately below the image receiving layer preferably has a specific electric resistance of 10 ¹⁰ Ωcm or less. The above-mentioned specific electric resistance value is more preferably 10 ⁸ Ωcm or less, and the smaller the resistance value, the more preferable.

In order to impart the above-mentioned conductivity to the portion of the support immediately below the image receiving layer on a substrate such as paper or film, a layer comprising a conductive filler such as carbon black and a binder is applied. Or a method of attaching a metal foil or vapor-depositing a metal.

On the other hand, examples of the support having conductivity as a whole include conductive paper impregnated with sodium chloride and the like, plastic films mixed with a conductive filler such as carbon black, and metal plates such as aluminum. Can be

When the charged ink droplets adhere to the image receiving layer in the electric field control type ink jet recording within the above conductivity range, the charges of the ink droplets quickly disappear through the ground plane, and no disturbance occurs. A clear image is formed. The measurement of the specific electric resistance (also called the specific electric resistance of the volume or the specific electric resistance) is carried out according to JIS K-
The test was performed by a three-terminal method in which a guard electrode was provided based on 6911.

Further, a case where the whole support has conductivity will be described. For example, it can be obtained by using a conductive base paper impregnated with sodium chloride or the like on a substrate and providing a water-resistant conductive layer on both surfaces thereof.

In the present invention, as the base paper used as the substrate, for example, wood pulp paper, synthetic pulp paper, or a mixed paper of wood pulp paper and synthetic pulp paper can be used as it is. The thickness of the base paper is 80 μm to 200 μm.
m is preferred.

Next, formation of the conductive layer will be described.

The formation of the conductive layer is achieved by applying a layer containing a conductive filler and a binder to both sides of the conductive paper. The thickness of the applied conductive layer is 5 μm to 2 μm.
0 μm is preferred.

Examples of the conductive filler include particulate carbon black, graphite, metal powder such as silver, copper and nickel, tin oxide powder, flake aluminum or nickel, fibrous carbon, brass, aluminum, copper, and the like. And stainless steel.

On the other hand, as the resin used as the binder, various resins are appropriately selected and used. Specifically, as the hydrophobic resin, for example, acrylic resin, vinyl chloride resin, styrene resin, styrene-butadiene resin, styrene-acrylic resin, urethane resin,
Vinylidene chloride-based resins, vinyl acetate-based resins, and the like, and examples of hydrophilic resins include polyvinyl alcohol-based resins, cellulose derivatives, starch and its derivatives, polyacrylamide-based resins, and styrene-maleic anhydride-based copolymers. Can be

Another method for forming the conductive layer is to laminate a conductive thin film. As the conductive thin film, for example, a metal foil, a conductive plastic film, or the like can be used. More specifically, an aluminum foil is used as a metal foil laminate, and a polyethylene resin mixed with carbon black is used as a laminate of a conductive plastic film. The aluminum foil may be either hard or soft and has a thickness of 5μ.
m to 20 μm are preferred.

The lamination of the polyethylene resin mixed with carbon black is preferably an extrusion lamination method.
The extrusion laminating method is a method in which a polyolefin is melted by heat, formed into a film, immediately pressed against base paper, and then cooled and laminated. Various apparatuses are known. The thickness of the laminate layer is preferably from 10 μm to 30 μm. When a plastic film or a metal plate having conductivity is used as a substrate as a substrate having conductivity as a whole, it can be used as it is as long as it has sufficient water resistance.

As a plastic film having conductivity, for example, a polypropylene or polyester film mixed with a conductive filler such as carbon fiber or carbon black can be used. As a metal plate, aluminum or the like can be used. The thickness of the substrate is preferably 80 μm to 200 μm. If it is less than 80 μm, the strength as a printing plate is insufficient,
If it exceeds 200 μ, handling properties such as transportability in the drawing apparatus deteriorate.

Next, a structure in which a layer having conductivity is provided will be described.

The water-resistant substrate has a thickness of 80 μm to 200 μm.
Paper, plastic film, paper or plastic film laminated with a metal film subjected to a water resistance treatment of μ can be used.

As a method of forming a conductive layer on the substrate, the method described above in the case where the whole support has conductivity can be used. That is, it can be obtained by applying a layer containing a conductive filler and a binder at a thickness of 5 μm to 20 μm on one surface of the substrate, or by laminating a metal foil or a conductive plastic film. As a method other than the above, for example, a metal film such as aluminum, tin, palladium, or gold may be provided on a plastic film. As described above, a water-resistant support having conductivity with an intrinsic electric resistance of 10 ¹⁰ Ωcm or less can be obtained.

Further, in the present invention, the smoothness of the surface of the support on the side adjacent to the image receiving layer is determined by a Beck smoothness of 300.
(Sec / 10 cc) or more, preferably 900 to 3000 (sec / 10 cc), more preferably 1000 to 3000 (sec / 10 cc).

By regulating the smoothness of the surface of the support on the side adjacent to the image receiving layer to a Beck smoothness of 300 (sec / 10 cc) or more, image reproducibility and printing durability can be further improved. . Such an improvement effect can be obtained even if the smoothness of the image receiving layer surface 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. Conceivable.

The highly smooth surface of the water-resistant support thus regulated refers to the surface on which the image-receiving layer is directly applied. For example, the underlayer of the conductive layer, the overlayer, When a coat layer is provided, it refers to 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 above range, various conventionally known methods can be used. Specifically, a method of adjusting the Beck smoothness of the surface of the support by a method such as a method of melting and bonding the substrate surface with a resin, a method of strengthening a calendar with a highly smooth heat roller, and the like can be used.

In the present invention, as described above, an under layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a curl preventing layer is provided on the surface of the support opposite to the image receiving layer. A backcoat layer (backside layer) can be provided for the purpose, but the backcoat layer preferably has a smoothness in the range of 150 to 700 (sec / 10 cc). 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.

In the case where the smoothness of the under layer and the back coat layer of such a support is individually adjusted, for example, a calendering process is performed once after the under layer is formed, and a calendering process is performed again after the back coat layer is formed. In addition, the process of calendar processing is performed multiple times,
For example, the proportion of the pigment in the under layer and the back coat layer
It is desirable to control the smoothness by a combination of adjustment on composition such as particle size and adjustment of calendering conditions.

Such a back coat layer is formed by applying a coating solution containing a resin, a pigment and the like on a support, drying and laminating. The resin used here is appropriately selected and used. Specifically, the same resin as that used for the above-described conductive layer (under layer) can be used.

The pigments 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. Since a lower smoothness is required in the back coat layer as compared with the under layer, a larger particle size, specifically, about 0.5 to 10 μm is used. Particle size pigments are preferably used. In addition, it is preferable to use the pigment as described above at a ratio of 80 to 200 parts by weight with respect to 100 parts by weight of the resin. In order to obtain excellent water resistance, the under layer and the back coat layer described above are effective 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 the lithographic printing plate precursor according to the present invention, a solution containing an under layer component is coated on one side of the support, if necessary, to form an under layer. A solution containing a component of a back coat layer is applied to the surface and dried to form a back coat layer, and then a coating solution containing a component of an image receiving layer is applied and dried to form an image receiving layer. The application amount of the back coat layer is 1 to 30 g /
m ² , especially 6 to 20 g / m ² is suitable.

More preferably, the water-resistant support provided with an under layer or a back coat layer has a thickness of 9
0-130 μm, preferably 100-120 μm
Range.

An image receiving layer is provided on the water-resistant support. The thickness of the provided image receiving layer is suitably in the range of 5 to 50 μm.

The image receiving layer comprises, for example, a water-soluble binder, an inorganic pigment and a water-proofing agent as main components. As the binder, PVA, modified PVA such as carboxy PVA, starch and derivatives thereof, CMC, hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer,
A water-soluble resin such as a styrene-maleic acid copolymer is used.

Examples of the water-proofing agent include initial condensates of aminoplasts such as glyoxal, melamine formaldehyde resin and urea formaldehyde resin, modified polyamide resins such as methylolated proamide resin, and polyamide / polyamine / epichlorohydrin resins. Examples of the inorganic pigment include kaolin, clay, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, and alumina. Among them, silica is preferable.

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

Next, a method of forming an image on the lithographic printing plate precursor (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 path 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 structure of an ink jet recording apparatus as in the apparatus system of FIG. 2 and 3, members common to FIG. 1 are denoted by common reference numerals. FIG. 2 is a schematic configuration diagram showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

As shown in FIGS. 2 and 3, the head 10 provided in the ink jet recording apparatus has a slit sandwiched between the upper unit 101 and the lower unit 102. Has become
The ejection electrode 10b is arranged in the slit, and the oil ink 11 is filled in the slit.

In the head 10, a voltage is applied to the ejection electrode 10b in accordance with a digital signal of image pattern information. As shown in FIG. 2, a counter electrode 10c is provided so as to face the discharge electrode 10b.
A master 2 is provided above. By applying the voltage, a circuit is formed between the discharge electrode 10b and the counter electrode 10c, and the oil-based ink 11 is discharged from the discharge slit 10a of the head 10 to form an image on the master 2 provided on the counter electrode 10c. Is done.

It is preferable that the width of the discharge electrode 10b is as narrow as possible in order to form a high-quality image, for example, for printing. For example, an oil-based ink is
And using the discharge electrode 10b having a tip of 20 μm width,
By setting the distance between the ejection electrode 10b and the counter electrode 10c to 1.5 mm and applying a voltage of 3 KV for 0.1 millisecond between the electrodes, a dot of 40 μm can be formed on the master 2.

[0173]

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

Production Example 1 of Dispersion Stabilizing Resin (P) 1: Resin (P-1) A mixed solution of 100 g of octadecyl methacrylate, 0.6 g of divinylbenzene and 200 g of toluene was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. did. 2,2'-
Azobis (isobutyronitrile) (abbreviated as AIB)
N. ) Was added and reacted for 4 hours. Further, A. I.
B. N. Was added and reacted for 2 hours. I.
B. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 1.5 l of methanol, and the powder was collected by filtration and dried to obtain 88 g of a white powder. The weight average molecular weight (abbreviated as Mw) of the obtained polymer was 3.3.
× 10 ⁴ (Mw represents a value in terms of polystyrene by the GPC method; the same applies hereinafter).

Production Examples 2-14 of Dispersion Stabilizing Resin (P):
Resins (P-2) to (P-14) In Production Example 1 of dispersion stabilizing resin (P), monomers (A) and (D) in Table 1 below were used instead of octadecyl methacrylate and divinylbenzene. The dispersion stabilizing resins were produced in exactly the same manner as in Production Example 1 except for using. Mw of each resin is 3.0 × 10 ^{4 to} 5 × 10
^{I got 4} .

[0176]

[Table 1]

Production Example 1 of Dispersion Stabilizing Resin (PA) Resin (PA-1) 97 g of octadecyl methacrylate, 3 g of thioglycolic acid, 5.0 g of divinylbenzene and 200 parts of toluene
g of the mixed solution was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 0.8 g of 1,1'-azobis (cyclohexane-1-carbonitrile) (abbreviated as ACHN) was added and reacted for 4 hours. Further, A. C. H. N. Was added and reacted for 2 hours. C. H. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 1.5 l of methanol, and the powder was collected by filtration and dried to obtain 88 g of a white powder. Mw of the obtained polymer is 3
× 10 ⁴ .

Production Examples 2-9 of Dispersion Stabilizing Resin (PA):
Resins (PA-2) to (PA-9) In Production Example 1 of dispersion stabilizing resin (PA), monomers (A) and (D) in Table 2 below were used instead of octadecyl methacrylate and divinylbenzene. The dispersion stabilizing resins were produced in exactly the same manner as in Production Example 1 except for using. Mw of each resin is 2.5 × 10 ⁴ to 4 × 10
^{I got 4} .

[0179]

[Table 2]

Production Example 10 of Dispersion Stabilizing Resin (PA) Resin (PA-10) 97 g of octadecyl methacrylate, 3 g of thiomalic acid
A mixed solution of 4.5 g of divinylbenzene, 150 g of toluene and 50 g of ethanol was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. A. I. B. N. 0.5g
The reaction was performed for 5 hours. Further, A. I. B. N. 0.3g
In addition, the reaction was carried out for 3 hours. I. B. N. To 0.
2 g was added and reacted for 3 hours. After cooling, the mixed solution was reprecipitated in 2 liters of methanol, and the powder was collected by filtration and dried to obtain 85 g of a white powder. Mw of the obtained polymer was 3.5 × 10 ⁴ .

Production Examples 11 to 1 of Dispersion Stabilizing Resin (PA)
6: Resins (PA-11) to (PA-16) Except for using the mercapto compounds shown in Table 3 below in place of thiomalic acid in Production Example 10 of the dispersion stabilizing resin (PA), exactly the same as in Production Example 10 By operation, each dispersion stabilizing resin was manufactured.

[0182]

[Table 3]

Production Example 17 of Resin for Stabilizing Dispersion (PA): Resin (PA-17) A mixture of 94 g of hexadecyl methacrylate, 0.5 g of divinylbenzene, 150 g of toluene and 50 g of isopropyl alcohol was stirred at a temperature of 9 while stirring under a nitrogen stream.
Warmed to 0 ° C. 6 g of 2,2'-azobis (4-cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours.
After cooling, the mixed solution was reprecipitated in 1.5 l of methanol, and the powder was collected by filtration and dried to obtain 83 g of a white powder. Mw of the obtained polymer was 6.5 × 10 ⁴ .

Production Example 18 of Dispersion Stabilizing Resin (PA): Resin (PA-18) 92 g of docosanyl methacrylate, ISP-22GA
A mixed solution of 1.5 g (manufactured by Okamura Oil Co., Ltd.), 150 g of toluene and 50 g of ethanol was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 4,4'-azobis (4-
8 g of (cyanopentanol) was added and reacted for 8 hours. After cooling, the mixed solution was reprecipitated in 1.5 l of methanol, and the powder was collected by filtration and dried to obtain 78 g of a white powder.
Mw of the obtained polymer was 4.1 × 10 ⁴ .

Production Example 19 of Dispersion Stabilizing Resin (PA) Resin (PA-19) A mixed solution of 95 g of octadecyl methacrylate, 5 g of 2-mercaptoethylamine, 5 g of divinylbenzene and 200 g of toluene was stirred at a temperature of 85 under a nitrogen stream.
Warmed to ° C. A. C. H. N. Was added and reacted for 8 hours. Next, 8 g of glutaconic anhydride and 1 ml of concentrated sulfuric acid were added and reacted at a temperature of 100 ° C. for 6 hours. After cooling, the reaction solution was reprecipitated in 1.5 liters of methanol, and the powder was collected by filtration and dried to obtain 83 g of a white powder.
I got Mw of the obtained polymer was 3.1 × 10 ⁴ .

Preparation Example of Latex Particle 1: Latex Particle (D-1) Dispersion stabilizing resin (P-1) 16 g, vinyl acetate 100 g
A mixture of 0.8 g of octadecyl methacrylate and 348 g of Isopar H was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 2,2′- as a polymerization initiator
Azobis (isovaleronitrile) (abbreviated as AIV.
N. ) Was added and reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of an initiator was added, and after reacting for 2 hours, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 93% and an average particle size of 0.22 μm. Particle size is CAPA-
500 (manufactured by Horiba, Ltd.).

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour), sedimented resin particles were collected and dried, and the weight average molecular weight (weight average molecular weight) of the resin particles was measured. Mw) and the glass transition point (Tg) were measured. As a result, Mw was 8 × 10 ⁴ (polystyrene conversion value by GPC; the same applies hereinafter), and Tg was 38 ° C.

Latex Particle Production Examples 2 to 11: Latex Particles (D-2) to (D-11) In the latex particle production example 1, the following table was used in place of the dispersion stabilizing resin (P-1) and octadecyl methacrylate. 4. The dispersion stabilizing resin and the monomer (B) according to 4.
Except for using (0.005 mol), the latex particles of the present invention (D-2) to
(D-11) was produced.

[0189]

[Table 4]

The polymerization rate of the obtained latex particles is 88 to
At 95%, the average particle size was in the range of 0.15 to 0.25 µm and the monodispersity was good. Further, Mw of each resin particle was 8 × 10 ⁴ to 2 × 10 ⁵ , and Tg was within a range of 36 to 39 ° C.

Production Example 12 of Latex Particles: Latex Particles (D-12) A mixed solution of 14 g of a dispersion stabilizing resin (PA-14) and 177 g of Isopar H was stirred at a temperature of 6 under a nitrogen stream.
Warmed to 0 ° C. 30 g of methyl methacrylate, 70 g of methyl acrylate, 0.6 of octadecyl acrylate
g, 200 g of Isopar G and A. I. V. N. Was added dropwise over 2 hours, followed by stirring for 2 hours. Further, A.I. I. V. N. Was added to the mixture, and the mixture was heated to 85 ° C. and stirred for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 100% and an average particle size of 0.22 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.). Mw of resin particles is 3 × 10 ⁵ , Tg is 28
° C.

Latex Particle Production Examples 13 to 21: Latex Particles (D-13) to (D-21) Monomer (A) (ie, methyl methacrylate and methyl acrylate) used in latex particle production example 12 Except that the compounds shown in Table 5 below were used in place of the monomer (B) (that is, octadecyl acrylate) and the dispersion stabilizing resin (PA-14), the present invention was carried out in the same manner as in Production Example 12 above. Latex particles (D-13) to (D-21) were produced.

[0193]

[Table 5]

The polymerization rate of the obtained latex particles is 95 to 95.
At 100%, the average particle size was in the range of 0.18 to 0.25 µm and the monodispersity was good. The Mw of each resin particle was in the range of 1 × 10 ^{5 to} 3 × 10 ⁵ .

Production Example 22 of Latex Particles: Latex Particles (D-22) [Comparative Example A] Except for using 0.8 g of octadecyl methacrylate as the monomer (B) used in Production Example 1 of latex particles, Comparative Latex Particles (D-22) were produced in exactly the same manner as in Production Example 1.

The polymerization rate of the obtained latex particles was 95%.
The average particle size was 0.21 μm. The Mw of the resin particles was 1 × 10 ⁵ , and the Tg was 38 ° C.

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

(Composition 1) Gelatin 10 g Silica: Sylysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 3 g Colloidal silica 20% solution Snowtec C (manufactured by Nissan Chemical Industries, Ltd.) 12.5 g Fluoroalkyl ester: FC430 (3M Co.) 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

A base metal ME 100TS having a vapor-deposited aluminum layer provided on a plate surface of a pet film having a thickness of 100 μm.
(Toyo Metallizing Co., Ltd.) as a support,
The above composition was applied thereon using a wire bar, and 1
After drying at 00 ° C. for 10 minutes, an image receiving layer having a coating amount of 15 g / m ² was formed, and a lithographic printing original plate was obtained. The surface Bekk smoothness was 300 (sec / 10 cc), and the contact angle with water was 0 degree.

<Preparation of oil-based ink (IK-1)> Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 9)
(5/5 weight ratio), 10 g of alkali blue and 30 g of Shellsol 71 were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of alkali blue. . 50 g (as solid content) of latex particles (D-1) of Production Example 1 of latex particles, 18 g of the above-mentioned alkali blue dispersion,
20 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol) and 0.10 g of octadecene-maleic acid octadecylamide copolymer were added to Isopar G.
Was diluted to 1 liter to obtain a blue oil-based ink.

Using the lithographic printing plate prepared as described above, a servoproter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing an output from a personal computer, was modified, and the ink ejection head shown in FIG. , 1.5
Printing was performed on the lithographic printing original plate placed on the counter electrode spaced at a distance of mm using the oil-based ink (IK-1) described above. At the time of plate making, the aluminum deposition layer immediately below the image receiving layer of the printing original plate and the counter electrode were electrically connected using a silver paste. Continue to RICOHFUSE
Using an R model 592 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 65 ° C. and heated for 10 seconds to sufficiently fix the image area.

When the copied image of the obtained plate-making product (that is, the printing plate) was visually observed with an optical microscope at a magnification of 200 times, there was no problem in the copied image, fine lines and fine characters were good, and bleeding, lack, and blur were observed. No abnormalities were observed, and no contamination was observed in the non-image area.

This printing plate was used as immersion water for SLM-O
D (manufactured by Mitsubishi Paper Mills Co., Ltd.) was diluted 50 times with water, and printing was performed with black ink for offset printing using Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) as a printing material.
As a result, a printed image has a sharpness of 3
More than 1,000 were obtained.

Next, when an ink ejection test was performed using the above-mentioned ink jet printer, stable ink ejection was obtained even for 800 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 the plate-making printing plate under these conditions was actually printed, 3,000 or more printed matters having clear images without background smear were obtained.

Further, the evaluation was performed under the forced redispersibility of the ink. That is, the ejection head used in the printer is filled with ink, removed, left at 35 ° C. for 3 days, then the ejection head is immersed in Isopar G for 30 minutes, and then lightly stirred, the ink (IK-1) is slit. Everything was removed from within. That is, it is considered that the ink (IK-1) adhering to the slit tip of the ejection head in a state of no fluidity when left undisturbed was easily redispersed by solvation with the dispersion.

Comparative Example A In Example 1, instead of the oil-based ink (IK-1), the following oil-based ink (IK-1) was used.
Except using KR-1), it carried out similarly to Example 1.

<Preparation of Comparative Oil-Based Ink (IKR-1)> In the oil-based ink (IK-1), the comparative latex particles (D-2) were used instead of the latex particles (D-1).
2) Except that 50 g (as solid content) was used, it was prepared in the same manner as the ink (IK-1).

The lithographic printing plate obtained using the above Comparative Example A was printed first, and as in Example 1, 3,000 or more printed matters having clear images without stains were obtained. However, in the ink ejection test, the ink ejection of Comparative Example A became unstable after about 300 hours. In the ink of Comparative Example A stored for 6 months, a coagulated sediment was deposited and did not redisperse even after shaking.

Further, for Comparative Example A, a forced test of the ink redispersibility was performed under the same conditions as in Example 1. As a result, extraneous matter remained in the slit at the ejection head portion.

As described above, the oil-based ink of the present invention has good ink ejection stability even when plate making is performed continuously for a long period of time.
Even when a clear image without stains is formed and printing is performed as a printing plate, high printing durability is exhibited.

Examples 2 to 8 A high-grade paper weighing 100 g / m ² was used as a substrate, and a coating for a back layer having the following composition was applied to one surface of the substrate using a wire bar, and the dry coating amount was 12 g / m 2. ^{After the second} backing layer was provided, calendering was performed so that the smoothness of the backing layer was about 50 (sec / 10 cc).

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

Next, under layer coatings A to G (detailed in Table 6) having the following composition were applied to the other surface of the substrate using a wire bar, and the under layer having a dry coating amount of 10 g / m ^{2 was} applied. Is provided, the smoothness of the under layer is 1500 (seconds / 1
Calendar processing was performed so as to be about 0 cc). The seven types of the thus obtained water-resistant supports were each used as a support sample No. in accordance with the coating amounts A to G as shown in Table 6.
2 to No. 8.

[0214]

[Table 6]

<Coating for under layer> Carbon black (30% aqueous dispersion) Clay (50% aqueous dispersion) SBR latex (solid content 50%, Tg 25 ° C.) Melamine resin (solid content 80%, Sumi Let's Resin SR
-613) The above components were mixed with the compositions shown in Table 6, and water was added so that the total solid content concentration was 25% to obtain coating solutions for underlayer coatings A to G.

1) Specific Electric Resistance Value of Under Layer The specific electric resistance value of the under layer was measured as follows. Each of the under layer coatings A to G was applied to a sufficiently degreased and washed stainless steel plate, and a dry coating amount of 10 g / g was applied.
and a coating film of m ^2. With respect to the obtained seven types of samples, the specific electric resistance value was measured by a three-terminal method provided with a guard electrode based on JIS K-6911. The results are shown in Table 7.

[0219]

[Table 7]

Next, on support sample Nos. 2 to 8,
The same image-receiving layer dispersion as used in Example 1 was dried, and the image-receiving layer was provided so that the coating amount was 6 g / m ² , thereby obtaining lithographic printing plate precursor samples No. 2 to No. 8, respectively. .

Using Samples No. 2 to No. 8 of the lithographic printing plate precursor prepared as described above, in the same manner as in Example 1,
Plate making was performed using an oil-based ink (IK-1). At the time of plate making, the under layer provided directly below the image receiving layer of the printing original plate samples No. 2 to No. 8 and the counter electrode were electrically connected using a silver paste.

Next, after making the plate as described above, using a fully automatic printing machine (AM-2850, trade name of AM Co., Ltd.), the SLM-OD was diluted 50 times with distilled water as dampening water. The diluted solution was placed in a fountain solution receiving pan, and printed using a black ink for offset printing and passed through a plate to a printing machine.

The image quality of the drawn image of the plate-making product thus obtained was evaluated as follows. Table 8 shows the results.

[0222]

[Table 8]

1) Image quality of plate making The drawing image of the plate making obtained was measured with an optical microscope for 200 hours.
It was observed and evaluated at a magnification of 1 ×. In the table, ◎, ◎, and × are shown. ◎ There is no problem in the drawn image, and fine lines and fine characters are very good. ○ There is no problem in the drawn image, fine lines and fine characters are good. × The fine line and fine characters are missing or blurred and defective.

2) Printed Image When the image of the obtained printed matter was evaluated in the same manner as in the above-described plate making image quality, the print image quality was exactly the same as the plate making image quality.

3) Printing Durability The number of printed sheets until the background smear of the printed matter or the lack of the image was visually discriminated was examined.

Referring to the specific electric resistance values in Table 7, Table 8
Let us consider the result. Specific electric resistance value is 10 ¹² -1
0 ¹¹ Ωcm and large original sample No. 2 and No. No. 3 lacks or blurs the image. Also, since the resin layer of the drawn image becomes thin as a result of bleeding, the printing durability is low, while the original sample No. ¹ having a specific electric resistance of as small as 10 ⁸ to 102 Ωcm. 5-No. No. 8 has no problem at all in the image, and fine lines and fine characters are very good. High printing durability.

That is, the higher the conductivity of the support underlayer immediately below the image receiving layer, the better the quality of plate making and printing.

Example 9 <Preparation of a lithographic printing plate precursor> A composition 2 having the following content was mixed with glass beads in a paint shaker (Toyo Seiki Co., Ltd.)
And dispersed for 60 minutes, and then the glass beads were separated by filtration to obtain a dispersion.

(Composition 2) Gelatin 10 g Silica: Sylysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 3 g Alumina sol 10% solution (manufactured by Nissan Chemical Industries, Ltd.) 10.3 g 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 0.30 g Water 54 g

Dispersion of Underlayer Formulation F used in Example 7 on a support of ELP-IX master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing The product was applied to a thickness of 6 g / m ² using a support provided with an under layer, and the composition was applied thereon using a wire bar and dried at 100 ° C. for 10 minutes. An image receiving layer having a coating amount of 18 g / m ² was formed.
A lithographic printing original plate was obtained. Surface Beck smoothness is 250
(Second / 10 cc), and the contact angle with water was 0 degree.

<Preparation of oil-based ink (IK-2)> 10 g of poly (dodecyl methacrylate), 10 g of nigrosine
g and 30 g of Isopar were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine. 50 g of latex particles (D-15) of Production Example 15 of latex particles
A black oil-based ink was prepared by diluting 35 g of the above nigrosine dispersion, 20 g of isostearyl alcohol and 0.08 g of [octadecyl vinyl ether-hemo maleic acid dodecylamide] copolymer (as solid content) into 1 liter of Isopar G. did.

Using this printing original plate and the oil-based ink (IK-2), plate making was performed in the same manner as in Example 1 to obtain a printing plate.
Offset printing was performed. The obtained printed matter was obtained in Example 1.
As in the case of the printing plate of No. 5, the image quality was clear with no stain on the non-image area, and the printing durability was as good as 3,000 or more.
Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 1000 hours showed the same performance as that of the ink (IK-1) and was excellent.

Examples 10 to 23 Plate making and printing were performed in the same manner as in Example 1 except that the oil-based ink (IK-1) was replaced with the oil-based ink shown in Table 9 below. The oil-based ink used was the oil-based ink (IK-1) in which latex particles (D-
It was prepared in the same manner except that 45 g (as solid content) of the resin particles shown in Table 9 below were used instead of 1).

[0234]

[Table 9]

It was found that each plate had the same image quality as the printing plate of Example 1, and the printing durability was 3,000 or more. Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 1000 hours showed the same performance as that of the ink (IK-1) and was excellent.

Example 24 Plate making and printing were performed in the same manner as in Example 9, except that the oil ink (IK-17) having the following content was used instead of the oil ink (IK-2). .

<Preparation of oil-based ink (IK-17)> The white dispersion (D-1) obtained in Production Example 11 of latex particles was prepared.
1) A mixture of 500 g and Sumicaron Black 7.5 g was heated to a temperature of 100 ° C. and stirred with heating for 6 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, thereby obtaining a black resin dispersion having an average particle size of 0.22 μm. 250 g of the above black resin dispersion,
0.08 g of charge control material (CD-3) with the following structure, FOC
A black oil-based ink was prepared by diluting 30 g of -1600 (hexadecyl alcohol, manufactured by Nissan Chemical Industries, Ltd.) into 1 liter of Isopar G.

[0238]

Embedded image

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 9.
The printing durability was as good as 5,000 or more. Also, as in Example 9, the ink ejection test and the redispersibility compulsory test for 1000 hours showed the same performance as that of the ink (IK-1) and was excellent.

Example 25 Plate making and printing were performed in the same manner as in Example 1, except that the oil ink (IK-18) having the following content was used instead of the oil ink (IK-1). .

<Preparation of oil-based ink (IK-18)> The white dispersion (D-2) obtained in Production Example 21 of latex particles was prepared.
1) A mixture of 300 g and 5 g of Victoria Blue B was heated to a temperature of 100 ° C. and heated and stirred for 4 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, thereby obtaining a black resin dispersion having an average particle size of 0.20 μm. 260 g of the above black resin dispersion, 0.07 g of zirconium naphthenate, FOC-1600
(Nissan Chemical Co., Ltd., hexadecyl alcohol) 20 g
Was diluted to 1 liter of Shellsol 71 to prepare a blue oil-based ink.

The obtained printed material has a clear image quality without stain on the non-image portion, similarly to the printing plate of Example 1.
The printing durability was as good as 3,000 sheets or more. Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 1000 hours showed the same performance as that of the ink (IK-1) and was excellent.

Example 26 <Preparation of a lithographic printing plate precursor> A composition 3 having the following content was mixed with glass beads in a paint shaker (Toyo Seiki Co., Ltd.)
And dispersed for 80 minutes, and then the glass beads were separated by filtration to obtain a dispersion.

(Composition 3) Silica: Silicia 445 (manufactured by Fuji Silysia Chemical Ltd.) 40 g Colloidal silica 20% solution Snowtec C (manufactured by Nissan Chemical Industries, Ltd.) 200 g Clay 50% dispersion 40 g polyvinyl alcohol: PVA-11710% solution (manufactured by Kuraray Co., Ltd.) 120 g Melamine resin 2.0 g Ammonium chloride 0.2 g Water 50 g

As the support, the support of Example 8 was used.
Apply the dispersion using a wire bar, dry,
An image receiving layer having a coating amount of 20 g / m ² was formed to obtain a lithographic printing original plate. The Beck smoothness of the surface of the image receiving layer of this master was 150 (sec / 10 cc), and the contact angle with water on the surface was 0 degree.

This printing original plate was prepared in the same manner as in Example 8,
Plate making was performed, and offset printing was performed as a printing plate. The obtained printed material had a clear image quality with no stain on the non-image area, as in the printing plate of Example 8, and the printing durability was as good as 5,000 or more.

Examples 27 to 36 Plate making and printing were carried out in the same manner as in Example 9 except that the oil-based ink (IK-2) was replaced with the oil-based ink shown in Table 10 below. The oil-based ink used is
In the oil-based ink (IK-2), the resin particles (D-1)
It was prepared in the same manner except that 45 g (as solid content) of the resin particles shown in Table 10 below were used instead of 5).

[0248]

[Table 10]

It was found that each plate had the same image quality as the printing plate of Example 9, and the printing durability was 3,000 or more. Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 1000 hours showed the same performance as that of the ink (IK-1) and was excellent.

[0250]

As described above, according to the present invention, ink jet recording is stably performed even when used repeatedly, and ink jet type plate making printing excellent in printing durability, redispersibility, storage stability and printing durability. It has become possible to realize an ink for an ink-jet type plate-making printing plate in which the plate manufacturing method and the ink discharge are stable without clogging of nozzles and ink supply paths.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system used in the present invention.

FIG. 2 is a schematic configuration diagram illustrating a main part of an inkjet recording apparatus used in the present invention.

FIG. 3 is a partial sectional view of a head of an ink jet recording apparatus used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ink jet recording apparatus 2 Master 3 Computer 4 Pass 10 Head 10a Discharge slit 10b Discharge electrode 10c Counter electrode 11 Oil-based ink 101 Upper unit 102 Lower unit

Claims (7)

[Claims] 1. A lithographic plate having a lithographically printable hydrophilic surface
On the printing master, an electric resistance of 10⁹ Ωcm or more and dielectric constant
In a non-aqueous carrier liquid of 3.5 or less, at least resin particles are separated.
Inject the scattered oil-based ink from the nozzle in the form of droplets.
Oil-based for plate-making printing plates that form images by ink jet method
In the ink, the dispersed resin particles are:
Non-aqueous solvents that are at least miscible with the non-aqueous carrier liquid
Monofunctional, soluble and insoluble by polymerization
At least one of the monomers (A), (ii) the monomer (A)
Represented by the following general formula (I) copolymerizable with
At least one of (B) and (iii) the following general formula (II)
A polymer containing a repeating unit represented by
Part of the polymer main chain is crosslinked and soluble in the non-aqueous solvent
Contains at least one kind of resin (P) for dispersion stability
A polymer obtained by polymerizing a solution
Oil-based ink for ink-jet plate-making printing plates. Embedded imageIn the general formula (I),¹Is an aliphatic group having 8 or more carbon atoms,
Is a total of 8 or more atoms (however, a hydrogen atom bonded to carbon and nitrogen
The substituent represented by the following general formula (III)
You. Formula (III)-(A¹ -B¹ )_m-(A^Two -B^Two )_n-R^{twenty one} In the formula (III), R^{twenty one}Is a hydrogen atom or a fatty acid having 1 to 18 carbon atoms
Represents an aliphatic group. B¹ And B^Two Are the same but different
Each may be -O-, -S-, -CO-, -C
O_Two-, -OCO-, -SO_Two-, -N (R^{twenty two})-, -C
ON (R^{twenty two})-, -N (R^{twenty two}) CO-, -N (R^{twenty two}) S
O_Two-, -SO_TwoN (R^{twenty two})-, -NHCO_Two-Or-
NHCONH- (where R^{twenty two}Is the above R^{twenty one}Synonymous with
Is). A¹ And A^Two Are the same but different
Or a group represented by the following general formula (III
a) a hydrocarbon group having 1 to 18 carbon atoms
At least one group selected from the following (provided that two or more
In the case of, these groups of formula (IIIa) and / or hydrocarbon groups
Represents a bond). Embedded imageIn the formula (IIIa), B^Three And B^Four Are the same but different
The above B ¹ , B^Two Represents the same content as^Four 
Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.
Then R^{twenty three}Is R^{twenty one}Indicates the same content as m, n and p
May be the same or different from each other, and each of 0 to 4
Represents an integer. However, there is no possibility that m + n + p = 0. formula
(I), U¹ Is -COO-, -CONH-, -CON
(R¹¹)-[Where R¹¹Is an aliphatic group or the general formula
Represents a substituent represented by (III)], -OCO-, -CO
NHCOO-, -CH_TwoCOO-,-(CH_Two)_kOCO
-, [Where k represents an integer of 1 to 4], -O-,-
C₆H_Four-Or -C₆H_FourRepresents -COO-. a¹and
a^TwoMay be the same or different from each other;
Atom, halogen atom, cyano group, alkyl group, -COO
-R¹²Or -CH_TwoCOO-R¹²(Where R¹²Is fat
Represents a group). Embedded imageIn the formula (II), X¹Is -COO-, -OCO-, -CH_TwoO
CO-, -CH_TwoCOO-, -O- or -SO_Two-
You. Y¹Represents an aliphatic group having 10 to 32 carbon atoms. b¹And
And b^TwoMay be the same or different from each other, and have the formula (I)
A in¹, A^TwoIs synonymous with 2. In the dispersion stabilizing resin (P), at least one polymer main chain has -PO ₃ H ₂ ,-
_{SO 3 H, -COOH, -P (} = O) (OH) R 1 [wherein R ¹ represents a hydrocarbon group or -OR ^2, (R ² represents a hydrocarbon group)], -OH, formyl group, -CONR ³ R ^4,
-SO ₂ NR ³ R ⁴ (where R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), containing at least one polar group selected from a cyclic acid anhydride-containing group and an amino group The oil-based ink for an ink-jet type plate-making printing plate according to claim 1. 3. An oily material comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5 on a lithographic printing plate having a lithographically printable hydrophilic surface. 3. A method for producing a plate-making printing plate for forming an image by an ink-jet method in which ink is ejected from a nozzle in the form of droplets according to claim 1 or 2. 4. The method according to claim 3, wherein the oil-based ink is discharged from a nozzle using an electrostatic field. 5. The lithographic printing plate precursor has an image-receiving layer capable of lithographic printing on a water-resistant support and having at least a hydrophilic surface, and the water-resistant support is provided at least immediately below the image-receiving layer. 5. The method for producing an ink-jet type plate-making printing plate according to claim 3, wherein the specific resistance of the portion is 10 ¹⁰ Ω · cm or less. 6. The specific resistance of the entire water-resistant support is 10
^The method for producing an ink-jet type plate-making printing plate according to claim 5, which has a resistivity of ¹⁰ Ω · cm or less. 7. The method according to claim 3, wherein the resin particles dispersed in the oil-based ink are positively or negatively charged.