JPH10251580A - Oily ink for ink jet type plate making of printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject product excellent in re-dispersion property, preservation stability and printing resistance by dispersing specific resin particles in a non-aqueous carrier liquid. SOLUTION: This oily ink for an ink jet type plate making of a printing plate, is obtained by dispersion resin particles obtained by polymerizing and granulating a solution containing (A) a mono-functional monomer soluble to a non-aqueous solvent and becoming insoluble by its polymerization, (B) a monofunctional macromonomer in which a polymerizable double bond of formula II (V<1> is COO, phenylene, etc.; b<1> , b<2> are each a<1> ) bonds only to one side of the terminals of a polymer main chain consisting of a unit of formula I (V<0> is COO, OCO, etc.; a<1> , a<2> are each H, cyano, etc.; D<0> is an 8-22C hydrocarbon, etc.), and (C) a comb type copolymer having a monofunctional macromonomer bonded with a polymerizable double bond to the one side of terminal of the polymer main chain as a copolymeric component as a non-aqueous soluble dispersion stabilizing resin having a unit of formula III (V<2> is COO, O, etc.; d<1> , d<2> are each a<1> ; D<1> is a 10-32C alkyl or an alkenyl) in main chain and/or comb part thereof, and dispersing the resin particles in a non-aqueous carrier liquid having >=10<9> Ωcm electric resistance and <=3.5 dielectric constant.

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.
The present invention relates to an oil-based ink having excellent redispersibility, storage properties, image reproducibility and printability.

[0002]

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

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

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

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

As such an ink jet recording method, a so-called drop-on-demand method (pressure pulse method) in which ink is ejected by utilizing electrostatic attraction, and bubbles are formed and grown by high heat. Various ink jet systems, such as a so-called bubble (thermal) system, for ejecting ink using the pressure generated by such a system have been proposed, and an extremely high-definition image can be obtained by these systems.

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

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

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

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

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

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

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

[0014]

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

It is another object of the present invention to provide an ink for an ink-jet type plate-making printing plate which can print a large number of prints of clear images.

Another object of the present invention is to provide an ink for an ink-jet plate-making printing plate in which the ejection of the ink is stable without clogging of the nozzle and the ink supply path.

[0017]

The above object is achieved by the following constitution. (1) Image reception 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 form a lithographic printing plate. In the above, the dispersed resin particles are soluble in a non-aqueous solvent, and are at least one kind of a monofunctional monomer (A) which is insoluble by polymerization, which is represented by the following general formula (I): Of polymer consisting of units At least one monofunctional macromonomer (MA) having a weight-average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the following general formula (II) to only one end of the main chain: A monofunctional macromonomer (MB) having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ^{4 formed} by bonding a polymerizable double bond group to only one end of the main chain of the polymer; A non-aqueous copolymer containing at least one component represented by the following general formula (III) as a repeating unit of a main chain portion and / or a comb portion of the copolymer. An oil-based ink for an ink-jet plate making plate, which is a polymer obtained by polymerizing and granulating a solution containing at least one dispersion stabilizing resin [P] soluble in a solvent.

[0018]

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[0019]

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In the general formula (I), V ⁰ is —COO—,
_{-OCO -, - (CH 2)} r COO -, - (CH 2) r
OCO -, - O -, - SO 2 -, - CONHCOO-,
^{-CONHCONH -, - COND 11 -,} - SO 2 ND
¹¹ -, or a phenylene group (wherein D ¹¹ represents a hydrogen atom or a number from 1 to 22 hydrocarbon group having a carbon, r is 1
4 indicates an integer). a ¹ and a ² may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹² , or —COO-D ¹² via a hydrocarbon group. (Where D ¹² represents a hydrogen atom or a hydrocarbon group which may be substituted). D ⁰
Represents a hydrocarbon group having 8 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (I ′). General formula ^{(I ') - (A 1} -B 1) m - (A 2 -B 2) n
-D ^{21 In the} general formula (I ′), D ²¹ is a hydrogen atom or a carbon number of 1 to 22
Represents a hydrocarbon group. B ¹ and B ² may be the same or different from each other, and are each -O-, -CO-, -C
O _2- , -OCO-, -SO _2- , -N (D ²² )-,-
CON (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^21). A ¹ and A ² may be the same or different from each other, and each may be substituted. Or a hydrocarbon group having 1 to 18 carbon atoms, which may be represented by the following formula 7 in the bond of the main chain.

[0021]

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In the chemical formula 7, B ³ and B ⁴ may be the same or different from each other, and have the same contents as B ¹ and B ² above, and A ⁴ has 1 to 18 carbon atoms which may be substituted. a hydrocarbon group, D ²³ represent the same contents as the D ^21. m,
n and p may be the same or different, and each represents an integer of 0 to 4. However, m, n and p do not become 0 at the same time. In the general formula (II), V ¹ is-
COO-, -CONHCOO-, -CONHCONH
-, -CONH- or a phenylene group. b ¹ and b ² may be the same or different from each other and represent the same contents as a ¹ and a ² in the formula (I).

[0023]

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In the formula (III), V ² represents —COO—, —OC
Represents an O-, -O- or phenylene group. d ¹ and d ²
May be the same or different, and represent the same contents as a ¹ and a ² in the formula (I). D ¹ has 10 to 3 carbon atoms
2 represents an alkyl group or an alkenyl group having 10 to 32 carbon atoms. (2) the dispersion stabilizing resin (P) is, at one terminal of the polymer main _{chain, -PO 3 H 2, -SO 3} H, -COOH,
—P (＝ O) (OH) R ¹ wherein R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group);
-OH, -SH, a formyl group, -CONR ³ R ^4, -S
O ₂ NR ³ R ⁴ wherein R ³ and R ⁴ are each independently
A hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group and at least one polar group selected from amino groups. (3) The ink jet method according to the above (1), wherein the dispersion stabilizing resin [P] contains a polymerizable functional group copolymerizable with the monomer (A) at one end of the polymer main chain. Oil-based ink for plate making and printing plates.

[0025]

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

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important components in the present invention, are a dispersion-stabilizing resin (P) which is soluble in the non-aqueous solvent in a non-aqueous solvent. And polymerized and granulated by polymerizing at least one of the monofunctional monomers (A) and at least one of the monofunctional micromonomers (MA) in the presence of

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, an alicyclic hydrocarbon, or an aromatic hydrocarbon. Group hydrocarbons and their halogen-substituted products. For example, octane, isooctane, decane, isodecane, decalin, nonane,
Dodecane, isododecane, isoper E, isoper G, isoper H, isoper L, shersol 70,
Shellsol 71, AMSCO OMS, AMSCO 460 solvent and the like are used alone or in combination.

Solvents that can be used by mixing with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.) and ketones (eg, acetone, methyl ethyl ketone, etc.). Cyclohexanone, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (eg,
Diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (for example, methylene dichloride, chloroform, carbon tetrachloride,
Dichloroethane, methyl chloroform, etc.).

It is desirable that the non-aqueous solvent used by mixing these is distilled off under heating or reduced pressure after polymerization granulation. Is within the range that can satisfy the condition of 10 ⁹ Ωcm or more.

In general, it is preferable to use the same solvent as the carrier liquid in the step of producing 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.

[0033]

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

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

E ¹ And e ² May be the same or different from each other, preferably a hydrogen atom, a halogen atom (for example,
A chlorine atom, a bromine atom), a cyano group, an alkyl group (e.g. methyl group having 1 to 3 carbon atoms, an ethyl group, a propyl group, etc.), - COO-Z ¹ or -CH ₂ -COO-Z
¹ [herein, Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group having 10 or less carbon atoms (eg, represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, etc.).

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

Two or more monomers (A) may be used in combination.

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

The monofunctional macromonomer (MA) has a polymerizable double monomer represented by the following general formula (II) only at one end of the main chain of a polymer comprising a repeating unit represented by the following general formula (I). Weight average molecular weight of 2 × 10
⁴ or less macromonomers.

[0041]

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[0042]

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In the formula (I), V ⁰ is -COO-, -OCO
_{-, - (CH 2) r} COO -, - (CH 2) r OCO-,
_{-O -, - SO 2 -,} - CONHCOO -, - CONH
^{CONH -, - COND 11 -,} - SO 2 ND 11 -, or a phenylene represents a group (-Ph-) (wherein D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, r is 1 4 indicates an integer).

A ¹ and a ² may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹² , or —COO-D ¹² through a hydrocarbon group. Represents ¹² (where D ¹² represents a hydrogen atom or a hydrocarbon group which may be substituted).

D ⁰ represents a hydrocarbon group having 8 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (I '). General formula ^{(I ') - (A 1} -B 1) m - (A 2 -B 2) n -D
^{twenty one}

In the general formula (I ′), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

B ¹ and B ² may be the same or different from each other, and are each -O-, -CO-, -CO ₂ -,-
_{OCO -, - SO 2 -,} - N (D 22) -, - CON (D
²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^21).

A ¹ and A ² may be the same or different from each other, and each may be substituted. Or a compound having 1 to 18 carbon atoms which may have the following
Represents a hydrocarbon group.

[0049]

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In formula 12, B ³ and B ⁴ may be the same or different from each other, and have the same contents as B ¹ and B ² described above, and A ⁴ has 1 to 18 carbon atoms which may be substituted. a hydrocarbon group, D ²³ represent the same contents as the D ^21.

M, n and p may be the same or different, and each represents an integer of 0-4. Where m,
n and p do not become 0 at the same time.

In the formula (II), V ¹ represents -COO-, -CO
Represents an NHCO-, -CONHCONH-, -CONH- or phenylene group.

B ¹ and b ² may be the same or different from each other and represent the same contents as a ¹ and a ² in the formula (I).

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

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

When V ⁰ represents -Ph- (phenylene group), the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.) and an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.).

A ¹ And a ² May be the same or different, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, and a carbon number of 1 to 3.
Alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), - COO-D ¹³ or -CH ₂ COO-D ^13,
(D ¹³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, these may be substituted, specifically, the D ¹¹ Are shown in the same manner as described above).

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

The case where D ⁰ represents a substituent represented by formula (I ') will be described in detail.

A ¹ and A ² may be the same or different from each other, may be substituted each, or may be
A hydrocarbon group having 1 to 18 carbon atoms (an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group may be mentioned as the hydrocarbon group; specific examples thereof include D ¹¹ has the same content as the specific example described in ¹¹ ).

A ¹ And A ² When further specific examples are given, these are -C (D ³¹ ) (D ³² )-[D ³¹ , D ³²
Represents a hydrogen atom, an alkyl group, a halogen atom, etc.],-
(CH = CH) -, phenylene group (-Pn-), a cyclohexylene group [hereinafter, "-C ₆ H a cyclohexylene
₁₀ - expressed in "" - C ₆ H ₁₀ - "xylene group 1,2-cyclohexylene, 1,3-cyclohexylene group, including xylene group] 1,4-cyclohexylene, the reduction 12 and the like Are composed of any combination of the atomic groups.

Further, in the bonding group in the general formula (I): -V ^0- (A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹ , V ⁰ to D ²¹ (that is, V ^0, A ^1, B
¹ , A ² , B ² , D ²¹ ) are preferably those having a total number of atoms of 8 or more. Here, -A ^3- (A ⁴ -B ⁴ ) _p in the case where A ¹ and A ² are a hydrocarbon group which causes the chemical formula 12 to intervene in the bond of the main chain.
-D ²³ is also included in the connecting backbone. As the number of atoms in the connecting main chain, for example, when V ⁰ represents -COO- or -CONH-, an oxo group (= O group) or a hydrogen atom is not included in 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. At the same time, when D ²¹ represents —C ₉ H ₁₉ , the number of hydrogen atoms is not included, and the number of carbon atoms is included.
Therefore, in this case, it is counted as 9 atoms.

In the above repeating unit represented by the general formula (I), when D ⁰ represents a substituent represented by the above general formula (I ′), that is, at least two or more of the repeating unit components in the molecule are used. When the specific polar group is contained, the following repeating unit can be more specifically mentioned as an example.

In the following formulas (1) to (19), each symbol represents the following.

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

[0066]

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[0067]

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[0068]

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

In the formula (II), V ¹ represents —COO—, —CO
Represents an NHCOO-, -CONHCONH-, -CONH- or phenylene group.

Here, the specific attitude of the phenylene group is the same as the phenylene group at V ⁰ in the formula (I).

B ¹ and b ² may be the same or different and have the same meaning as a ¹ or a ^{2 in} formula (I), and represent the same contents.

More preferably, ^one of b ¹ and b ^{2 in} the formula (II) is a hydrogen atom.

Examples of the group linking the components of the formula (I) and the component of the formula (II) include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom and sulfur atom). Atoms, nitrogen atoms, silicon atoms, etc.) and any combination of heteroatom-heteroatom bond atomic groups.

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

[0076]

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In the general formula (V), the contents other than Z have the same contents as the respective symbols in the formulas (I) and (II).

Z is a mere bond or —C (D ⁴¹ )
(D ⁴² )-[D ⁴¹ and D ⁴² each independently 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, Represents an ethyl group, a propyl group, etc.),-
(CH = CH) -, - C 6 H 10 - ( cyclohexylene group), - Ph- (phenylene group), - O -, - S -, -
CO-, -N ( ^D43 )-, -COO-, -SO-, -C
^{ON (D 43) -, -} SON (D 43) -, - NHCOO
-, - NHCONH -, - Si (D 43) (D 44) - [D
⁴³ and D ⁴⁴ each independently represent a hydrogen atom or a hydrocarbon group having the same content as that of the above D], and a single linking group selected from an atomic group such as a linking group shown in Chemical Formula 18 below. It represents a single linking group selected from atomic groups or a linking group composed of any combination.

[0079]

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In the formula (V), a ¹ , a ² , b ¹ , b
Particularly preferred examples of each of ² , V ⁰ and V ¹ are shown below.

As V ⁰ , -COO-, -OCO-,
-O -, - CH ₂ COO- or -CH ₂ OCO- is,
As V ¹ , all of the above are a ¹ , a ² , b
^1, a b ² may be mentioned a hydrogen atom or a methyl group.

Hereinafter, specific examples of the portion represented by the following general formula (II ') in the general formula (V) will be shown. However, the present invention is not limited to these.

[0083]

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

[0085]

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[0086]

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[0087]

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[0088]

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Further, in the macromonomer (MA) used in the present invention, other repeating units may be contained as a copolymerization component together with the repeating units represented by the general formula (I).

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

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

In the total of the repeating units of the macromonomer (MA), the repeating unit component represented by the general formula (I) is preferably contained in an amount of 60% by weight or more, more preferably 80 to 100% by weight. It is.

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

Within the above-mentioned predetermined ranges, excellent effects are obtained in the dispersion stability, re-dispersion stability and storage stability of the dispersed resin particles.

The macromonomer (MA) of the present invention can be produced by a conventionally known synthesis method. For example, a macromer is obtained by reacting various reagents with the terminal of a living polymer obtained by anionic or cationic polymerization. Ion polymerization method, terminal reactive group bond obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxy group, or an amino group in the molecule. A polymerizable double bond group is introduced into an oligomer obtained by reacting an oligomer of the above with various reagents to give a macromer by a radical polymerization method, or an oligomer obtained by a polyaddition or polycondensation reaction in the same manner as in the above radical polymerization method. Examples thereof include a method based on a polyaddition condensation method.

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

Examples of the polymerization initiator containing a reactive group in the molecule include, for example, 4,4'-azobis (4-cyanovaleric acid) and 4,4'-azobis (4-cyanovaleric chloride). 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propioamide], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl ) -2-Hydroxyethyl] propioamide}, 2,
2'-azobis (2-amidinopropane), 2,2'-
Azobis [2-methyl-N- (2-hydroxyethyl)
-Propioamide], 2,2'-azobis [2- (5-
Methyl-2-imidazolin-2-yl) propane],
2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane], 2,2'-azobis [2- (3,4,5 , 6-Tetrahydropyrimidin-2-yl) propane], 2,
2'-azobis [2- (5-hydroxy-3,4,5,
6-tetrahydropyrimidin-2-yl) propane],
2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,
2'-azobis [N- (2-hydroxyethyl) -2-
Azobis compounds such as methyl-propionamidine] and 2,2'-azobis [N- (4-aminophenyl) -2-methylpropionamidine].

Examples of the chain transfer agent containing a specific reactive group in the molecule include, for example, a mercapto compound containing a reactive group or a substituent capable of being induced to the reactive group (for example, thioglycolic acid, Thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid,
3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, −
Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, etc.), or the reactive group or an iodized alkyl compound containing a substituent capable of being induced to the reactive group (for example,
Iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

The amount of the chain transfer agent or the polymerization initiator used is 0.5 to 100 parts by weight of the total monomers.
Preferably, it is used in an amount of 1 to 20 parts by weight, more preferably 1 to 10 parts by weight. The dispersion resin of the present invention comprises at least one kind of each of the monomer (A) and the monofunctional macromonomer (MA). Importantly, the resin synthesized from these monomers is used in a non-aqueous solvent. If it is insoluble, a desired dispersion resin can be obtained.

More specifically, the monomer (A) to be insolubilized
To the monofunctional macromonomer (MA)
It is preferable to use 20% by weight, more preferably 0.3 to
It is preferable to use 15% by weight.

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

Within the above ranges, the dispersion stability, re-dispersion stability, and storage stability of the dispersed resin particles of the oil-based ink of the present invention are excellent, and the fast fixability after image formation is good. The image is retained during printing, and high printing durability is exhibited.

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.

The dispersion stabilizing resin [P] of the present invention is a macromolecular compound having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ comprising a polymerizable double bond bonded to only one end of the polymer main chain. A comb copolymer containing at least one monomer (MB) as a copolymer component, and a component represented by the above general formula (III) as a repeating unit of a main chain portion and / or a comb portion of the copolymer. It is a resin soluble in the non-aqueous solvent at least.

The dispersion stabilizing resin [P] is represented by the above general formula (II) as a repeating unit of the main chain and / or comb portion.
It contains at least one component represented by I). Preferably, both the main chain portion and the comb portion contain the repeating unit represented by the general formula (III).

The proportion of the repeating unit represented by the general formula (III) in the dispersion stabilizing resin [P] is determined by comparing the repeating unit as a copolymer component other than the macromonomer (MB) in the main chain with the comb portion. Constituent macromonomer (MB)
Is preferably from 50 to 100,
wt%, more preferably 70 to 100 wt%. When the content of the repeating unit of the general formula (III) is less than 50% by weight, the redispersibility of the resin particles obtained by polymerization granulation tends to decrease.

The proportion of the macromonomer (MB) as a copolymer component of the comb-type copolymer is preferably 5 to 80 wt%, more preferably 5 to 80 wt%, based on all components of the dispersion stabilizing resin [P]. Is 10 to 60 wt%. When the proportion of the macromonomer (MB) is less than 5 wt%, the number of comb portions tends to be significantly reduced, and the redispersibility of the resin particles, which is an effect of the present invention, is reduced. On the other hand, when the proportion of the macromonomer (MB) exceeds 80% by weight, the copolymerizability of the macromonomer (MB) with the monomer to be copolymerized at the time of synthesizing the comb copolymer tends to decrease. It is in.

The weight average molecular weight (hereinafter abbreviated as “Mw”) of the dispersion stabilizing resin [P], which is the comb copolymer of the present invention, is preferably 2 × 10 ⁴ to 1 × 10 ⁶ , and more preferably. Is 3 × 10 ^{4 to} 5 × 10 ⁵ . Mw is 2 ×
If less than 10 ⁴ or more than 1 × 10 ⁶ ,
The redispersibility of resin particles obtained by polymerization granulation tends to decrease.

The Mw of the macromonomer (MB) is 1
× 10 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to
It is 1 × 10 ⁴ .

The dispersion stabilizing resin [P] is soluble in an organic solvent, and specifically, a resin in which at least 5 parts by weight or more of the dispersion stabilizing resin is dissolved at 25 ° C. in 100 parts by weight of a toluene solvent. Is preferred. Hereinafter, the dispersion stabilization [P] of the present invention will be described in more detail. In the formula (III), V ² represents —COO—, —OCO—, —O— or a phenylene group.

When V ² represents -Ph- (phenylene group), the benzene ring may have a substituent. As the substituent, a halogen atom (eg, a chlorine atom, a bromine atom, etc.),
Alkyl group (for example, methyl group, ethyl group, propyl group,
A butyl group, a chloromethyl group, a methoxymethyl group and the like; an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group and a butoxy group).

D ¹ and d ² may be the same or different from each other and represent the same contents as a ¹ and a ² in the formula (I).

D ¹ represents an alkyl or alkenyl group having 10 to 22 carbon atoms, such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl,
Octadecyl group, docosanyl group, eicosanyl group, octenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, linoleyl group, dococenyl group and the like.

As the repeating unit of the main chain portion and the comb portion of the dispersion stabilizing resin [P] of the present invention, other repeating units may be contained in addition to the repeating unit represented by the above general formula (II). Other repeating units include those represented by the above general formula (II)
The repeating unit is not particularly limited as long as it is a repeating unit composed of another monomer copolymerizable with the monomer corresponding to the repeating unit represented by.

The other copolymerizable monomer may be any as long as it contains a polymerizable double bond group. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid. Acid; ester derivative or amide derivative of unsaturated carboxylic acid having 6 or less carbon atoms; vinyl ester or allyl ester of carboxylic acid; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compound having polymerizable double bond group and the like. Is mentioned. More specifically, a compound having the same content as the monomer (A) to be insolubilized is mentioned.

The monofunctional macromonomer of the present invention (MB)
Examples of the polymerizable double bond group include those having the same contents as those represented by the formula (II) in the monofunctional macromonomer (MA).

Further, the polymerizable double bond group may be directly bonded to the terminal of the polymer main chain or may be bonded via a linking group. “-V ¹ -Z-” in the general formula (IV) exemplified by (MA)
And the same contents as above.

The micromonomer (MB) of the present invention can be produced by a conventionally known synthesis method, and specifically, can be produced in the same manner as the micromonomer (MA).

As a method for producing the dispersion stabilizing resin polymer [P] used in the present invention, specifically, a known method, a monomer corresponding to the repeating unit represented by the general formula (III) is used. In addition, a method in which at least the above-mentioned macromonomer (MB) is allowed to coexist and polymerization is carried out with a polymerization initiator (for example, an azobis compound, a peroxide or the like) is simple and preferable.

The polymerization initiator used here is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the total amount of all monomers and all macromonomers (MB). is there.

As the dispersion stabilizing resin [P] to be used in the present invention, a resin obtained by bonding a specific polar group to one end of the polymer main chain is preferable. [Hereinafter referred to as dispersion stabilizing resin [PA] or [PA]. ]

Specific polar groups include -PO ₃ H ₂ ,-
_{SO 3 H, -COOH, -P (} = O) (OH) R 1 [wherein R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, -SH , Formyl group,
—CONR ³ R ⁴ , —SO ₂ NR ³ R ⁴ [where R ³
And R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from an amino group.

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

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

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

Examples of the aliphatic dicarboxylic anhydride include:
Succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylic anhydride, 2 , 3-bicyclo [2,2,2] octanedicarboxylic anhydride and the like, and these aliphatic dicarboxylic anhydrides include, for example,
It may be substituted with a hagelon atom such as a chlorine atom or a bromine atom, or an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group.

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

In the polar group of the present invention, the amino group is represented by -N
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ , R ⁶
Represents a hydrocarbon group having 1 to 8 carbon atoms, and preferably represents a hydrocarbon group having 1 to 7 carbon atoms.
Those having the same contents as the hydrocarbon group represented by ¹ can be mentioned.

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

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

More specific examples of the linking group include those having the same contents as those exemplified for the above-mentioned micromonomer (MA).

The resin polymer [PA] for dispersion stabilization used in the present invention is, specifically, a monomer corresponding to the repeating unit represented by the general formula (III), the above-mentioned macromonomer (MB), A method of polymerizing a mixture of the above-mentioned chain transfer agent containing a specific polar group with a polymerization initiator (for example, an azobis compound, a peroxide or the like) or containing the polar group without using the above chain transfer agent A method of polymerizing using a polymerization initiator, a method of using a compound containing the polar group as both a chain transfer agent and a polymerization initiator, and further, in the above three methods, a chain transfer agent or a polymerization initiator After a polymerization reaction using a compound containing an amino group, a halogen atom, an epoxy group, an acid halide group, or the like as a substituent of the above, the polar group is further reacted by a polymer reaction with these functional groups. Can be produced using a method in which ON.

Specific examples of the above-mentioned chain transfer agent containing a specific polar group or a substituent capable of deriving to the polar group include mercapto described above as a reactive group-containing chain transfer agent in a method for synthesizing a macromonomer (MA). And iodide alkyl compounds. Preferably, a mercapto compound is used.

The above-mentioned azobis-based compound as a polymerization initiator containing a reactive group in the macromonomer (MA) can also be used as the polymerization initiator containing a specific polar group or a substituent which can be induced to the above-mentioned polar group. .

The amount of the chain transfer agent or the polymerization initiator used is determined by the total monomer and the total macromonomer (MB), respectively.
Is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of

More preferably, as the dispersion stabilizing resin [P] used in the present invention, a polymerizable functional group copolymerizable with the monomer (A) is bonded to one end of the polymer main chain. What is. [Hereinafter referred to as dispersion stabilizing resin [PB] or resin [PB]. ]

The specific content of the polymerizable functional group of the dispersion stabilizing resin [PB] is the same as the functional group represented by the general formula (II) described as the polymerizable functional group in the micromonomer (MA). Is mentioned.

Further, the polymerizable functional group may be directly bonded to one end of the polymer main chain, or may be bonded via a linking group. As the linking group, the dispersion stabilizing resin [P
A] and those having the same contents as those of the linking group.
Specifically, it can be carried out in the same manner as the method of introducing a polymerizable double bond group at the terminal of the polymer main chain in the method for synthesizing the micromonomer (MA).

To produce the dispersion resin particles used in the present invention, generally, the dispersion stabilizing resin (P) as described above,
The monomer (A) and the macromonomer (MA) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutylnitrile, and butyllithium. Specifically, a dispersion stabilizing resin (P),
A method in which a polymerization initiator is added to a mixed solution of a monomer (A) and a macromonomer (MA), and a monomer (A) and a macromonomer (MA) are added to a solution in which a dispersion stabilizing resin (P) is dissolved. ) Is added dropwise together with the polymerization initiator, or in a mixed solution containing the whole amount of the dispersion stabilizing resin (P) and a part of the monomer (A) and the macromonomer (MA) together with the polymerization initiator. A method of arbitrarily adding the monomer (A) and the macromonomer (MA), and further adding the dispersion stabilizing resin (P), the monomer (A) and the macromonomer (MA) in a non-aqueous solvent. There is a method of arbitrarily adding the mixed solution together with the polymerization initiator, and any method can be used to produce the mixed solution.

The monomer (A) and the macromonomer (M
The total amount of A) is 10 to 10 parts by weight of the non-aqueous solvent.
It is about 100 parts by weight, preferably 10 to 80 parts by weight.

The dispersion stabilizing resin (P) is used in an amount of 3 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of the polymerization initiator is 0.1 to 10 of the total monomers.
% By weight is appropriate. The polymerization temperature is 40 to 180 ° C.
Degree, preferably 50 to 120 ° C. The reaction time is preferably 3 to 15 hours.

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

As described above, the non-aqueous dispersion resin particles produced according to the present invention exist as fine particles having a uniform particle size distribution. The average particle size is 0.08 to 0.5
μm, and preferably 0.1 to 0.4 μm. The particle size can be determined using CAPA-500 (trade name, manufactured by Horiba, Ltd.) or the like. At the same time, it shows extremely stable dispersibility, and especially in a recording device, has good dispersibility even when used repeatedly for a long time, and is easy to re-disperse. Is not recognized at all.

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

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

That is, in the dispersed resin particles of the present invention, the dispersion stabilizing resin [P] interacts with the insoluble resin particles and is adsorbed on the insoluble resin particles. Since the resin [P] adsorbed on the resin particles is soluble in the non-aqueous solvent, the resin [P] has a so-called steric repulsion effect which is known as stabilization of dispersion of the non-aqueous latex. At the same time, since the resin [P] is a soluble resin containing a comb structure, the affinity for a non-aqueous solvent is significantly improved, and the adsorbed resin [P]
Is present in the vicinity of the particle interface because of having a comb-type structure, which is presumed to improve the affinity for the particles in the vicinity of the particle interface.

Further, together with the monomer (A) which is polymerized and insolubilized, a macromonomer (MA) comprising a co-component soluble in a non-aqueous solvent is simultaneously present in a small amount with respect to the monomer (A). These are dispersed resin particles produced by polymerization granulation, and a macromonomer (M
The soluble component contained in A) is present, the particle surface is improved in some way, the affinity with the dispersion medium is improved, the solvation with the dispersion medium is increased, and the aggregation of the resin particles is prevented. It is thought to be due to this.

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

In the present invention, when a dispersion stabilizing resin [PA] containing a specific polar group at at least one end of the polymer main chain, which is a preferred embodiment, the interaction with the insoluble resin particles is reduced. It is considered that the effect of the above-mentioned dispersion stabilization is further improved by further improving the adsorption property to the particles.

In a further preferred embodiment, a dispersion stabilizing resin [PB having a polymerizable functional group at one end of the polymer main chain]
Is used, it is copolymerized with the insoluble monomer (A) and the micromonomer (MA) at the time of the dispersion polymerization reaction, and is more efficiently bonded to the insoluble resin particles.

As described above, when the dispersion stabilizing resin [P] of the present invention is used, the dispersion stability is improved.
When the resin [PA] or the resin [PB] is used, the same or more effect can be obtained even if the amount used is reduced. On the other hand, in the case of the resin [PA] or the resin [PB], the stabilization of the dispersion can be achieved with a small use amount, and the amount of the resin [P] not adsorbed on the particles is reduced. These are concentrated in the developer when the oil-based ink is repeatedly used for a long period of time, so that the fear of causing various problems is improved.

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.

Regarding 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, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigments, 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 0.01 to 5% by weight based on the whole ink. desirable.

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

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

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

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

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

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

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 contact angle with water. ,
Preferably 50 ° to 130 °, more preferably 50 °
To 120 °, particularly preferably 55 ° to 110 °.

When the contact angle with water is in the above range, the strength of the image layer is sufficiently maintained as described above, and a clear image is formed without disturbing the image such as fine lines, fine characters and halftone dots. Is done.

[0167] The contact angle is a value measured by a contact angle meter using a droplet method with distilled water.

On the other hand, the apparatus disclosed in JP-A-54-117203 uses an ink-jet system using an oil-based ink 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 from the present invention. 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, and more preferably 45 to 500 (sec / 10), in Beck smoothness.
cc).

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 area 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 is a tester in which a test piece is pressed at a constant pressure (1 kg / cm ² ) on a highly smooth finished circular glass plate having a hole at the center, and a fixed amount (10 cc) is obtained 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 white 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 called 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.

Further, the content of zinc oxide in the image receiving layer is preferably 10 to 25 wt%, more preferably 12 to 22 wt%.

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 used in the image receiving layer of the present invention constitutes an image receiving layer together with zinc oxide, and has a hydrophobic property such that the contact angle on the surface thereof is within the above-mentioned predetermined range. The resin has a weight average molecular weight Mw of preferably 10 ³ to 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . Further, the glass transition point of this resin is preferably from 0 ° C to 120 ° C, more preferably from 10 ° C to 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 components described above.

As other components that may be contained, there are other inorganic pigments of the 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 30 parts by weight based on the zinc oxide of the present invention.

Further, in order to improve the desensitization of the image receiving layer, Japanese Patent Application Laid-Open Nos. 4-201387 and 4-223196.
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 is sufficiently performed by the desensitization treatment, 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 cross-linking agent include compounds which are usually used as a cross-linking agent. Specifically, see “Crosslinker Handbook”, edited by Tozo Yamashita and Tosuke Kaneko, published by Taiseisha (19
1981), edited by the Society of Polymer Science, “Polymer Data Handbook,
Compounds described in Basic Edition, Baifukan (1986) and the like 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 a 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.) and phenols (phenol, phenol, Chlorophenol, nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamine) Acid salts), tinouram disulfide compounds (tetramethyltinouram disulfide, etc.), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic 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 with 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 rays may be any of visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, γ-rays, α-rays, etc., but are preferably ultraviolet rays, more preferably from 310 nm to 500 nm.
Light rays in the nm range. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp, or the like is used.
Light irradiation is usually performed for 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes can be performed sufficiently.

[0193] The thickness of the image receiving layer in the invention is preferably about 3~30g shows the coating amount of the image-receiving composition per original 1 m ² (after drying). This image quality receiving layer is usually 3 to 50 vol%, preferably 10 to 40 vol%.
It is preferable to have a porosity of about l%.

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

The support provided in the present invention has a surface smoothness on the side adjacent to the image receiving layer having 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, an underlayer and an overcoat layer described later are provided on the support. In this case, 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 any irregularities on the surface of the support, and the image quality can be further improved.

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

In the present invention, as a method for melt-bonding the resin, it is preferable that the resin is coated by an extrusion lamination method. By coating by this extrusion lamination method, a support having a desired smoothness can be produced. The extrusion laminating method is a method in which a resin is melted, formed into a film, immediately pressure-bonded to base paper, and then cooled and laminated, and various apparatuses are known.

The thickness of the resin layer laminated in this manner is 10 μm or more from the viewpoint of production stability. Preferably it is 10 μm to 30 μm.

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 support surface opposite to the image receiving layer. A backcoat layer (backside layer) can be provided for the purpose, but the smoothness of the backcoat layer is preferably in the range of 150 to 700 (sec / 10 cc).

Thus, when the printing plate is supplied to the offset printing press, the printing plate is accurately set on the printing press without causing displacement or slippage.

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

Examples of the substrate used for the original plate of the present invention include wood pulp paper, synthetic pulp paper, mixed paper of wood pulp and synthetic pulp, non-woven fabric, plastic film, cloth, metal sheet, and composite sheet materials thereof. The substrate can be used as it is. Further, in order to obtain the smoothness specified in the present invention, and to adjust the water resistance and other properties, a hydrophobic resin used for an under layer or a back coat layer described below on the substrate, water dispersibility or A coating made of a water-soluble resin, a pigment, or the like may be impregnated.

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

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

To prepare the lithographic printing plate precursor according to the present invention, a solution containing an under layer component is coated on one side of the support, if necessary, to form an under layer, and if necessary, the other layer is formed on the other side. 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. Note that the image-receiving layer, the under layer, the coating amount of the backcoat layer are each 1 to 30 g / m ^2, in particular 6~20g / m ²
Is appropriate.

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

Next, a method for 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 shown in FIG. 1 has an ink jet recording apparatus 1 using oil-based ink.

As shown in FIG. 1, first, pattern information of an image (figure or text) to be formed on the master 2 is transmitted from an information supply source such as the computer 3 through a transmission means such as 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, ejects minute droplets of the ink to the master 2 according to the information. Thereby, ink adheres to the master 2 in the pattern.

[0213] 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 structure of an ink jet recording apparatus as in the apparatus system shown in FIG. 2 and 3, members common to FIG. 1 are denoted by common reference numerals. FIG. 2 is a schematic configuration diagram showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

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 in accordance with 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.

It is preferable that the width of the discharge electrode 10b is as narrow as possible to form a high-quality image, 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 formed 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 a non-image portion to prepare a printing plate.

Desensitization of zinc oxide has been conventionally performed by 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. There are known 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 liquid,
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 phytic acid compound-containing treatment solution 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-53-104301.
No. 140103, No. 54-18304, Tokuhei 43-
No. 28404.

Examples of the treatment liquid 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 those described in JP-A-56-111695.

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.

The desensitizing treatment is usually carried out 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.

[0229]

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

Production Example 1 of Macromonomer (M) A mixed solution of 100 g of macromonomer M-1 decyl methacrylate, 2 g of mercaptopropionic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviated as AIBN) was added, and the mixture was reacted for 4 hours. I. B. N. Was added for 3 hours, and A. I. B. N. 0.3 g
The reaction was performed for 3 hours. Next, 6 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. The weight-average molecular weight of the polymer was 9,000 (the weight-average molecular weight is expressed in terms of polystyrene by the GPC method; the same applies hereinafter).

[0231]

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Production Examples 2 to 15 of Macromonomer (M)
Macromonomer M-2 to M-15 The reaction was performed in the same manner as in Production Example 1 except that in Example 1 for producing a macromonomer, only methyl methacrylate was replaced with a compound corresponding to Table 1 below. M
-15 was synthesized. The weight average molecular weight of each obtained macromonomer was in the range of 7,000 to 9,000.

[0233]

[Table 1]

Production Example 16 of Macromonomer (M): Macromonomer M-16 70 g of dodecyl methacrylate, 30 g of octadecyl acrylate, 4 g of thioethanol and 200 g of toluene
Was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. A. I. B. N. Was added and reacted for 4 hours. Further, A.I. I. B. N. Was added for 3 hours, and then A. I. B. N. Was added and reacted for 3 hours. The reaction solution was cooled to room temperature, 18.2 g of 2-carboxyethyl acrylate was added, and 24 g of dicyclohexylcarbodiimide (abbreviated as DCC) was added thereto.
And a mixed solution of 150 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred as it was for 4 hours.

The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was collected by decantation, and 150 ml of methylene chloride was collected.
And reprecipitated again in 1 liter of methanol. The oil was collected and dried under reduced pressure to obtain a polymer having a weight average molecular weight of 8,000 in a yield of 54 g.

[0236]

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Production Examples 17 to 2 of Macromonomer (M)
1: Macromonomer M-17 to M21 In the production example of macromonomer M-16, unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate)
In the same manner as in the production example of M-16, and the macromonomers shown in Table 2 below were produced. Each of the obtained macromonomers had a weight average molecular weight of about 8,000.

[0238]

[Table 2]

Production Example 22 of Macromonomer (M) Macromonomer M-22 A mixed solution of 100 g of octadecyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated to a temperature of 75 ° C. under a nitrogen stream. 4,4 '
-Azobis (4-cyanovaleric acid) (abbreviation: A.C.
V. ) Was added and reacted for 5 hours. C. V.
Was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liters of methanol, and the oil was collected by decantation and dried under reduced pressure. The yield was 85 g.

50 g of the obtained oil (oligomer) was obtained.
15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 1.0 g of 2,2'-methylenebis (6-t-butyl-p-cresol) were added,
The mixture was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in 1 liter of petroleum ether to obtain a white powder 42
g was obtained. The weight average molecular weight was 7,500.

[0241]

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Production Example 1 of Dispersion Stabilizing Resin [P]: Resin P
-1 Octadecyl methacrylate 70 g, macromonomer M
A mixed solution of 30 g of -3 and 200 g of toluene was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 2,2'-
Azobis (isobutyronitrile) (abbreviated as AIB)
N. ) Was added and reacted for 4 hours. Further, A. I.
B. N. Was added and reacted for 2 hours. I.
B. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 1.5 l of methanol, and the powder was collected by filtration and dried to obtain 88 g of a white powder.

The obtained polymer had a weight average molecular weight (abbreviated as Mw) of 4.5 × 10 ⁴ .

Production Examples 2 to 11 of Dispersion Stabilizing Resin [P]:
Resins P-2 to P-11 In Production Example 1 of dispersion stabilizing resin [P], the monomers of Table 3 below and macromonomer (M) were used instead of octadecyl methacrylate and macromonomer M-3, respectively. Each dispersion stabilizing resin was produced in exactly the same manner as in Production Example 1. Mw of each resin is 4.0 × 10 ^{4 to} 6 × 10 ⁴
Met.

[0245]

[Table 3]

Preparation Example of Dispersion Stabilizing Resin [PA] 1: Resin PA-1 80 g of octadecyl methacrylate, macromonomer M
A mixed solution of 20 g of -7 and 150 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A. C.
V. Was added and reacted for 4 hours. C. V. Was added for 2 hours. C. V. Was added and reacted for 3 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, collected by filtration and dried to obtain 76 g of a white powder. Mw
Was 4.8 × 10 ⁴ .

[0247]

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Preparation Example 2 of Resin for Stabilizing Dispersion [PA]: Resin PA-2 40 g of isopropyl methacrylate, macromonomer M
-4, 60 g, thiomalic acid 0.8 g, toluene 100
g and 50 g of isopropyl alcohol were heated to a temperature of 80 ° C. under a nitrogen stream. 1,1′-azobis (cyclohexane-1-carbocyanide) (abbreviation: A.
B. C. C. ) Was added and reacted for 4 hours.
B. C. C. Was added for 3 hours. B.
C. C. Was added and reacted for 4 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, collected by filtration and dried to obtain 78 g of a white powder. Mw of the obtained resin is 3.8 × 10
^{Was 4} .

[0249]

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Production Examples 3 to 7 of dispersion stabilizing resin [PA]:
Resins PA-3 to PA-7 In Production Example 2 of Resin PA-2, Production Example 16 was repeated except that isopropyl methacrylate, macromonomer M-4, and mercapto compound (thiomalic acid) were replaced with compounds corresponding to Table 4 below. In the same manner, each resin PA-3
PA-7 was produced.

The Mw of each resin is 3.0 × 10 ⁴ to 4 × 10
^{Was 4} .

[0252]

[Table 4]

Production Example 1 of Dispersion Stabilizing Resin [PB] Resin PB -1 Resin PA synthesized in Production Example 1 of Dispersion Stabilizing Resin [PA]
-1 was stirred at a temperature of 25 ° C. while stirring a mixed solution of 50 g, allyl alcohol 5 g and tetrahydrofuran 100 g.
Set to. To this solution, 8 g of dicyclohexyl dicarbodiimide (abbr. DCC), 0.2 g of 4- (N, N-diethylamino) pyridine and methylene chloride 2 g
0 g of the mixed solution 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 1 liter of methanol. After the precipitate was collected by filtration, it was dissolved again in 90 g of toluene, the insoluble matter was removed by filtration, and the filtrate was reprecipitated in 500 cc of methanol.
The precipitate was collected by filtration and dried.

The yield of the obtained polymer was 32 g, and Mw was 3 × 10 ⁴ .

[0255]

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Production Examples 2 to 7 of dispersion stabilizing resin [PB]:
Resins PB-2 to PB-7 In Production Example 1 of dispersion stabilizing resin [PB], the same operation as in Production Example 1 was carried out except that a polymerizable group-introducing compound shown in Table 5 below was used instead of allyl alcohol. A dispersion stabilizing resin was manufactured.

[0257]

[Table 5]

Production Example 8 of dispersion stabilizing resin [PB]: Resin PB-8 hexadecyl methacrylate 60 g, macromonomer M
A mixed solution of 40 g of -13 and 200 g of tetrahydrofuran was heated to a temperature of 75 ° C. under a nitrogen stream. 2,2'-azobis (2-cyanoheptanol) (abbreviation: AB
C. H. ) Was added and reacted for 4 hours. B. C.
H. Was added and reacted for 4 hours.

Next, the reaction mixture was cooled to 25 ° C.
6 g of methacrylic acid was added thereto, and D.I. C.
C. 9.5 g, 0.4 g of 4- (N, N-diethylamino) pyridine and 40 g of methylene chloride in
The mixture was added dropwise over a period of time, and further stirred for 4 hours.

Next, 10 g of an 85% aqueous formic acid solution was added, and the mixture was stirred for 1 hour. After filtering off insolubles, the filtrate was reprecipitated in 2 liters of methanol. The precipitate was collected by filtration and dried. Mw of the obtained polymer was 5.5 × 10 ⁴ .

[0261]

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Preparation Example 1 of Latex Particle 1: Latex Particle L-1 12 g of dispersion stabilizing resin P-1, vinyl acetate 100 g,
2 g of macromonomer (M) -4 and 3 g of Isopar H
70 ° C. while stirring 84 g of the mixed solution under a nitrogen stream.
Was heated. As a polymerization initiator, 2,2'-azobis (isovaleronitrile) (abbreviated as AIVIN) was added in an amount of 0.8.
g., and reacted for 3 hours. I. V. N. To 0.
8 g was added and reacted for 2 hours. Subsequently, A.I.
I. B. N. Was added, and the temperature was raised to 80 ° C. and reacted for 3 hours.
The mixture was stirred at 0 mmHg for 2 hours to distill off unreacted monomers.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 98% and an average particle size of 0.20 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour).
The sedimented resin particles were collected and dried, and the weight average molecular weight (Mw) and glass transition point (Tg) of the resin particles were measured. The Mw was 2 × 10 ⁵ (according to GPC). (Polystyrene equivalent value; the same applies hereinafter), glass transition point: Tg was 38 ° C.

Latex Particle Production Examples 2 to 7: Latex Particles L-2 to L-7
Table 6 below in place of -1 and micromonomer M-4
The latex particles L-2 to L-2 of the present invention were operated in exactly the same manner as in Production Example 1 except that the dispersion stabilizing resin described in
-7 was produced. The polymerization rate of each of the obtained latex particles was 95 to 98%, the average particle size was in the range of 0.18 to 0.23 μm, and the monodispersity was good.

[0265]

[Table 6]

[Production Examples 8 to 11 of Latex Particles: Resin Particles L-8 to L-11]
Except that the respective monomers (A) and macromonomers (M) shown in Table 7 below were used in place of vinyl acetate (monomer A) and macromonomer M-1, exactly the same as in Production Example 1 above. Thus, latex particles L-8 to L-11 of the present invention were produced.

[0267]

[Table 7]

The average particle size of each latex particle is from 0.2 to
0.24 μm, and the conversion was in the range of 93 to 98%.

The Mw of each resin particle is from 8 × 10 ⁴ to 1 × 1.
0 ⁵ was in the range of.

Production Example 12 of Latex Particles: Latex Particles L-12, 12 g of dispersion stabilizing resin PA-2 and Isopar H177
g of the mixed solution was heated to a temperature of 60 ° C. while stirring under a nitrogen stream.

20 g of methyl methacrylate, 80 g of methyl acrylate, 3 g of micromonomer M20, 200 g of Isopar H, and I. V. N. Was added dropwise over 2 hours, followed by stirring for 2 hours.
Further, A. I. B. N. Was added and the temperature was raised to 80 ° C., followed by stirring for 3 hours. After cooling, the mixture was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 100% and an average particle size of 0.22 μm.

Mw of resin particles is 2 × 10 ⁵ , Tg is 2
6 ° C.

Preparation Examples 13 to 18 of Latex Particles: Latex Particles L-13 to L-18 In Preparation Example 12 of latex particles, the compounds shown in Table 8 below were used in place of the dispersion stabilizing resin P-2. Except for this point, latex particles were produced in the same manner as in Production Example 12.

The resulting latex particles had a polymerization rate of 90.
〜95%, the average particle size was in the range of 0.18-0.25 μm, and the monodispersity was good.

The Mw of each resin particle is from 8 × 10 ⁴ to 2 ×
10 ^5, Tg ranged from 36 to 39 ° C..

[0276]

[Table 8]

Latex Particle Production Examples 19 to 27: Latex Particles L-19 to L-27 Monomer (A) (namely, methyl methacrylate and methyl acrylate) and macromonomer M used in Latex Particle Production Example 12 Latex particles were produced in the same manner as in Production Example 12 except that the compounds shown in Table 9 below were used instead of -20 and the dispersion stabilizing resin PA-2, respectively.

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

[0279]

[Table 9]

Production Example 28 of Latex Particles: (Comparative Example A) Production example of latex particles except that a mixed solution of 20 g of dispersion stabilizing resin (RP-1) having the following structure, 100 g of vinyl acetate and 380 g of Isopar H was used. The same treatment as in Example 1 was carried out to obtain a white dispersion as latex particles having a polymerization rate of 93% and an average particle size of 0.23 μm.

[0281]

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Production Example 29 of Latex Particles: (Comparative Example B)
A white dispersion was synthesized in exactly the same manner as in Production Example 1, except that instead of -1, 15 g, a conventionally known dispersion stabilizing resin RP-2 having the following structure was used, 14 g. Latex particles having a polymerization rate of 95% and an average particle size of 0.21 μm were obtained.

[0283]

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Example 1 <Preparation of a lithographic printing original plate> 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)
A mixture of 17.0 g, 0.15 g of benzoic acid (A-1) and 155 g of toluene 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.).

[0285]

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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 light 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, the temperature was 102 degrees. (The lower the value, the better the wettability to water and the more hydrophilic.)

The smoothness of the image receiving layer was determined by measuring the smoothness (second / 10 cc) of the printing plate using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 10 CC. , 220 (sec / 10 cc).

Incidentally, 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. Was.

Preparation of Latex Particles The resin particles (L
-1) 50 g (as solid content), 18 g of the above-mentioned alkali blue dispersion, FOC-1400 (Nissan Chemical Co., Ltd.)
30 g of octadecene-hema maleic acid octadecylamide copolymer 0.0
8 g was diluted to 1 liter of Isopar G to obtain a blue oily ink.

Using the lithographic printing plate precursor 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. , 1.5
Printing was performed on the lithographic printing plate precursor placed on the opposing electrode with a gap of mm by using the above-described oil-based ink (IK-1). Subsequently, using an 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 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 recognized. No contamination was observed in the non-image area.

The above plate-making product was treated with a desensitizing solution: ELP-
E2 (manufactured by Fuji Photo Film Co., Ltd.) was immersed for 5 seconds in a processing solution diluted twice with water, and the non-image area was hydrophilized to form a printing plate.

The printing plate was used as immersion water,
Printing was performed using black ink for offset printing using a solution obtained by diluting -E2 10 times with water and using Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.) as a printing material.

As a result, 3,000 or more printed matters were obtained with clear images without background smear.

Next, an ink ejection test was performed using the above-described ink jet printer, and stable ink ejection was obtained even after 500 hours. The ink stored at room temperature for 6 months showed no generation of aggregates, and stable ink ejection was obtained even when the same ejection test was performed.

Further, when the plate-making printing plate under these conditions was actually printed, 3,000 or more printed matters having clear images without background smear were obtained.

Further, the ink was evaluated for redispersibility under forced conditions. That is, after filling the ejection head used in the printer with the ink, removing the ink, leaving it at 35 ° C. for 3 days, immersing the ejection head in Isopar G for 30 minutes, and then gently stirring, the ink IK-1 is removed from the slit. All have been removed. That is, it is considered that the ink of IK-1 which had adhered to the tip of the slit of the ejection head in a state of no fluidity when left undisturbed was easily redispersed by solvation with the dispersion medium.

[Comparative Example A] In Example 1, oil-based ink IKR- having the following content was used instead of oil-based ink IK-1.
Example 1 was repeated except that No. 1 was used.

<Comparative oil-based ink IKR-1> In the oil-based ink IK-1, instead of the resin particles (L-1),
The ink was prepared in the same manner as the ink IK-1, except that 50 g (as solid content) of comparative latex particles (L-28) were used.

Example 2 <Preparation of a lithographic printing plate precursor> 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.
A lithographic printing original plate was obtained in the same manner as in Example 1 except that a laminated paper support [trade name of the product under the trade name] [smoothness of support underlayer 1800 (sec / 10 cc)] was used.

<Preparation of oil-based ink (IK-2)> 10 g of poly (dodecyl methacrylate) and 10 g of nigrosine
g and 30 g of Isopar were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Preparation of Latex Particles 50 g of resin particles (L-12) of Example 12 (in terms of solid content) 35 g of the above nigrosine dispersion, 40 g of isostearyl alcohol and [octadecylvinyl ether-dodecylamide hemimaleate] copolymer. By diluting 10 g to 1 liter of Isopar G, a black oil-based ink was prepared.

Using this printing original plate and oil-based ink (IK-2), plate-making was performed in the same manner as in Example 1 to obtain a printing plate.
Offset printing was performed.

The obtained printed matter has a clear image quality without stain on the non-image portion, similarly to the printing plate of Example 1.
The printing durability was as good as 10,000 sheets or more.

In the same manner as in Example 1, in the ink ejection test for 500 hours and the forced redispersibility test, the ink IK
The performance was completely equivalent to -1 and was excellent.

Examples 3 to 22 Plate making and printing were performed in the same manner as in Example 1 except that the oil-based ink (IK-2) was replaced with the oil-based ink shown in Table 10 below. The oil-based ink used is
In the oil-based ink (IK-2), the resin particles (L-1)
It was prepared in the same manner except that 50 g (as a solid content) of the resin particles shown in Table 10 below were used instead of 2).

[0309]

[Table 10]

[0310] The obtained printed matter had clear image quality without stain on the non-image portion, similarly to the printing plate of Example 2.
The printing durability was as good as 10,000 sheets or more.

Also, as in Example 2, the ink IK test was performed in the 800-hour ink ejection test and the redispersibility compulsory test.
The performance was exactly the same as -2, which was excellent.

Example 23 <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 for a backcoat layer having the following composition was applied to the other surface of the substrate using a wire bar to provide a backcoat layer having a dry coating amount of 12 g / m ² . Calendar processing was performed by setting calendar conditions so that the smoothness was about 50 (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 49%, Tg 0 ° C.) 100 parts Melamine resin initial condensation 5 parts (solid content 80%, Sumiretz Resin SR-613)

<Preparation of a lithographic printing plate precursor> 90 g of the same dry zinc oxide (manufactured by Seido Chemical Co., Ltd.) for Example 1, 10 g of silica gel, 16 g of a binder resin (B-3) having the following structure, and a binder resin ( B-4) 4 g, 3-propoxybenzoic acid [A-1
2] A mixture of 0.36 g and 155 g of toluene was mixed at 30 rpm at a rotation speed of 1 × 10 ⁴ rpm by using a wet type disperser Kedi mill.
Dispersed for minutes.

[0317]

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This dispersion was applied onto the above-mentioned water-resistant support using a wire bar so as to have an application amount of 20 g / m ² , and dried to obtain a lithographic printing plate having a surface smoothness of 200 (sec / 10 cc). A master version was created. The contact angle of the surface with water is 102
Degree.

This printing original plate was prepared in the same manner as in Example 1,
Plate making and desensitization treatment were performed to obtain a printing plate, and offset printing was performed.

However, the oil-based ink used in Example 1 (IK
Instead of -1), an oil-based ink (IK-2) having the following content
3) was used.

<Oil-based ink IK-23> White dispersion (L-26) 5 obtained in Production Example 26 of latex particle particles
00g and 7.5 g of Sumikaron Black
The mixture was heated to a temperature of 100 ° C. and stirred for 6 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, whereby a black resin dispersion having an average particle size of 0.23 μm was obtained.

250 g of the above black resin dispersion, 0.08 g of a charge control material (CD-3) having the following structure, FOC-160
0 (Nissan Chemical Co., Ltd., hexadecyl alcohol) 30
g to 1 liter of Isopar G,
A black oil-based ink was prepared.

[0323]

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[0324] The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 10,000 sheets or more.

Also, in an ink jet test for 800 hours and a forced redispersibility test in the same manner as in Example 1, the performance was completely equivalent to that of the ink IK-1 and was excellent.

Example 24 <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 having the following contents 1.5 g (as solid content) of an acid resin particle dispersion, m-toluic acid (A-
11) A mixture of 0.20 g and 230 g of toluene was dispersed together with 200 g of glass beads having a particle diameter of 0.7 to 1 mm using a Dynomill disperser (manufactured by Shinmaru Enterprise Co., Ltd.) at a rotation speed of 5 × 10 ³ rpm for 10 minutes. Thereafter, the glass beads were filtered off to obtain a coated product for an image receiving layer.

[0327]

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Acrylic Acid Resin Particle Dispersion 8 g of acrylic acid, 2 g of AA-6 (trade name of a macromonomer of methyl methacrylate 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 (monodispersion: 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 that the coating amount was 22 g / m ^2, and dried to obtain a lithographic printing plate precursor.

The surface Beck smoothness of the obtained image receiving layer was 300 (sec / 10 cc). The contact angle of the surface with water was 97 degrees.

This printing original plate was prepared in the same manner as in Example 1.
The plate was made and desensitized to form a printing plate, and offset printing was performed.

However, the oil-based ink of Example 1 (IK-1)
Was replaced by an oil-based ink (IK-24) having the following content.

<Oil-based ink IK-18> White dispersion (L-27) 300 obtained in Production Example 27 of latex particles
g and Victoria Blue B, 5 g, at a temperature of 1
The mixture was heated to 00 ° C and stirred for 4 hours. After cooling to room temperature 2
The remaining dye was removed by passing through a 00 mesh nylon cloth to obtain a blue resin dispersion having an average particle size of 0.22 μm.

By diluting 260 g of the above blue resin dispersion, 0.18 g of zirconium naphthenate, and 20 g of FOC-1600 (manufactured by Nissan Chemical Co., Ltd., hexadecyl alcohol) into 1 liter of Shellsol 71, a blue oil-based ink was prepared. It was created.

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 3,000 sheets or more.

In the same manner as in Example 1, the ink IK test was performed in the 800-hour ink ejection test and the redispersibility compulsory test.
The performance was completely equivalent to -1 and was excellent.

[Brief description of the drawings]

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

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

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

[Explanation of symbols]

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

Claims (3)

[Claims] 1. 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 comprising at least resin particles dispersed in a non-aqueous carrier liquid having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5 is ejected in a droplet form from a nozzle onto the image receiving layer. After the image is formed by the method, the non-image part of this image receiving layer is desensitized by a chemical reaction treatment to be a lithographic printing plate. In the oil-based ink, the dispersed resin particles are at least one kind of a monofunctional monomer (A) which is soluble in a non-aqueous solvent and becomes insoluble by polymerization, and is represented by the following general formula (I). Consists of repeating units A polymer having a weight average molecular weight of 2 × which is obtained by bonding a polymerizable double bond group represented by the following general formula (II) to only one end of the main chain of the polymer
At least one monofunctional macromonomer (MA) having a molecular weight of 10 ⁴ or less, and a weight average molecular weight of 1 × 10 ³ to 2 having a polymerizable double bond bonded only to one end of a polymer main chain. × 10
⁴ is a comb-type copolymer containing at least one monofunctional macromonomer (MB) as a copolymer component, and a main chain part and / or a comb part of the copolymer represented by the following general formula: (III) An ink-jet plate-making printing plate which is a polymer obtained by polymerizing and granulating a solution containing at least one kind of a dispersion stabilizing resin [P] soluble in a non-aqueous solvent, which contains at least the component represented by (III). Oil-based ink. Embedded image Embedded image In the general formula (I), V ⁰ is -COO-, -OCO-,
_{- (CH 2) r COO -} , - (CH 2) r OCO -, -
_{O -, - SO 2 -,} - CONHCOO -, - CONHC
Represents ONH—, —COND ¹¹ —, —SO ₂ ND ¹¹ —, or a phenylene group (where D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents an integer of 1 to 4) . a ¹ and a ^2, through the mutually may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ^12, or a hydrocarbon group, -
It represents a COO-D ¹² (wherein D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group). D ⁰ has 8 carbon atoms
To 22 hydrocarbon groups, or a substituent selected from the substituents represented by the following general formula (I '). General formula ^{(I ') - (A 1} -B 1) m - (A 2 -B 2) n -
D ^{21 In the} general formula (I ′), D ²¹ is a hydrogen atom or a carbon atom having 1 to 22 carbon atoms.
Represents a hydrocarbon group. B ¹ and B ² may be the same or different from each other, and are each -O-, -CO-, -C
O _2- , -OCO-, -SO _2- , -N (D ²² )-,-
CON (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^21). A ¹ and A ² may be the same or different from each other, and each may be substituted. Alternatively, it represents a hydrocarbon group having 1 to 18 carbon atoms which may have the following formula 3 intervening in the bond of the main chain. Embedded image In Chemical Formula 3, B ³ and B ⁴ may be the same or different from each other, and have the same contents as B ¹ and B ² above, and A ⁴ is a hydrocarbon group having 1 to 18 carbon atoms which may be substituted. Indicates that
D ²³ indicates the same contents as the D ^21. m, n and p
May be the same or different, and each represents an integer of 0 to 4. However, m, n and p do not become 0 at the same time. In the general formula (II), V ¹ represents —COO—,
-CONHCOO-, -CONHCONH-, -CON
Represents an H- or phenylene group. b ¹ and b ² are
They may be the same or different from each other, and a in formula (I)
¹ represents a ² same content as. Embedded image In the formula (III), V ² represents -COO-, -OCO-, -O-
Or represents a phenylene group. d ¹ and d ² may be the same or different from each other, and represent the same contents as a ¹ and a ² in the formula (I). D ¹ represents an alkyl group having 10 to 32 carbon atoms or an alkenyl group having 10 to 32 carbon atoms. 2. The dispersion stabilizing resin [P] is provided at one end of the polymer main chain with -PO ₃ H ₂ , -SO ₃ H, -CO
OH, -P (= O) ( OH) R 1 [wherein R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, -SH, formyl group, - CONR
³ R ⁴ , —SO ₂ NR ³ R ⁴ [where R ³ and R ⁴ are
Each independently represents a hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from an amino group. 3. The ink-jet printer according to claim 1, wherein the dispersion stabilizing resin [P] contains a polymerizable functional group copolymerizable with the monomer (A) at one end of the polymer main chain. Oil-based ink for formula plate printing.