JPH1178226A - Oil based ink for ink jet type process printing plate and method for forming of ink jet type process printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve conservation stability by a method wherein a solution containing at least one kind of specific monofunctional monomer, at least one kind of a monomer expressed by the formula I capable of being copolymerized with the monomer, and at least one kind of dispersion stabilizing resin containing copolymer constituent expressed by the formula II, is reacted by polymerization to prepare a dispersible resin particle. SOLUTION: A dispersible resin particle of oil based ink is polymerized by reacting with solution containing at least one kind of monofunctional monomer which is soluble in non-aqueous soluvent miscible in non-aqueous carrier liquid and polymerized to become insoluble, at least one kind of a monomer expressed by the formula I capable of being copolymerized with the polymer (in the formula, E' expresses a substitute indicated by the formula III -(A1 -B1 )m-(A2 -B2 )n -R21 of 8 or over C aliphatic group or the like, U<1> expresses -COO-, -CONH-, etc., and a<1> , a<2> express hydrogen atom, halogen atom, etc.), and at least one kind of dispersion stabilizing resin containing a copolymeric constituent indicated by the formula II which is soluble in non aqueous solvent (in the formula, R<1> expresses 10 to 32C alkyl group or the like, b<1> expresses hydrogen atom or the like, X<1> , X<2> are the same one as U<1> in the formula I, and X, Y express a weight composition ratio of the copolymer).

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 preparing a plate-making printing plate using the same.
The present invention relates to an oil-based ink excellent in storage stability, image reproducibility, and printing durability, and a method of making a plate-making printing plate using the oil-based ink.

[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. 2. Description of the Related Art Offset lithographic printing, in which a plate is made, that is, an image is formed to create a printing plate, 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 electrostatic attraction, and a so-called drop-on-demand in which ink is ejected by using the vibration pressure of a piezo element. Various types of ink jet recording methods, such as a so-called bubble (thermal) jet method, in which ink is ejected using pressure generated by forming and growing bubbles by high heat, and a so-called bubble (thermal) jet method, have been proposed. With these methods, extremely high-precision images can be obtained.

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.

With these ink jet printers,
Plate making is also performed on the above-described direct drawing type lithographic printing plate precursor, and at this time, an aqueous ink using water as a dispersion medium is also used. There is a problem that the drawing speed is reduced due to the low speed. In order to reduce such a problem, a method using an oil-based ink in which a dispersion medium is a non-aqueous solvent is disclosed in Japanese Patent Application Laid-Open No. 54-117.
No. 203.

However, even in this method, the image quality of the plate making is actually bleeding, and when the printing is further performed, bleeding of the image portion is seen. Further, the number of printed sheets is limited to several hundreds at most and is insufficient. there were.

In addition, clogging of a nozzle for discharging minute ink droplets that enables a high-resolution plate-making image is liable to occur.

In general, an ink jet recording method is to eject ink from a nozzle after passing through a filter. Therefore, in this recording method, clogging of a nozzle, clogging of a filter, or deterioration of fluidity of ink with the passage of time. It is easy to cause abnormal ink ejection due to various other factors such as a change in the ink ejection.

Various proposals have been made for improving the abnormal discharge of the ink. For example, the abnormal discharge of the ink occurs not only in the aqueous ink composition but also in the oil ink composition. In order to prevent abnormal ink ejection when an oil-based ink composition is used, as described in JP-A-49-50935, an ink-jet recording method using an electric field control method is used. In addition, proposals have been made to control the specific resistance and specific resistance of a solvent used in an ink composition as described in JP-A-53-29808.

In order to prevent clogging of nozzles of a general oil-based ink for an ink jet printer, for example, a method of improving the dispersion stability of pigment particles (JP-A-4-255)
No. 73, JP-A-5-25413, JP-A-5-6544
No. 3, etc.) and a method of containing a specific compound as an ink composition (Japanese Patent Application Laid-Open Nos. Hei 3-79677 and Hei 3-6437).
7, JP-A-4-202386, JP-A-7-1094
No. 31, etc.) have been proposed.

However, none of these methods, even when used for forming an image on a lithographic printing plate, provides satisfactory printing durability due to insufficient image strength at the time of printing.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-based ink for plate-making printing of an ink jet type having excellent redispersibility, storage stability and printing durability.

Another object of the present invention is to provide an ink for an ink-jet type plate-making printing plate in which the nozzle and the ink supply path are not clogged and the ink discharge is stable.
Another object of the present invention is to provide a method of preparing an ink-jet type plate-making printing plate for forming a lithographic printing plate that can stably perform ink-jet recording even when used repeatedly and has excellent printing durability.

Another object of the present invention is to provide a method for producing an ink-jet type plate-making printing plate capable of printing a large number of clear printed images.

[0018]

This and other objects are achieved by the present invention which is defined below as (1) to (6). (1) Image receiving of a lithographic printing plate precursor having an image receiving layer containing zinc oxide and a binder resin on a water-resistant support, and having a contact angle of 50 ° or more with water on the surface of the image receiving layer. An oil-based ink composed of at least resin particles 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 ejected from a nozzle in a droplet form on the layer by an ink jet method. After forming an image, the non-image portion of this image receiving layer is desensitized by a chemical reaction treatment to obtain a lithographic printing plate. Wherein the dispersed resin particles are (i) a monofunctional monomer (A) that is soluble in a non-aqueous solvent that is at least miscible with the non-aqueous carrier liquid, and becomes insoluble by polymerization. At least one of (ii) the single substance At least one monomer (C) represented by the following general formula (I) copolymerizable with the isomer (A), and (iii) a copolymer represented by the following general formula (II) soluble in the non-aqueous solvent. An oil-based ink for an ink-jet plate-making printing plate, which is a copolymer resin obtained by polymerizing a solution containing at least one dispersion stabilizing resin (P) containing a polymerization component.

[0019]

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In the formula (I), E ¹ is 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) represented by the following general formula (III). Represents a substituent.

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. B₁And B_TwoAre the same or different
Each may be -O-, -S-, -CO-, -CO
_Two-, -OCO-, -SO_Two-, -N (R_{twenty two})-, -CO
N (R _{twenty two})-, -N (R_{twenty two}) CO-, -N (R_{twenty two}) SO
_Two-, -SO_TwoN (R_{twenty two})-, -NHCO_Two-Or -N
HCONH- (where R_{twenty two}Is R_{twenty one}Same as
It shows the contents). A₁And A_TwoAre 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).

[0022]

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In the formula (IIIa), B_ThreeAnd B_FourAre the same as each other
The same or different. ₁, B_TwoSame contents as
And A_FourIs a carbonized carbon atom having 1 to 18 carbon atoms which may be substituted
R represents a hydrogen group;_{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 represents an integer of 0 to 4. Where m, n and p
Do not become 0 at the same time. In the formula (I), U¹Is -C
OO-, -CONH-, -CON (E^Two)-[Where E
^TwoIs an aliphatic group or a unit represented by the above general formula (III)
Represents a substituent], -OCO-, -CONHCOO-, -C
H_TwoCOO-,-(CH_Two)_sOCO- [where s is 1 to 4
Represents an integer of the formula), -O-, -C₆H_Four-Or -C₆H_Four−
Represents COO-. a¹And a^TwoAre the same but different
May be hydrogen, halogen, cyano, respectively.
Group, alkyl group, -COO-E^ThreeOr -CH_TwoCOO-
E^Three(Where E^ThreeRepresents an aliphatic group).

[0024]

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In the formula (II), R¹Represents a group having 10 to 32 carbon atoms.
Represents an alkyl group or an alkenyl group. b¹Is a hydrogen atom
Or a methyl group. X¹And X^TwoAre each in the formula (I)
U¹And the contents of the same. W is a bonding group X¹And bonding group X
^TwoA carbon-carbon bond which may be via a heteroatom connecting
(However, an oxygen atom, a sulfur atom,
A silicon atom or a nitrogen atom). d¹, D^Two,
e¹And e^TwoMay be the same or different from each other, and the formula
A in (I) ¹, A^TwoAnd the contents of the same. x and y are
It represents the weight composition ratio of the polymer, and is 90/10 to 99/1 (weight
Quantitative ratio).

(2) An ink-jet printing method comprising forming an image of the oil-based ink described in (1) above on a lithographic printing plate precursor having a hydrophilic surface capable of lithographic printing by an ink-jet method to form a lithographic printing plate. How to make a formula plate printing plate. (3) The method for producing an ink-jet plate-making printing plate according to the above (2), wherein the image formation of the ink-jet method is a method of discharging the oil-based ink using an electrostatic field. (4) The lithographic printing plate precursor is provided on a water-resistant support, provided with an image receiving layer having a lithographically printable hydrophilic surface,
(2) or (3), wherein the water-resistant support is a support having a specific electrical resistance of at least 10 ¹⁰ Ωcm or less directly below the image receiving layer. . (5) The above-mentioned (2) to (2), wherein the water-resistant support is a support having a specific electrical resistance value of 10 ¹⁰ Ωcm or less for the entire support.
(4) The method for producing an ink-jet type plate-making printing plate according to any of (4). (6) The method according to any one of the above (2) to (5), wherein the resin particles dispersed in the oil-based ink are oil-based inks which are charge detection particles formed by being charged with a positive charge or a negative charge. How to make an ink-jet type plate-making printing plate.

The present invention is characterized in that an oil-based ink is ejected on a lithographic printing original plate 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 planographic printing plate can print a large number of clear images.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The oil-based ink used in the present invention will be described below in detail.

The electric resistance used in the present invention is 10 ⁹ Ωcm or more,
The non-aqueous carrier liquid of the oil-based ink having a dielectric constant of 3.5 or less is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon, or a halogen-substituted product thereof. Can be used. For example, octane, isooctane, decane, isodecane, decalin,
Nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; trade name of Exxon), Shersol 70, Shersol 71 ( Shelsol; trade name of Shell Oil Company), Amsco OM
S, Amsco 460 solvent (Amsco; trade name of Spirits) and the like can be used alone or in combination. The upper limit of the electric resistance of such a non-aqueous carrier liquid is 10 ¹⁶
It is about Ωcm, and the lower limit of the dielectric constant is about 1.85.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are used as a monofunctional mono-functional monomer in a non-aqueous solvent as a copolymerization component of a random copolymer. The monomer (A) in the presence of the dispersion-stabilizing resin (P) soluble in the non-aqueous solvent and containing a polymerizable double bond group capable of copolymerizing with the monomer (A). It is polymerized and granulated by co-polymerizing at least one kind of monomer (C) containing one kind and a specific substituent.

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 the like. Examples thereof include aromatic hydrocarbons and halogen-substituted products thereof. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shelsol 70, Shelsol 71, AMSCO OMS, AMSCO 460 solvent and the like can be used alone or in combination.

Solvents which can be used by mixing with these organic solvents include alcohols (eg, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol monomethyl ether, fluorinated alcohol), ketones (eg, methyl ethyl ketone, Acetophenone, cyclohexanone, etc.), carboxylic esters (eg, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, ethyl benzoate, ethylene glycol monomethyl ether acetate, etc.), ethers (eg, dipropyl ether) , Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, chloroform, dichloroethane) , Methyl chloroform), and the like.

It is desirable that the non-aqueous solvent used by mixing these is distilled off under heating or under reduced pressure after the polymerization granulation. There is no problem as long as the conditions that the liquid resistance is 10 ⁹ Ωcm or more and the dielectric constant is 3.5 or less can be satisfied.

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

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

[0037]

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In the formula (IV), T ¹ is -COO-, -OCO
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, - C
ONHCOO -, - CONHOCO -, - SO 2 -, -
CON (W ¹ ) —, —SO ₂ N (W ¹ ) — or a phenylene group (hereinafter, a phenylene group is referred to as “—Ph-”. In addition, phenylene groups are 1,2-, 1,3- and 1 , 4-
Includes phenylene groups. ). Where W ¹ is
A hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2
-Cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3- Methoxypropyl group).

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- Pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4
-Sulfobutyl group, 2-carboxyamidoethyl group, 3
-Sulfamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

F ¹ and f ² may be the same or different from each other, and each of a ^{1 and} a ² in the general formula (I)
And the contents of the same.

Specific examples of the monofunctional monomer (A) include:
For example, vinyl ester acids 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, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, Bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-
Hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) ethyl group, 2-carboxyethyl group,
2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-
Furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-
Styrene derivatives (eg, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, “Polymer Data Handbook-
Basic Edition- ", pages 175-184, Baifukan (1986), for example, N-vinylpyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
And the like. Two or more monomers (A) may be used in combination.

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

The case where E ¹ in the monomer (C) 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.

U ¹ is preferably -COO-, -CONH
-, -CON (E ² )-[where E ² preferably represents an aliphatic group having 1 to 22 carbon atoms (for example, an aliphatic group represents an alkyl group, an alkenyl group or an aralkyl group)],- OCO -, - represents a CH ₂ OCO- or -O-. More preferably, -COO -, - CONH- or -CON (E ²⁾ - represents a.

A¹And a^TwoAre the same but different
And preferably a hydrogen atom or a halogen atom (eg,
For example, fluorine atom, chlorine atom, bromine atom, etc.), cyano
Group, alkyl group having 1 to 3 carbon atoms, -COO-E^ThreeOr
-CH_TwoCOO-E^Three(Where E ^ThreePreferably has 1 carbon atom
Represents an aliphatic group of ~ 32, for example, methyl group, ethyl
Group, propyl group, butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl
Group, hexadecyl group, octadecyl group, docosanyl group,
Pentenyl, hexenyl, heptenyl, octenyl
Group, decenyl group, dodecenyl group, tetradecenyl group,
Hexadecenyl group, octadecenyl group, etc.
These aliphatic groups are represented by E¹Having the same substituents as those represented by
May be represented). More preferably, a¹And a^Two
Are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg,
For example, methyl group, ethyl group, propyl group, etc.), -COO-
E^ThreeOr -CH_TwoCOO-E^Three(Where E^ThreeIs more preferred
Or an alkyl or alkenyl group having 1 to 12 carbon atoms
Represents, for example, a methyl group, an ethyl group, a propyl group,
Tyl, hexyl, octyl, decyl, dodecyl
Group, pentenyl group, hexenyl group, heptenyl group, octyl group
And a phenyl group, a decenyl group and the like.
Group or alkenyl group may have a substituent, for example,
If a halogen atom (fluorine atom, chlorine atom, bromine atom
Etc.), hydroxyl group, cyano group, alkoxy group (meth
Xy, ethoxy, propoxy, butoxy, etc.)
Is mentioned.

In the monomer (C) represented by the general formula (I) as described above, when E ¹ represents an aliphatic group having 8 or more carbon atoms, specific examples thereof include those having a total of 10 to 32 carbon atoms. 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, or the like; Acrylic acid, methacrylic acid, crotonic acid, maleic acid, which may have a carbon bond
Esters of unsaturated carboxylic acids such as itaconic acid (for example, aliphatic groups such as decyl group, dodecyl group, tridecyl group, tetradecyl group, 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.

In the monomer (C) represented by the general formula (I), E ¹ is a group represented by the general formula (III) in which the total number of atoms is 8 or more (excluding a hydrogen atom bonded to carbon and nitrogen). 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 above general formula (IIIa) and the hydrocarbon group having 1 to 18 carbon atoms (however, when two or more groups, Of the formula (IIIa) and / or a hydrocarbon group). More specifically, these are represented by -C (R
₂₄₎ (R ₂₅₎ - [R _24, R ₂₅ is a hydrogen atom, an alkyl group, a halogen atom, etc.], - (CH = CH) - , cyclohexylene group [hereinafter, "-C ₆ H cyclohexylene _Ten
- expressed in "" - C ₆ H ₁₀ - "is 1,2-cyclohexylene group, 1,3-cyclohexylene group, include 1,4-cyclohexylene group], represented by the general formula (IIIa) And any combination of atomic groups such as groups.

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.

U ¹ represents —CON (E ² ) —, and E ² represents a substituent represented by the general formula (III), that is,
When it represents a _{[- - (A I -B 1)} m (A 2 -B 2) n -R 21 ], also linked backbone consists of E ² contained in the "binding main chain". Furthermore, A _1, A ₂ is the formula [-B ₃ in the case of having a group represented by _{(IIIa) - (A 4 -B} 4) p -R
₂₃ ] is also included in the aforementioned “linking main chain”.

In the above-mentioned monomer (C) 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 formula, each symbol represents the following contents. r ₁ ; H, —CH ₃ , —Cl or —CN, r ₂ ; H,
-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

[0055]

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[0056]

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[0057]

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The dispersion stabilizing resin (P) of the present invention 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.

Dispersion stabilizing resin (P) used in the present invention
Is a polymerizable double bond copolymerizable with the monomer (A) at least at the terminal of the side chain of the copolymerizable component (component X) soluble in the non-aqueous solvent represented by the general formula (II). It is a random copolymer containing a copolymer component (Y component) containing a group and soluble in the non-aqueous solvent.

In the formula (II), R ¹ represents an alkyl group or an alkenyl group having 10 to 32 carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Examples include a hexadecyl group, an octadecyl group, an eicosanyl group, a docosanyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, an eicosenyl group, a docosenyl group, and a linolel group.

B ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), preferably a hydrogen atom or methyl group. Two or more types of the X component in the general formula (II) may be contained in the resin (P).

X ¹ and X ² each represent U ^{1 in} formula (I)
Represents the same content as W is a carbon-carbon bonding group which may be connected via a hetero atom connecting the bonding group X ¹ and the bonding group X ² (provided that the hetero atom is an oxygen atom, a sulfur atom,
A silicon atom or a nitrogen atom).

The bonding group includes a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen atom,
Silicon atom), a heteroatom-heteroatom bond atomic group, a heterocyclic group and the like. For example, as the above atomic group,

[0064]

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

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

In the Y component in the general formula (II), the connecting main chain composed of the bonding group: [-X ¹ -WX ^2- ] has a total number of atoms of 8 or more. preferable. As the number of atoms in the connecting main chain, for example, when X ¹ represents —COO— or —CONH—, an oxo group (＝ O group) or a hydrogen atom is not included as the number of atoms, and carbon atoms constituting the connecting main chain are not included. Atoms, ether-type oxygen atoms, and nitrogen atoms are included in the number of atoms. Therefore, -COO- and -CONH- are counted as 2 atoms.

Hereinafter, specific examples of the Y component containing a polymerizable double bond group will be shown, but the present invention is not limited thereto. In the following formula, each symbol represents the following contents.

[0069]

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[0070]

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[0071]

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The dispersion stabilizing resin (P) of the present invention can be easily synthesized by a conventionally known synthesis method. That is, as a method of introducing a copolymerizable component (Y component) containing a polymerizable double bond group into a resin, a “specific reactive group” (for example, —OH, —COOH, —SO ₃ H,
_{-NH 2, -SH, -PO 3 H} 2, -NCO, -NCS,
-COCl, -SO ₂ Cl, After polymerization reaction with the monomers corresponding to the X component of a monomer containing an epoxy group) in the formula (II), containing a polymerizable double bond group reaction After reacting the reactive reagent, a method of introducing a polymerizable reactive group by a polymer reaction may be used.

Specifically, P. Dreyfuss & RPQuirk Enc
ycl. Polym. Sci. Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30, 232 (1985), Akira Ueda, Susumu Nagai, "Chemistry and Industry", 60 , 57 (1986) ), PFRempp & E. Fra
nta, Advances in Polymer Science, 58 , 1 (1984), Koichi Ito "Polymer Processing", 35 , 262 (1986), V. Percec, App
A polymerizable double bond group can be introduced according to a method described in a review such as lied Polymer Science, 285 , 97 (1984) and references cited therein.

As another method, a bifunctional monomer having a different copolymerization reactivity in a radical polymerization reaction is used to carry out a polymerization reaction together with a monomer corresponding to the X component.
A method described in JP-A-60-185962 for synthesizing a copolymer represented by the general formula (I) without causing a gelation reaction is exemplified.

In the resin represented by the general formula (II), X
The proportion of the component to the Y component is 90/10 to 99/1 by weight, preferably 92/8 to 98/2 by weight. Within this range, during the polymerization granulation reaction, the gelation of the reaction mixture or the generation of coarse particles of the resin particles does not occur, and the dispersion stability of the obtained particles is not increased.
Good re-dispersion stability.

The dispersion stabilizing resin (P) used in the present invention may contain other repeating units as copolymer components together with each repeating unit represented by the general formula (II). The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with a monomer corresponding to each repeating unit of the general formula (II). But,
It is preferably used in an amount not exceeding 20 parts by weight in all polymer components (100 parts by weight). When the content is 20 parts by weight or less, good dispersion stability of the dispersed resin particles can be obtained.

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

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

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

The total amount of the monomers (A) and (C) is preferably from 10 to 1 based on 100 parts by weight of the non-aqueous solvent.
It is about 00 parts by weight, more preferably 10 to 80 parts by weight.

The monomer (C) represented by the general formula (I) is preferably used in an amount of 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, based on the monomer (A). It is.
The dispersion stabilizing resin (P) is composed of all monomers 1 used in the above.
It is 1 to 25 parts by weight, preferably 5 to 20 parts by weight, based on 00 parts by weight.

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

The amount of the polymerization initiator is 0.1 to 1 of the total monomer amount.
0% by weight is suitable. Further, the polymerization temperature is 40 to 180.
C is preferable, and more preferably 50 to 120C. 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) to be polymerized and granulated is used alone. When the unreacted product of the monomer (C) 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.

The non-aqueous dispersed resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution. The average particle size is preferably from 0.1 to
It is 1.0 μm, more preferably 0.2 to 0.8 μm. The particle size is determined by CAPA-500 (trade name, manufactured by Horiba, Ltd.).

The average molecular weight by weight (Mw) of the dispersion resin of the present invention is preferably from 5 × 10 ³ to 1 × 10 ⁶ , more preferably from 8 × 10 ^{3 to} 5 × 10 ⁵ . Further, the dispersing resin of the present invention has a glass transition point of 15
C. to 80.degree. C. or a softening point of 35.degree.
More preferably, the glass transition point is 20 ° C to 60 ° C or the softening point is 38 ° C to 90 ° C.

Within the above ranges, the dispersion stability, re-dispersion stability and storage stability of the dispersed resin particles in the oil-based ink of the present invention are excellent, and the rapid fixability after image formation is good. In addition, sufficient strength is maintained during printing, and high printing durability is exhibited. At the same time, it shows extremely stable dispersibility, and especially in a recording apparatus, has good dispersibility even when used repeatedly for a long time, and is easy to re-disperse. unacceptable. Furthermore, when fixing was performed by rapid processing by heating or the like after the formation of the ink image, a strong film was easily formed on the surface of the lithographic printing plate support, and good fixability was exhibited. Thereby, even in offset printing, printing of a large number of sheets (high printing durability) becomes possible.

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

In the dispersion resin particles of the present invention, the dispersion stabilizing resin (P) is chemically bonded to the insoluble resin particles during the polymerization granulation reaction. Since the resin (P) to which the resin particles are bonded is soluble in the non-aqueous solvent, the dispersion stabilization of the non-aqueous latex, that is, a so-called steric repulsion effect is provided.

Further, the monomer (C) having a specific substituent is copolymerized with the monomer (A) which is insolubilized at the time of polymerization granulation. Since the substituent portion forms the particles by non-aqueous dispersion polymerization, it is designed to have good affinity with the non-aqueous solvent. Has good solvability, so that it is oriented at the interface (surface) of the particle structure. As a result, together with the dispersion stabilizing resin (P), the affinity for the dispersion medium on the particle surface is improved, It is presumed that the effect of preventing aggregation is significantly enhanced. It is considered that these factors suppress the aggregation and precipitation of the insoluble particles, and significantly improve the redispersibility.

The oil-based ink used in the present invention preferably contains a coloring material as a coloring component together with the above-mentioned 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 appropriate combination, but may be contained in the range of 0.05 to 5% by weight based on the whole ink. desirable.

These coloring materials may be dispersed in a non-aqueous solvent as dispersed particles themselves in addition to the dispersed resin particles, or may be contained in the dispersed resin particles. One of the methods for adding the dye is to dye the dispersed resin material with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, there is a method of chemically bonding a dispersing resin material and a dye as disclosed in JP-A-53-54029 or the like, or described in JP-B-44-22955. As described above, there is a method in which a monomer containing a dye is used in advance to produce a dye-containing copolymer when producing by a polymerization granulation method.

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

[0098] The particles can be imparted with an electric detecting property by appropriately utilizing a technique of a wet electrostatographic 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.

Specifically, for example, British Patent No. 8934
No. 29, No. 934038, U.S. Pat. No. 112239
No. 7, No. 3900412, No. 460989,
These are described in JP-B-6-19596, JP-B-6-19595, JP-B6-23865, JP-B4-51023, JP-A-2-13965, JP-A-60-185963 and the like.

The charge control agent described above is preferably used in an amount of 0.001 to 1.0 part by weight with respect to 1000 parts by weight of 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.

The oil-based ink containing the detectable resin particles of the present invention is a preferable embodiment in an electric field control type ink-jet recording system utilizing an electrostatic attraction by applying an electrostatic field. Ease of discharge from the nozzle is further improved. However, if the electrical 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.
It is necessary to control within this limit.

Next, the lithographic printing original plate used in the present invention will be described.

In this case, the image receiving layer contains zinc oxide and a binder resin, and its surface has a degree of hydrophobicity of 50 ° or more in terms of a contact angle with water. ,
Preferably it is 50 ° to 130 °, more preferably 50 ° to 120 °, particularly preferably 55 ° to 110 °.

When the contact angle with water is within the above range, the strength of the image layer as described above is sufficiently maintained, and a clear image is formed without disturbing the image such as fine lines, fine characters, and halftone dots. Is done. In addition, the contact angle is a value measured by a contact angle meter and a droplet method using distilled water.

On the other hand, the apparatus disclosed in JP-A-54-117203 uses an ink-jet system using an oil-based ink in the same manner as in the present invention, but differs from the present invention in that the surface of the image receiving layer of the printing original plate is different. Is hydrophilic and has a contact angle with water of 40 ° or less. In such a case, the image reproducibility is remarkably inferior and the printing durability is remarkably reduced as compared with the present invention.

In the present invention, the smoothness of the surface of the image receiving layer is preferably 30 (sec / 10 cc) or more, more preferably 45 to 300 (sec / 10 c) in Beck smoothness.
c).

When the smoothness of the surface of the image receiving layer is within the above-mentioned range, a clear image with no image defects or the like is formed, and the adhesion between the image portion and the image receiving layer is improved. The printing durability is significantly improved to 3000 sheets or more.

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

Further, a method for producing a plate-making printing plate of the present invention will be described.

First, a lithographic printing plate precursor having an image-receiving layer containing at least zinc oxide and a binder resin on a water-resistant support provided in the present invention will be described.

The zinc oxide to be used in the present invention may be, for example, zinc oxide, zinc oxide or zinc oxide, as described in “Pigment Handbook” edited by Japan Pigment Technical Association, p. 319, Seibundo Co., Ltd. (1968). Any of those commercially available as wet zinc white or activated zinc white may be used.

That is, depending on the starting materials and the production method, zinc oxide is classified into a dry method, a French method (indirect method), an American method (direct method) and a wet method. For example, Shodo Chemical Co., Ltd. Examples include those commercially available from companies such as Sakai Chemical Co., Ltd., Hakusui Chemical Co., Ltd., Honjo Chemical Co., Ltd., Toho Zinc Co., Ltd., and Mitsui Kinzoku Kogyo Co., Ltd.

The content of zinc oxide in the image receiving layer is preferably 90 to 75% by weight, more preferably 88 to 78% by weight.

With such a content, the effect of the present invention is improved. On the other hand, if the amount of zinc oxide is reduced, the surface of the image receiving layer is not sufficiently hydrophilized by the desensitizing treatment, and the effect of the present invention cannot be obtained.If the amount is too large, the necessary amount of the binder resin cannot be secured. Not preferred.

As described above, the binder resin provided for the image receiving layer of the present invention constitutes the image receiving layer together with zinc oxide, and has a hydrophobic property such that the contact angle of the surface thereof is within the above-mentioned predetermined range. Resin, and the weight average molecular weight (M
w) is preferably 10 ³ to 10 ⁵ , more preferably 5 ×
It is 10 ^{3 to} 5 × 10 ⁵ . Further, the glass transition point of this resin is preferably 0 ° C to 120 ° C, more preferably 10 ° C to 120 ° C.
90 ° C.

Specifically, vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl butyral, Alkyd resins, epoxy resins, epoxy ester resins, polyester resins, polyurethane resins, and the like. These resins may be used alone or in combination of two or more.

The content of the resin in the image receiving layer is preferably from 9/91 to 20/80 in terms of resin / zinc oxide weight ratio.

The image receiving layer of the present invention may contain other components in addition to the above components.

As other components that may be contained, there are other inorganic pigments of zinc oxide used in the present invention. Examples of such inorganic pigments include kaolin, clay, calcium carbonate, barium carbonate, and sulfuric acid. Examples include calcium, barium sulfate, magnesium carbonate, titanium oxide, silica, and alumina. When these other inorganic pigments are used in combination, they can be used in an amount not exceeding 20 parts by weight with respect to the zinc oxide of the present invention.

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

When these other inorganic pigments or resin particles are used within the above-mentioned usage range, the desensitization (hydrophilicity) of the non-image area due to the desensitization treatment is sufficiently performed, and the background stain on the printed matter is reduced. In addition, the image portion is sufficiently adhered to the image receiving layer, and sufficient printing durability can be obtained without causing image loss even when the number of printed sheets increases.

Pigment (including zinc oxide) in image receiving layer /
In general, the proportion of the binder resin is based on 100 parts by weight of the pigment.
The content of the binder resin is 10 to 25 parts by weight, preferably 13 to 22 parts by weight. Within this range, the effects of the present invention are effectively exhibited, and at the same time, film strength is maintained during printing or high hydrophilicity is maintained during desensitization treatment.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. Examples of the crosslinking agent include compounds that are usually used as a crosslinking agent. To be more specific, refer to “Bridge Handbook” edited by Tozo Yamashita and Tosuke Kaneko, Taiseisha (1981), “Polymer Data Handbook, Basic Edition”, edited by The Society of Polymer Science, Japan, Baifukan (1986)
) Can be used.

In the present invention, a reaction accelerator may be added as necessary to accelerate the crosslinking reaction in the image receiving layer.

In the case of a reaction mode in which the crosslinking reaction forms a chemical bond between functional groups, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, phenol, Chlorophenol, nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc., organometallic compounds (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetone cobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamic acid) Salts), tinouram disulfide compounds (such as tetramethyltinouram disulfide), carboxylic anhydrides (phthalic anhydride,
Maleic anhydride, succinic anhydride, butyl succinic anhydride, 3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.). When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator is used, and examples thereof include a peroxide and an azobis compound.

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

Further, a specific functional group in the resin may be photo-cured. As a method of curing by light irradiation, a step of irradiating light with a chemically active ray may be included. The chemical actinic ray may be any of visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X ray, γ ray, α ray, etc.
Range of rays. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp, or the like is used. The light irradiation treatment can be sufficiently carried out by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

The thickness of the image receiving layer in the present invention is preferably about 3 to 30 g as indicated by the coating amount (after drying) of the image receiving layer composition per 1 m ² of the original plate. Also, the image receiving layer is usually 3 to 50 vol%, preferably 10 to 40 v%.
Those having a porosity of about ol% are preferred.

The image receiving layer of the present invention is provided on a water-resistant support. Examples of the aqueous support include a plastic sheet, printing-resistant paper, an aluminum plate, a zinc plate, and copper-
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-described 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 or 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 range of the conductivity described above, 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, the 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 base, 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 a 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, nickel, etc., 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 the metal foil laminate, and a polyethylene resin mixed with carbon black is used as the laminate of the 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 the plastic film having conductivity, for example, polypropylene or polyester film mixed with a conductive filler such as carbon fiber or carbon black can be used. As the 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 for 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.

Furthermore, in the present invention, the smoothness of the surface of the support 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 described above, the overcoat, 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 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 prevention 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 order to adjust the smoothness of the under layer and the back coat layer of the support as described above, 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 coating solution. 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.

Examples of the pigment include clay, kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica and the like. These pigments are used to achieve the desired smoothness.
It is preferable to appropriately select and use the particle size. 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 of 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.

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 source such as a computer 3 through a transmission means such as a path 4 to an 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, sprays minute droplets of the ink on the master 2 according to the information. Thereby, ink adheres to the master 2 in the pattern.

Thus, the image formation on the master 2 is completed.
Obtain a plate making master (plate making printing plate).

FIGS. 2 and 3 show examples of the configuration 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 structural view showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

The head 10 provided in the ink jet recording apparatus has a slit sandwiched between the upper unit 101 and the lower unit 102, as shown in FIGS. 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 according to a digital signal of pattern information of an image. 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.

The width of the discharge electrode 10b is preferably as narrow as possible to form high-quality images, for example, for printing.

For example, the head 10 shown in FIG. 3 is filled with oil-based ink, the tip of the ejection electrode 10b is 20 μm wide, and the distance between the ejection electrode 10b and the counter electrode 10c is 1.5 mm.
By applying a voltage of 3 KV between the electrodes for 0.1 millisecond, a dot of 40 μm can be printed on the master 2.

As described above, on the lithographic printing plate precursor,
A plate making master obtained by forming an image by an ink jet method using an oil-based ink is subjected to a surface treatment with a desensitizing treatment liquid to desensitize non-image portions to prepare a printing plate.

Desensitization of zinc oxide has been conventionally performed using a desensitizing treatment liquid of this type, a treatment liquid containing a cyanide compound containing ferrocyanate and ferricyanate as main components, an ammine cobalt complex, phytic acid and derivatives thereof, Known are a cyan-free treatment liquid containing a guanidine derivative as a main component, a treatment liquid containing an inorganic acid or an organic acid that forms a chelate with zinc ions as a main component, and a treatment liquid containing a water-soluble polymer.

For example, as a cyanide-containing treatment solution,
JP-B-44-9045, JP-B-46-39403, JP-A-52-76101, JP-A-57-107889, and JP-A-57-107889.
4-117201 and the like.

Examples of the treatment solution containing a phytic acid compound include:
JP-A Nos. 53-83807, 53-83805, 53-102102, 53-109701, and 5
Nos. 3-127003, 54-2803, 54-4
No. 4901 and the like.

Examples of the treating solution containing a metal complex compound such as a cobalt complex include JP-A-53-104301 and JP-A-53-301301.
No. 140103, No. 54-18304, Tokuhei 43-
No. 28404.

Examples of the treating solution containing an inorganic or organic acid include JP-B-39-13702, JP-B-40-10308, and JP-B-39-10308.
Nos. 3-28408 and 40-26124, JP-A-Sho 51
-118501 and the like. Examples of the guanidine compound-containing treating solution include JP-A-56-1116.
No. 95 and the like.

Examples of the processing solution containing a water-soluble polymer include JP-A Nos. 52-126302 and 52-134501,
Nos. 53-49506, 53-59502, 53
-104302, JP-B-38-9665, 39-
No. 22263, No. 40-763, No. 40-2202
And JP-A-49-36402.

In any of the above desensitizing treatments,
Zinc oxide in the surface layer ionizes into zinc ions,
It is believed that these ions cause a chelation reaction with a compound forming a chelate in the desensitizing solution to form a zinc chelate, which is deposited in the surface layer and hydrophilized. Desensitization treatment is usually performed at room temperature (15 ° C to 35 ° C
) For about 2 to 60 seconds. Using this printing plate, about 5000 sheets of offset printing can be performed by using dampening water.

[0174]

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

Synthesis Example 1 of Dispersion Stabilizing Resin (P) 1: Resin (P-1) A mixed solution of 96 g of octadecyl methacrylate, 4 g of 4- (2-methacryloyloxyethyloxycarbonyl) butyric acid and 200 g of toluene was placed in a nitrogen stream. , Temperature 75
Warmed to ° C. As an initiator, 1.5 g of 2,2'-azobisisobutyronitrile (abbreviated as AIBN) was added and reacted for 4 hours. I. B. N. 0.8 g was added, the mixture was heated to a temperature of 80 ° C., and reacted for 4 hours.

After the reaction mixture was cooled to 25 ° C., 6 g of allyl alcohol was added with stirring, followed by 10 g of dicyclohexyl dicarbodiimide (abbreviated as DCC).
A mixed solution of 0.1 g of 4- (N, N-diethylamino) pyridine and 30 g of methylene chloride was added dropwise over 1 hour.
Further, the reaction was continued for 3 hours to complete the reaction. Next, 10 g of 80% formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. Then, insolubles were filtered off, and the filtrate was reprecipitated in 2.5 liters of methanol. After the precipitate was collected by filtration, toluene 2
After dissolving in 00 g and filtering off the insoluble matter, the filtrate was reprecipitated in 1 liter of methanol. The precipitate was collected by filtration and dried.

The yield of the obtained polymer was 70 g and Mw was 5
× 10 ⁴ (polystyrene-equivalent value according to GPC; the same applies hereinafter).

[0178]

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Synthesis Example 2 of Dispersion Stabilizing Resin (P): Resin (P-2) A mixed solution of 50 g of dodecyl methacrylate, 45 g of octadecyl acrylate, 5 g of glycidyl methacrylate and 200 g of toluene was stirred at a temperature of 75 ° C. under a nitrogen stream. Heated. A. I. B. N. Was added and reacted for 4 hours. I. B. N. Was added for 3 hours. I. B. N. Was added and reacted for 3 hours. Next, 9 g of 3-acryloyloxypropionic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution.
g was added and stirred at a temperature of 100 ° C. for 10 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. Weight average molecular weight (Mw) of polymer
Was 4 × 10 ⁴ .

[0180]

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Synthesis Example 3 of Dispersion Stabilizing Resin (P): Resin (P-3) A mixed solution of 96 g of tridecyl methacrylate, 4 g of 11-methacrylamidoundecanoic acid and 200 g of toluene was stirred at a temperature of 75 ° C. under a nitrogen stream. And heated. A. I. B. N. Was added and reacted for 4 hours. I. B. N. Was added for 3 hours, and A. I. B. N. Was added and reacted for 3 hours. After cooling to a temperature of 40 ° C., 0.2 g of hydroquinone was added. Further, 6.9 g of vinyl acetate and 0.05 g of mercury acetate were added and reacted for 2 hours. Raise temperature to 70 ° C again 10
7.5% × 10 ^-3 ml of 0% sulfuric acid was added and reacted for 6 hours. After the reaction, 0.04 g of sodium acetate trihydrate was added to the reaction solution, and the mixture was stirred well, and then poured into 4.5 L of methanol for reprecipitation purification. 75 g of a slightly brownish viscous substance
I got Mw of the polymer was 5.3 × 10 ⁴ .

[0182]

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Synthesis Example 4 of Resin for Stabilizing Dispersion (P): Resin (P-4) A mixed solution of 97 g of hexadecyl methacrylate, 3 g of monomer (Y-1) having the following structure and 400 g of isodecane was heated at a temperature of nitrogen under a stream of nitrogen. Warmed to 70 ° C. 2,2 'under stirring
-Azobis (isovaleronitrile) (abbreviated as A.I.V.
N. ) 1.5 g was added and reacted for 4 hours. Continue to A.
I. V. N. Add 0.8 g for 3 hours, then add A. I.
V. N. 0.5 g was added and reacted for 3 hours. The solid concentration of the obtained solution was 19.9% by weight. Mw of the obtained polymer was 4 × 10 ⁴ .

[0184]

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Production Example 1 of Latex Particle 1: Latex Particle (D-1) 8 g of dispersion stabilizing resin (P-1), 100 g of vinyl acetate,
A mixed solution of 3 g of octadecyl methacrylate and 352 g of Isopar H was stirred at a temperature of 7 while stirring under a nitrogen stream.
Warmed to 5 ° C. 1.0 g of 2,2'-azobis (isovaleronitrile) (abbreviated AIVN) was added as a polymerization initiator, and the mixture was reacted for 3 hours. Further, the initiator A.
I. B. N. 0.8 g was added, and the mixture was heated to a temperature of 80 ° C. and reacted for 4 hours. Subsequently, 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 polymerization rate of 97% and an average particle diameter of 0.43 μm [particle diameter was measured using a CAPA-500 (manufactured by Horiba, Ltd.)] did. The same applies hereinafter.

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour), and the precipitated resin particles were collected and dried, and the weight average molecular weight of the resin particles was measured. When (Mw) and the glass transition point (Tg) were measured, Mw was 2 × 10 ⁵ , and the glass transition point: Tg was 36 ° C.
Met.

Preparation Example 2 of Latex Particles: Latex Particles (D-2) 10 g of dispersion stabilizing resin (P-2) and 17 g of Isopar H
7 g of the mixed solution was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 25 g of methyl methacrylate, 75 g of methyl acrylate, 4 g of octadecyl acrylate, 200 g of Isopar G and A.I. I. V. N. Was added dropwise over 2 hours, followed by stirring for 2 hours.
Further, A. I. B. N. And add 80g at 80 ℃
And stirred for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth.
Was a latex having an average particle size of 0.38 μm. The Mw of the resin particles was 2 × 10 ⁵ , and the Tg was 26 ° C.

Preparation Examples of Latex Particles 3 to 12: Latex particles (D-3) to (D-12) 8 g of dispersion stabilizing resin (P-3), 100 g of vinyl acetate,
After preparing a mixed solution of the monomer (C) in Table 1 below and 350 g of Isopar G, the mixture was reacted in the same manner as in Production Example 1 of latex particles to obtain each latex particle. The polymerization rate of each of the obtained white dispersions was 96 to 98%. Mw of each resin particle is in the range of 1 × 10 ^{5 to} 3 × 10 ⁵ , and Tg is 35 ° C.
It was in the range of 38 ° C.

[0189]

[Table 1]

Production Examples 13 to 19 of Latex Particles: Latex Particles (D-13) to (D-19) In Production Example 2 of latex particles, instead of 12 g of the dispersion stabilizing resin (P-2), the following Table 2 was used. Latex particles were produced in the same manner as in Production Example 2 except that the dispersion stabilizing resin (P) was used. The polymerization rate of each of the obtained latex particles is 95 to 100%, and the average particle size is 0.30 to 0.40 μm.
m and the monodispersibility was also good. Mw of each resin particle is in the range of 1 × 10 ^{5 to} 3 × 10 ⁵ , and Tg is 24 to
It was in the range of 28 ° C.

[0191]

[Table 2]

Latex Particle Production Examples 20 to 26: Latex Particles (D-20) to (D-26) Monomer (A) (namely, methyl methacrylate and ethyl acrylate) used in Latex Particle Production Example 2 A latex was prepared in the same manner as in Production Example 2 except that the compounds shown in Table 3 below were used instead of the monomer (C) (that is, octadecyl acrylate) and the dispersion stabilizing resin (P-2). Particles were produced. The polymerization rate of each obtained latex particle is 95 to 100%,
The average particle size was in the range of 0.30 to 0.40 μm, and the monodispersity was also good.

[0193]

[Table 3]

Production Example 27 of Latex Particles: Comparative Latex Particles (D-27) Except for using 3 g of octadecyl methacrylate equivalent to monomer (C) in Production Example 1 of latex particles, it was completely the same as Production Example 1 described above. Similarly, a white dispersion was synthesized.
Latex particles having a polymerization rate of 95% and an average particle size of 0.40 μm were obtained. The Mw of the resin particles was 1 × 10 ⁵ , and the Tg was 38 ° C.

Example 1 <Preparation of a lithographic printing plate precursor> 100 g of dry zinc oxide, 3.0 g of a binder resin (B-1) having the following structure, and a binder resin (B-2)
17.0 g, benzoic acid 0.15 g and toluene 155
g of the mixture was dispersed for 8 minutes at a rotation speed of 6 × 10 ³ rpm using a wet disperser homogenizer (manufactured by Nippon Seiki Co., Ltd.).

[0196]

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A support of ELP-1 type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing plate for transfer printing (smoothness of support underlayer: 500 (sec / 10 cc)) The above composition was applied thereon using a wire bar and dried at 100 ° C. for 1 minute to form an image receiving layer having a coating amount of 20 g / m ² , thereby obtaining a lithographic printing original plate.

The contact angle of the image receiving layer with water was determined by placing 2 μl of distilled water on the surface of the printing original plate, and measuring the surface contact angle (degree) after 30 seconds using a surface contact angle meter (CA-D, Kyowa Interface). As a result of measurement using Scientific Co., Ltd., the value was 102 degrees (the lower the value, the better the wettability to water and the higher the hydrophilicity). The smoothness of the image receiving layer The flat printing plate was measured for its smoothness (second / 10 cc) using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air volume of 10 cc,
(Sec / 10 cc). In addition, the smoothness of the support shown above was also measured in the same manner.

<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. .

Preparation of Latex Particles 55 g (as solid content) of the latex particles (D-1) of Preparation Example 1, 18 g of the above-mentioned alkali blue dispersion, 10 g of FOC-1400 (manufactured by Nissan Chemical Industries, Ltd., tetradecyl alcohol), and A blue oil-based ink was prepared by diluting 0.09 g of the octadecene-half-maleic acid octadecylamide copolymer into 1 liter of Isopar G.

Using the lithographic printing original plate prepared as described above, a servoproter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing a personal computer output, was modified, and the ink ejection head shown in FIG. 1.
Printing was performed on the lithographic printing original plate placed on the counter electrode spaced at a distance of 5 mm using the above-described oil-based ink (IK-1) to make a plate. Subsequently, using RICOH FUSER model 592 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 70 ° C. and heated for 20 seconds to sufficiently fix the image area.

When the copied image of the obtained plate-making product 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 abnormalities such as bleeding, missing, and blurring were observed. No contamination was observed, and no contamination was observed in the non-image area.

The above plate-making product was treated with a desensitizing solution: ELP-
It was immersed in E2 (manufactured by Fuji Photo Film Co., Ltd.) for 5 seconds, and the non-image portion was subjected to a lower oil-sensitizing treatment to obtain a printing plate.

This printing plate was used as immersion water and the ELP
Using a solution obtained by diluting -E2 with water 15-fold, and using Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) as a printing material, printing was performed with black ink for offset printing. As a result, more than 3,000 printed images with clear images free of background stains were obtained.

Next, when an ink ejection test was performed using the above-mentioned ink jet printer, stable ink ejection was obtained even after 600 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 a plate-making printing plate was actually printed under these conditions, 3,000 or more printed matters having clear images without background stains were obtained.

Further, the re-dispersibility of the ink was evaluated under strong printing conditions. That is, the ejection head used in the above printer was filled with ink, removed, left at 35 ° C. for 3 hours, then immersed in the Isopar G for 3 minutes, and then gently stirred, the ink (IK-1) was slit. Everything was removed from within. That is, it is considered that the ink of IK-1 which had adhered to the slit tip of the ejection head in a non-fluid state when left undisturbed was easily redispersed by solvation with the dispersion medium.

Comparative Example A The procedure of Example 1 was repeated, except that the comparative oil-based ink (IKR-1) described below was used in place of the oil-based ink (IK-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).
7) 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 by using the oil-based ink of Comparative Example A was prepared first, and as in Example 1, 3,000 or more printed matters having clear images without stains were obtained. Was. However, in the ink ejection test, Comparative Example A showed 20
In about 0 hours, the ejection of the ink became unstable. Also,
In the ink of the comparative example stored for 6 months, a coagulated precipitate was deposited and did not redisperse even when shaken. 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 slits of the ejection head portion.

As described above, the oil-based ink of the present invention has good ink ejection stability, forms a clear image with no stain, and can be printed as a printing plate even when plate making is performed continuously for a long period of time. However, it shows high printing durability.

Example 2 <Preparation of lithographic printing original plate> In Example 1, an ELP-IIX type master (Fuji Photo Film Co., Ltd.) was used instead of the ELP-1 type master support used as the water-resistant support.
Except for using a PET laminated paper support (trade name of support underlayer 1800 (second / 10 cc))
A lithographic printing original plate was obtained in the same manner as in Example 1.

<Preparation of oil-based ink (IK-2)> 10 g of poly (dodecyl methacrylate) and 10 g of nigrosine
g and 30 g of Isopar H 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.

Preparation of Latex Particles 50 g (in terms of solid volume) of the latex particles (D-2) of Preparation Example 2, 35 g of the above nigrosine dispersion and 0.10 g of [octadecylvinyl ether-heme maleic acid dodecylamide] copolymer were mixed with Isopar G. To 1 liter to produce a black oil-based ink.

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 form a printing plate, and offset printing was performed. The obtained printed matter had a clear image quality with no stain on the non-image area, as in the printing plate of Example 1, and had excellent printing durability of 10,000 sheets or more. Also, as in Example 1, the ink (IK-IK-
The performance was exactly the same as that of 1) and was excellent.

Examples 3 to 7 and Comparative Examples B to C Using a high-quality paper weighing 100 g / m ² as a substrate, a back layer paint having the following composition was applied to one surface of the substrate using a wire bar. After providing a back layer having a dry coating amount of 12 g / m ² , calender treatment was performed so that the smoothness of the back layer was about 50 (second / 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 4) 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). As shown in Table 4, each of the seven types of water-resistant supports obtained in this manner was used as a support sample N in accordance with the coating amount A to G.
o. 01-No. 07.

[0218]

[Table 4]

<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)

Each of the above components was mixed with the composition shown in Table 4 and
Water was added so that the total solid content concentration was 25% to obtain coating liquids 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 underlayer coatings A to G was applied to a sufficiently degreased and washed stainless steel plate, and the applied amount was 10 g / m ² on a dry basis.
Was formed. 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 5.

[0222]

[Table 5]

<Preparation of a lithographic printing original plate> 01-No. 07, an image receiving layer was provided so that the applied amount of the dispersion of the following composition after drying was 6 g / m ² , to prepare lithographic printing original plates. The surface smoothness of each master was in the range of 200 to 230 (sec / 10 cc), and the contact angle with water was 98 degrees or less.

100 g of dry zinc oxide (manufactured by Seido Chemical Co., Ltd.) as in Example 1, and a binder resin (B-3) 1 having the following structure
A mixture of 6 g, 4 g of the binder resin (B-4), 0.36 g of 3-propoxybenzoic acid, and 155 g of toluene was dispersed at a rotation speed of 1 × 10 ⁴ rpm for 20 minutes using a wet type disperser Kedimill.

[0225]

Embedded image

The sample No. of the lithographic printing original plate prepared as described above was used. 1 to No. 7, plate-making was performed in the same manner as in Example 1 using the oil-based ink (IK-1).
At the time of plate making, the printing plate sample No. 1 to No.
The underlayer provided immediately below the image receiving layer 2 and the counter electrode were electrically connected using silver paste.

Next, after making the plate as described above, using a fully automatic printing machine (AM-2850, trade name, manufactured by Am Co., Ltd.), the SLM-OD was made 50 times with distilled water as the dampening water. The diluted solution was put in a fountain solution tray, and printing was performed through a plate using a printing machine using black ink for offset printing.

The quality of the drawn image of the plate-making product thus obtained was evaluated as follows. Table 6 shows the results.

[0229]

[Table 6]

Note 1) Plate making image quality The drawing image of the obtained plate making product 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.

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

Note 3) Printing durability The number of printed sheets until the background stain or missing image of the printed matter can be visually discriminated was examined.

With reference to the specific electric resistance values in Table 5, Table 6
Let us consider the result. In Examples 3 to 7 of the present invention, the underlayer has a small specific resistance of 10 ⁸ to 10 ³ Ωcm, and has no problem in the image, and the fine lines and characters are very good. High printing durability. On the other hand, in the masters of Comparative Examples E and F having specific electric resistance values as large as 10 ¹² to 10 ¹¹ Ωcm, images are chipped or blurred. In addition, since the resin layer of the drawn image becomes thin as a result of bleeding, printing durability is low.
That is, the higher the conductivity of the support underlayer immediately below the image receiving layer, the higher the plate making quality and printing quality.

Examples 8 to 30 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 7 below. The oil-based ink used was a latex particle (D-D) in the oil-based ink (IK-1).
Latex particles (D) shown in Table 7 below were replaced with 50 in place of 1).
g (as a solid content) except that g was used.

[0235]

[Table 7]

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. Further, in the same manner as in Example 1, even in the ink ejection test and the redispersibility forced test for 600 hours or more, the performance was completely equivalent to or higher than that of the ink (IK-1), and was excellent.

Example 31 <Preparation of Water-Resistant Support> A high-quality paper weighing 100 g / m ² was used as a substrate, and an underlayer paint having the following composition was applied to one surface of the substrate using a wire bar. Dry coating amount 10
An under layer of g / m ² was provided. The smoothness of the under layer surface was 150 sec / 10 cc, and the smoothness was adjusted to 1500 (sec / 10 cc) by calendering.

<Under layer coating> Silica gel 10 parts by weight SBR latex (50% by weight aqueous dispersion, Tg 25 ° C.) 92 parts by weight Clay (45% by weight aqueous dispersion) 110 parts by weight Melamine (80% by weight) Aqueous solution) 5 parts by weight ・ Water 191 parts by weight

Further, a coating material for a back coat layer having the following composition was applied to the other surface of the substrate by using a wire bar.
After providing a back coat layer having a dry coating amount of 12 g / m ² , calender treatment was performed by setting calender conditions so that the smoothness of the back coat layer was about 50 (second / 10 cc).

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

<Preparation of a lithographic printing original plate> 100 g of dry zinc oxide (manufactured by Seido Chemical Co., Ltd.) as in Example 1, 14 g of a binder resin (B-5) having the following structure, and acrylic resin particles having the following contents A mixture of 1.5 g of the dispersion (as solid content), 0.20 g of m-toluic acid, and 230 g of toluene was used to prepare a mixture having a particle size of 0.1 g.
After dispersing for 8 minutes at a rotation speed of 6 × 10 ³ rpm using a Dynomill disperser (manufactured by Shinmaru Enterprise Co., Ltd.) for 8 minutes together with 200 g of glass beads having a size of 7 to 1 mm, the glass beads were filtered off to obtain a coating material for an image receiving layer. did.

[0242]

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Acrylic Acid Resin Particle Dispersion 8 g of acrylic acid, 2 g of AA-6 (trade name: methyl methacrylate macromonomer manufactured by Toa Gosei Chemical Co., Ltd.), 2 g of ethylene glycol dimethacrylate, 0.1 g of methyl 3-mercaptopropionate And a mixed solution of 55 g of methyl ethyl ketone was heated to a temperature of 60 ° C. under a nitrogen stream. 0.2 g of 2,2'-azobis (isovaleronitrile) was added thereto and reacted for 3 hours, and 0.1 g of this initiator was further added and reacted for 4 hours. The resulting dispersion is
At a reaction rate of 95%, the average particle size of the dispersed resin particles is 0.20 μm.
m (monodispersibility: CAPA)
-500 (trade name, manufactured by Horiba, Ltd.).

This dispersion was coated on a water-resistant support similar to that used in Example 1 with a wire bar so as to have a coating amount of 18 g / m ² and dried to obtain a lithographic printing plate precursor. The surface Beck smoothness of the obtained image receiving layer is 350 (sec / 10 c
c). The contact angle of the surface with water was 95 degrees.

This printing original plate was prepared in the same manner as in Example 2.
The plate was made and desensitized to form a printing plate, and offset printing was performed. However, the oil-based ink of Example 2 (IK-2)
Was replaced by an oil-based ink (IK-26) described below.

<Preparation of Oil Ink (IK-26)> The white dispersion (D-6) 30 obtained in Production Example 26 of resin particles
0 g and a mixture of 5 g of Victoria Blue B at a temperature of 10
The mixture was heated to 0 ° C and stirred with heating for 4 hours. 20 after cooling to room temperature
By removing the remaining dye through a 0-mesh nylon cloth, a black resin dispersion having an average particle size of 0.38 μm was obtained. 260 g of the above blue resin dispersion and 0.16 g of zirconium naphthenate were diluted to 1 liter of Shellsol 71 to prepare a blue oil-based ink.

The obtained printed matter was of a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 2.
The printing durability was as good as 3,000 sheets or more. Also, as in Example 2, the ink ejection test and the redispersibility compulsory test for 600 hours showed the same performance as that of the ink (IK-2) and was excellent.

[0248]

According to the present invention, an oil-based ink for ink-jet plate-making printing having excellent redispersibility, storage stability and printing durability can be obtained. Further, if the oil-based ink of the present invention is used, the nozzle and the ink supply path are not clogged,
Ink ejection becomes stable. Furthermore, by using the oil-based ink of the present invention, even when repeatedly used, ink-jet recording is performed stably, and a lithographic printing plate having excellent printing durability can be prepared, and a large number of prints of clear images can be printed. It is possible.

[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 Bus 10 Head 10a Discharge slit 10b Discharge electrode 10c Counter electrode 11 Oil-based ink 101 Upper unit 102 Lower unit

Claims (6)

[Claims] Claims: 1. A method according to claim 1, wherein zinc oxide and a binder are provided on a water-resistant support.
An image receiving layer containing a resin, and the surface of the image receiving layer
Of a lithographic printing plate with a contact angle of 50 ° or more with water
On the image receiving layer, an electric resistance of 10⁹Ωcm or more and dielectric constant
Separate at least the resin particles into a non-aqueous carrier liquid of 3.5 or less.
Spray the oil-based ink, which is scattered, into droplets from the nozzle
After forming an image by the inkjet method,
The non-image area of the layer is desensitized by chemical reaction
Method of making ink-jet type plate making printing plate as plate printing plate
Oil-based ink for ink-jet plate-making printing plates used for printing
In the, the dispersed resin particles, (i) in the non-aqueous carrier liquid
Soluble in non-aqueous solvents that are at least miscible
Monofunctional monomer that becomes insoluble by polymerization
At least one of (A), (ii) co-polymer with the monomer (A)
Of the monomer (C) represented by the following general formula (I)
At least one, and (iii) soluble in the non-aqueous solvent
Dispersion containing a copolymer component represented by the general formula (II)
A solution containing at least one of the standard resin (P) is
It is a copolymer resin obtained by
Oil-based ink-jet printing plate making plate
H. Embedded imageIn the formula (I), E¹Is an aliphatic group having 8 or more carbon atoms, or
8 or more atoms (however, hydrogen atoms bonded to carbon and nitrogen are
Excluding) and a substituent represented by the following general formula (III). one
General 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. B₁And B_TwoAre the same or different
Each may be -O-, -S-, -CO-, -CO
_Two-, -OCO-, -SO_Two-, -N (R_{twenty two})-, -CO
N (R _{twenty two})-, -N (R_{twenty two}) CO-, -N (R_{twenty two}) SO
_Two-, -SO_TwoN (R_{twenty two})-, -NHCO_Two-Or -N
HCONH- (where R_{twenty two}Is R_{twenty one}Same as
It shows the contents). A₁And A_TwoAre 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_ThreeAnd B_FourAre the same or different
The above B ₁, B_TwoShows 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 as or different from each other;
Represents an integer. However, m, n and p are simultaneously 0.
Never. In the formula (I), U¹Is -COO-, -CO
NH-, -CON (E^Two)-[Where E^TwoIs an aliphatic group
Or represents a substituent represented by the general formula (III)],
-OCO-, -CONHCOO-, -CH_TwoCOO-,
− (CH_Two)_sOCO- [where s represents an integer of 1 to 4
), -O-, -C₆H_Four-Or -C₆H_Four-COO-
Represent. a¹And a^TwoAre the same or different
Often, hydrogen, halogen, cyano, and alkyl
Group, -COO-E^ThreeOr -CH_TwoCOO-E^Three(here
In E^ThreeRepresents an aliphatic group). Embedded imageIn the formula (II), R¹Is an alkyl group having 10 to 32 carbon atoms or
Represents an alkenyl group. b¹Is a hydrogen atom or a methyl group
Represents X¹And X^TwoAre each U in formula (I)¹Same as-
Represents the contents of W is a bonding group X¹And bonding group X^TwoConcatenate with
Carbon-carbon bond which may be via a heteroatom
B atoms include oxygen, sulfur and silicon atoms.
Or a nitrogen atom). d¹, D^Two, E¹And e^Two
May be the same or different from each other, and in the formula (I)
a ¹, A^TwoAnd the contents of the same. x and y are weights of the copolymer.
The composition ratio is 90/10 to 99/1 (weight ratio).
You. 2. An ink-jet plate making method, wherein an image of the oil-based ink according to claim 1 is formed on a lithographic printing plate having a hydrophilic surface capable of lithographic printing by an ink-jet method to form a lithographic printing plate. How to make a printing plate. 3. The image forming method according to claim 1, wherein:
3. The method according to claim 2, wherein the oil-based ink is discharged using an electrostatic field. 4. The lithographic printing plate precursor is provided with an image receiving layer having a lithographically printable hydrophilic surface on a water-resistant support, and as the water-resistant support, at least immediately below the image receiving layer. 4. The method for preparing an ink-jet type plate making printing plate according to claim 2, wherein a support having a specific electric resistance value of 10 ¹⁰ Ωcm or less is used. 5. The water-resistant support is a support having a specific electric resistance of 10 ¹⁰ Ωcm or less for the whole support.
5. The method for producing an ink-jet type plate-making printing plate according to any one of items 1 to 4. 6. The ink-jet ink according to claim 2, wherein the resin particles dispersed in the oil-based ink are oil-based inks that are positively or negatively charged. How to make a formula plate printing plate.