JPH10324834A - Oil-base ink for ink jet printing process printing plate and method for forming ink jet process printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil-base ink improved in redispersibility, image reproducibility, storability and plate wear by dispersing copolymer resin particles obtained by polymerizing a solution containing a monofunctional monomer being soluble in a nonaqueous solvent miscible with an aqueous carrier fluid and becoming insoluble therein when polymerized, a specified macromonomer and a dispersion-stabilizing in the nonaqueous solvent in the nonaqueous carrier fluid. SOLUTION: Copolymer resin particles obtained by polymerizing a solution containing a monofunctional monomer being soluble in a nonaqueous solvent miscible with a nonaqueous carrier fluid, a monofunctional macromonomer prepared by bonding a polymerizable double bond group of formula II to either terminal of a polymer main chain comprising repeating units of a monomer of formula I and having a weight - average molecular weight of 1×10<4> and a dispersion-stabilizing resin containing repeating units derived from a monomer of formula III, partly crosslinked in the polymer main chain and being soluble in the non-aqueous solvent are dispersed in the nonaqueous carrier fluid having an electric resistance of 10<9> Ω cm or above and a permittivity of 3.5 or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based ink used for an ink-jet type plate-making printing plate and a method for preparing a plate-making printing plate using the same.
The present invention relates to an oil-based ink excellent in storage stability, image reproducibility, and printing durability, and a method of making a plate-making printing plate using the oil-based ink.

[0002]

2. Description of the Related Art With the recent development of office equipment and the development of OA, in the field of light printing, a direct-drawing lithographic printing plate precursor having a hydrophilic surface image-receiving layer on a water-resistant support is produced by various methods. 2. Description of the Related Art Offset lithographic printing, in which a plate is made, that is, an image is formed to create a printing plate, has become widespread.

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

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

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

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

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

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

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

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

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

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

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

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

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-based ink for ink-jet plate making which is excellent in redispersibility, storage stability and printing durability. Another object of the present invention is to provide an ink for an ink-jet type plate-making printing plate capable of printing a large number of clear printed images. Another object of the present invention is to provide an ink for an ink-jet type plate-making printing plate in which ejection of the ink is stable without clogging of a nozzle and an ink supply path.

[0016]

The above object is achieved by the following constitution.

(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. On the image receiving layer of the above, an oil-based ink obtained by dispersing at least resin particles 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 the form of droplets. After an image is formed by an ink jet method, the non-image portion of the image receiving layer is desensitized by a chemical reaction treatment to form a lithographic printing plate. In the oil-based ink, the dispersed resin particles are (i) a monofunctional monomer that is soluble in a non-aqueous solvent that is at least miscible with the non-aqueous carrier liquid and becomes insoluble by polymerization. (A) at least one (ii) a polymerizable double bond group represented by the following general formula (II) is bonded to only one terminal of a main chain of a polymer containing a repeating unit corresponding to a monomer represented by the following general formula (I) Has a weight average molecular weight of 1 × 10 ³ to
At least one monofunctional macromonomer (MA) having 2 × 10 ⁴ , and (iii) at least one of the following general formula (II)
A polymer containing a repeating unit represented by I),
A part thereof is cross-linked, and is soluble in the non-aqueous solvent, wherein a polymerizable double bond group copolymerizable with the monomer (A) is bonded to only one end of at least one polymer main chain. An oil-based ink for an ink-jet type plate-making printing plate, which is a copolymer resin obtained by polymerizing a solution containing at least one kind of the dispersion stabilizing resin (P).

[0018]

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In the general formula (I), V ⁰ is -COO-, -O
_{CO -, - (CH 2)} r COO -, - (CH 2) r OCO-,
_{-O -, - SO 2 -,} - CONHCOO -, - CONH
^{CONH -, - CON (D 11} ) -, - SO 2 N (D 11)
Or represents a phenylene group (where D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents 1 to 4
Is an integer). a ¹ and a ² may be the same or different 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 is
It represents a hydrocarbon group having 8 to 22 carbon atoms or a substituent represented by the following general formula (Ia) having a total number of atoms of 8 or more (excluding a hydrogen atom bonded to carbon and nitrogen).

Formula (Ia)-(A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹

In the general formula (Ia), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² are
They may be the same or different, and each represents -O-, -C
_{O -, - CO 2 -,} - OCO -, - SO 2 -, - N (D
^{22) -, - CON (D} 22) - or -N (D ²²⁾ CO-
The expressed (here D ²² denote the same contents as the D ^21).
A ¹ and A ² may be the same or different from each other, and are each selected from a group represented by the following general formula (Ib) and a hydrocarbon group having 1 to 18 carbon atoms which may be substituted. It represents at least one group (however, in the case of two or more, a bond of the group of the formula (Ib) and / or the hydrocarbon group).

[0022]

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In the general formula (Ib), 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 carbon atom which may be substituted. ~ 18
Indicates 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. However, m, n and p do not become 0 at the same time.

[0024]

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In the general formula (II), V ¹ is -COO-, -C
ONHCOO-, -CONHCONH-, -CONH-
Or represents a phenylene group. b ¹ and b ² may be the same or different from each other, and a ¹ and a ² in the formula (I)
Represents the same content as

[0026]

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In the general formula (III), X ¹ represents —COO—, —O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O- or -SO ₂ - represents a. Y ¹ represents an aliphatic group having 8 to 32 carbon atoms. 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), respectively.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The oil-based ink used in the present invention will be described below in detail. The non-aqueous carrier liquid of the oil-based ink having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon or Aromatic hydrocarbons and their halogen-substituted products can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E,
Isopar G, Isopar H, Isopar L (Isoper; trade name of Exxon), Shelsol 70, Shelsol 71 (Shelsol; trade name of Shell Oil), AMSCO OMS, AMSCO 460 solvent (AMSCO; Spirits) ) Can be used alone or in combination. The upper limit of the electric resistance of such a non-aqueous carrier liquid is about 10 ¹⁶ Ωcm, and the lower limit of the dielectric constant is about 1.85.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are 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 monofunctional monomer (A) and at least one monofunctional macromonomer (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, alicyclic hydrocarbon, or aromatic hydrocarbon. And halogen-substituted products thereof. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E, isoper G,
Isopar H, Isopar L, Shellsol 70, Shellsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

Other organic solvents that can be used in combination with these non-aqueous solvents include alcohols (eg, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol monomethyl ether, fluorinated alcohol, etc.), ketones ( For example, methyl ethyl ketone, acetophenone, cyclohexanone, etc.), carboxylic esters (eg, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, ethyl benzoate, ethylene glycol monomethyl ether acetate, etc.), ethers (eg, , Dipropyl ether, ethylene glycol dimethyl ether,
Propylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, chloroform, dichloroethane, methyl chloroform, etc.).

It is desirable that the organic solvent used by mixing these is distilled off under heating or under reduced pressure after polymerization granulation. However, even if the solvent is brought into the oil-based ink as a latex particle dispersion, the resistance of the ink is reduced. There is no problem as long as the condition of 10 ⁹ Ωcm or more can be satisfied.

In general, it is preferable to use the same solvent as the carrier liquid at the stage 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 is
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.

[0035]

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

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

E¹And e^TwoAre the same but different
And preferably a hydrogen atom, a halogen atom (eg,
Chlorine atom, bromine atom, etc.), cyano group,
Alkyl group (for example, methyl group, ethyl group, propyl group
Etc.), -COOZ¹Or -CH _Two-COOZ¹〔here
And Z¹Is a hydrogen atom or an optionally substituted carbon atom 1
0 or less hydrocarbon group (for example, alkyl group, alkenyl
Group, an aralkyl group, an aryl group, etc.].

Specific monofunctional monomers (A) include:
For example, vinyl ester acids or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, C1-C4 alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, Bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-
Hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) ethyl group, 2-carboxyethyl group,
2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-
Furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-
Styrene derivatives (eg, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, “Polymer Data Handbook-
Basic Edition- ", pages 175-184, Baifukan (1986), for example, N-vinylpyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
And the like. Two or more monomers (A) may be used in combination.

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 general formula (II) only at one end of the main chain of the polymer comprising the repeating unit represented by the general formula (I). Weight average molecular weight of 2 × 10
⁴ or less macromonomers.

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 preferred 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. As the substituent, a halogen atom (eg, a chlorine atom, a bromine atom, etc.),
Alkyl group (for example, methyl group, ethyl group, propyl group,
Butyl group, chloromethyl group, methoxymethyl group, etc.).

A ¹ and a ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, and a carbon number of 1 to 3.
Alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), - COO-D ¹³ or -CH ₂ COO-D ^13,
(D ¹³ 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 the same as those described for ().

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

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

A ¹ and A ^{2 each} represent a group represented by the above formula (Ib) and a hydrocarbon group having 1 to 18 carbon atoms (an example of the hydrocarbon group is an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group). is, specific examples represents at least one group selected from among the specific examples include the same contents as) listed in D ¹¹ (however, if two or more of these formulas (Ib) group And / or any bond of a hydrocarbon group).

A₁ And A_Two More specific examples
Then, these are -C (D³¹) (D ³²)-[D³¹, D³²
Represents a hydrogen atom, an alkyl group, a halogen atom, etc.],-
(CH = CH)-, phenylene group (-Pn-), cyclo
Hexylene group [hereinafter, cyclohexylene group is referred to as “-C₆ H
_Ten− ”And“ −C₆ H_Ten“-” Is 1,2-cyclohexyl
Silene group, 1,3-cyclohexylene group, 1,4-cycloalkyl
Lohexylene group], represented by the above formula (Ib)
It is composed of any combination of atomic groups such as groups.
You.

When D ⁰ represents a substituent represented by the general formula (Ia) having a total number of atoms of 8 or more, the bonding group [-V ⁰ in the formula (I)
-(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 ) preferably has a total number of atoms of 8 or more constituting the connecting main chain.

Here, the number of atoms constituting the “linking main chain” means, for example, when V ⁰ represents —COO— or —CONH—, an oxo group (＝ O group) or a hydrogen atom The carbon atoms, ether-type oxygen atoms, and nitrogen atoms constituting the connecting main chain are included as the number of atoms, which is different from the total number of atoms defined by D ⁰ . 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.

[-B ^3- (A ⁴ -B ⁴ ) _p ] wherein A ¹ and A ² each have a group represented by the formula (Ib).
-D ²³ ] group is also included in the aforementioned “linking main chain”.

The monomer represented by the above general formula (I)
In a repeating unit equivalent to a body, D ⁰ Is the aforementioned general formula (I
a) represents a substituent represented by a), that is,
At least two or more specific polarities in the molecule as a unit component
When containing a group, more specifically,
Can be given as an example. The following equation (1)
In (19), each symbol represents the following.

R ₁ : —H, —CH ₃ , —Cl or —CN, r ₂ : —H or —CH ₃ l: an integer of 2 to 10, p: an integer of 2 to 6, q: an integer of 2 to 4 An integer, m: an integer of 1 to 12, n: an integer of 4 to 18,

[0055]

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[0056]

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[0057]

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

In the formula (II), V ¹ represents -COO-, -CO
Represents an NHCOO-, -CONHCONH-, -CONH- or phenylene group. Here, a specific embodiment of the phenylene group represents the same content as the phenylene group for V ⁰ in the formula (I).

B ¹ and b ² may be the same or different from each other and have the same meaning as a ¹ or a ² in the formula (I), and represent the same contents. More preferably, ^one of b ¹ and b ^{2 in} the formula (II) is a hydrogen atom.

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

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

[0063]

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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 D above) or a single bond group such as a single bond group selected from the following bond groups and the like. It represents a selected single connecting group or a connecting group composed of any combination.

[0066]

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In the formula (V), a¹ , A^Two , B¹ , B
^Two , V⁰ And V¹ For each of the particularly preferred examples
It is shown below. V⁰ As -COO-, -OCO-,
-O-, -CH_Two COO- or -CH_Two OCO-
V¹ All of the above are a¹ , A^Two , B
¹ , B ^Two Represents a hydrogen atom or a methyl group
You.

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

[0069]

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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.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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The macromonomer (MA) polymer component used in the present invention contains, in addition to a repeating unit corresponding to the monomer represented by the general formula (I), another repeating unit as a copolymerization component. Is also good.

The other copolymer component may be any compound 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 aforementioned monomer (A)
And the like, but are not limited thereto.

In the total of the repeating units of the macromonomer (MA), the repeating unit component corresponding to the monomer represented by the general formula (I) is preferably contained in an amount of 60% by weight or more, more preferably 80 to 100% by weight. The macromonomer (MA) of the present invention has a weight average molecular weight of preferably 1 × 10 ³ to 2 × 10 ⁴ , more preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ . Within each of the above-mentioned predetermined ranges, the dispersion resin particles exhibit excellent effects of dispersion stability, re-dispersion stability, and storage stability.

The macromonomer (MA) of the present invention can be produced by a conventionally known synthesis method. For example, a living monomer obtained by anionic or cationic polymerization is reacted with various reagents to form a macromonomer. 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 obtain a macromonomer by a radical polymerization method, or an oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. And the like by a polyaddition condensation method.

Specifically, P. Dreyfuss & RPQuirk, En
cycl.Polym.Sci.Eng., 7, 551 (1987), PFRempp & E.Fr
anta, Adv.Polym.Sci., 58, 1 (1984), V. Percec, Appl.P
olym. Sci., 285, 95 (1984), R. Asami, M. TakaRi, Makro
mol. Chem. Suppl., 12, 163 (1985), P. Rempp et al., Makro
mol.Chem.Suppl., 8,3 (1984), Yusuke Kawakami `` Chemical Industry''3
8, 56 (1987), Yuya Yamashita, `` Polymer '' 31, 988 (1982), Shiro Kobayashi, `` Polymer '' 30, 625 (1981), Toshinobu Higashimura, `` Journal of the Adhesion Society of Japan '' 18, 536 (1982), Ito Koichi "Polymer Processing" 35,
262 (1986), Kishiro Higashi, Takashi Tsuda "Functional Materials" 1987, No.1
It can be synthesized according to the methods described in reviews such as 0, 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 the reactive group or a substituent capable of being induced to the reactive group (for example, thioglycolic acid, Thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid,
3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, −
Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, etc.), or the reactive group or an iodized alkyl compound containing a substituent capable of being induced to the reactive group (for example,
Iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

The amount of the chain transfer agent or polymerization initiator to be used is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of all monomers.

The dispersing 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 non-functional. Insoluble in a water solvent, whereby a desired dispersed resin can be obtained. More specifically, the monofunctional macromonomer (MA) is preferably used in an amount of 0.1 to 20% by weight, more preferably 0.3 to 15% by weight, based on the insoluble monomer (A). Is preferred.

The weight average molecular weight of the resin in the dispersion of the present invention is preferably from 1 × 10 ³ to 1 × 10 ⁶ ,
More preferably, it is 8 × 10 ^{3 to} 5 × 10 ⁵ . The resin in the dispersion of the present invention preferably has a glass transition point of 15 to 80 ° C. or a softening point of 38 to 120 ° C. as a thermophysical property, and particularly has a glass transition point of 20 to 60 ° C. or a softening point of 40 to 40 ° C. A range of 90 ° C. is preferred.

Within the above range, the dispersion stability, redispersion 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. Also retains an image and exhibits high printing durability.

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 polymer containing at least one repeating unit corresponding to the monomer represented by the above general formula (III), and a part of the polymer main chain. Is a resin soluble in the non-aqueous solvent, wherein the resin is crosslinked and a polymerizable double bond group capable of copolymerizing with the monomer (A) is bonded only to one end of the polymer main chain.

In the repeating unit represented by formula (I), the aliphatic group and the hydrocarbon group may be substituted.

In the general formula (III), in the general formula (I), X ¹ represents —COO—, —OCO—, —CH ₂ OCO
_{-, - CH 2 COO -,} - O- or -SO ₂ - represents,
Preferably -COO -, - OCO -, - CH 2 OCO
-, - CH ₂ COO- or an -O-, more preferably -COO -, - OCO -, - represents a CH ₂ COO- or -O-.

Y ¹ represents an aliphatic group having 8 to 32 carbon atoms,
It preferably represents an alkyl group, an alkenyl group or an alkenyl group having 10 to 22 carbon atoms, which may be substituted. Examples of the substituent include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, ^{etc.), - O-D 30,} -COO
-D ^30, -OCO-D ³⁰ (wherein, D ³⁰ is a carbon number 6-2
And represents, for example, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group and the like. More preferably, Y
¹ represents an alkyl group or an alkenyl group having 10 to 22 carbon atoms. For example, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl,
Examples include an octadecyl group, a docosanyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group, and the like.

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

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

The other monomer which can be copolymerized may be any monomer containing a polymerizable double bond group. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid; Ester derivatives or amide derivatives of unsaturated carboxylic acids of 8 or less; vinyl esters or acrylic esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. . More specifically, a compound having the same content as the above-mentioned monomer (A) to be insolubilized may be used.

In the polymer component of the dispersion stabilizing resin (P), the component of the repeating unit represented by the general formula (III) accounts for at least 70% by weight, preferably at least 80% by weight, and more preferably at least 80% by weight of the polymer component. It is preferably at least 90% by weight.

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

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

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

Specific examples of the polymerizable functional group include CH_Two =
CH-, CH_Two = CH-CH_Two -, CH_Two = CH-CO
-O-, CH_Two = C (CH_Three) -CO-O-, CH_Three -C
H = CH-CO-O-, CH_Two = CH-CONH-, C
H_Two = C (CH_Three9-CONH-, CH_Two = C (CH_Three) −
CONHCOO-, CH_Two = C (CH_Three) -CONHCO
NH-, CH_Three -CH = CH-CONH-, CH_Two = C
H-O-CO-, CH _Two = C (CH_Three) -O-CO-, C
H_Two = CH-CH_Two -O-CO-, CH_Two = CH-NH
CO-, CH_Two = CH-CH_Two -NHCO-, CH_Two =
CH-SO_Two -, CH_Two = CH-CO-, CH_Two = CH
-O-, CH_Two = CH-S- and the like.
Is a monomer having two or more polymerizable functional groups
Are the same or different for these polymerizable functional groups.
And monomers having two or more of these.

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

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

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

The dispersion stabilizing resin (P) of the present invention further comprises
A polymerizable double bond group copolymerizable with the monomer (A) is bonded to at least one terminal of the polymer main chain.

The polymerizable dipolymerizable group may be any functional group copolymerizable with the monomer (A), and may be directly bonded to one end of the polymer main chain, or may have an arbitrary linking group. Having a chemical structure linked through .

More specifically, the above-mentioned macromonomer (M
Those having the same contents as the polymerizable double bond group represented by the formula (II) in A) can be mentioned. Further, when the polymerizable double bond group is bonded to the terminal of the polymer main chain via a linking group, as a specific embodiment, the macromonomer (M
Include those having the same content as "-V ¹ -Z-" in the illustrated general formula A) (V ').

The method for introducing a polymerizable double bond group into the dispersion stabilizing resin (P) of the present invention can be produced by a conventionally known synthesis method. Specifically, it is the same as the above-mentioned macromonomer (MA). Can be done.

The dispersion stabilizing resin (P) of the present invention is soluble in an organic solvent. More specifically, the dispersion stabilizing resin is at least 5 parts by weight at a temperature of 25 ° C. with respect to 100 parts by weight of a toluene solvent. Those that dissolve are preferred.

The weight average molecular weight (Mw) of the dispersion stabilizing resin (P) of the present invention is from 1 × 10 ⁴ to 1 × 10 ⁶ , preferably from 3 × 10 ^{4 to} 5 × 10 ⁵ . Within this range, the average particle size of the resin particles obtained by polymerization granulation is preferably in the range of 0.1 to 0.4 μm, and particles having uniform particle size and excellent monodispersity can be obtained.

To produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin (P) as described above,
The monomer (A) and the 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 suitably from 0.1 to 10% by weight of the total monomers. Also,
The polymerization temperature is about 40 to 180 ° C, preferably 50 to 180 ° C.
~ 120 ° C. The reaction time is preferably 3 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination in the non-aqueous solvent used in the reaction, or when the monomer (A) and the 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 by the present invention exist as fine particles having a uniform particle size distribution. The average particle size is preferably 0.0
8 to 0.5 μm, more preferably 0.1 to 0.4 μm.
μm. The particle size can be determined using CAPA-500 (trade name, manufactured by Horiba, Ltd.) or the like. In addition, at the same time, it shows very stable dispersibility, especially in a recording device, good dispersibility even if used repeatedly for a long time,
In addition, re-dispersion is easy, and it is not recognized at all that the toner adheres to each part of the apparatus to cause contamination.

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

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

The dispersion resin particles of the present invention are prepared by dispersing the dispersion-stabilizing resin (P) and the macromonomer (M
A) is chemically bonded to the insoluble resin particles. Since the resin (P) to which the resin particles are bound is soluble in a non-aqueous solvent, a so-called steric repulsion effect known as stabilization of dispersion of a non-aqueous latex is brought about. At the same time,
Since the resin (P) is a soluble resin containing a crosslinked structure, the affinity for a nonaqueous solvent is remarkably improved, and the bound resin (P) exists near the particle interface because of the crosslinked structure. It is presumed that the affinity increases near the particle interface.

Further, a soluble component contained in the macromonomer (MA) is present at the particle interface of the resin, the surface of the particle is improved to some extent, the affinity with the dispersion medium is further improved, and the dispersion medium is improved. It is considered that the solvation of the resin particles is increased, and aggregation of the resin particles is prevented.

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

As described above, when the dispersed resin particles of the present invention are used, the dispersion stability is improved, and when the oil-based ink is repeatedly used for a long time, the oil-based ink is concentrated in the ink, which may cause various problems. Has been 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.

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

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

One of the methods is described in JP-A-57-487.
No. 38, etc., there is a method of dyeing a dispersed resin material with a preferable dye. 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 or negatively charged electro-detectable particles.

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

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

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

The lithographic printing plate precursor according to the present invention has an image receiving layer. In this case, the image receiving layer contains zinc oxide and a binder resin, and the degree of hydrophobicity of the surface thereof is such that contact with water is prevented. 5 at the corner
0 ° or more, preferably 50 ° to 130 °, more preferably 50 ° to 120 ° in consideration of ink receptivity.
°, particularly preferably 55 ° to 110 °.

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

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 Japanese Patent Application Laid-Open No. Sho 54-117203 uses an ink-jet system using an oil-based ink in the same manner as in 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, more preferably 45 to 300 (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 portion and the image receiving layer is improved. The printing durability is significantly improved to 3000 sheets or more.

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

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

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

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

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 the hydrophobic resin is 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.

More 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 the weight ratio of resin / zinc oxide.

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

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

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

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

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

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

Examples of the 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 needed 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 (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetone cobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamic acid) Salts), tinouram disulfide compounds (such as tetramethyltinouram disulfide), carboxylic anhydrides (phthalic anhydride,
Maleic anhydride, succinic anhydride, butyl succinic anhydride, 3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.). When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator is used, and examples thereof include a peroxide and an azobis compound.

It is preferable that the binder resin is cured by light and / or heat after the image receiving layer composition is applied. In order to carry out thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of preparing the conventional image receiving layer. For example, it is preferable to set the drying conditions to a high temperature and / or a long time, or to further heat after drying the coating solvent.
For example, the treatment is performed at 60 ° C. to 150 ° C. for 5 to 120 minutes. When 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.

The thickness of the image receiving layer in the present invention is preferably about 3 to 30 g, as indicated by the coating amount (after drying) of the image receiving composition per 1 m ² of the original plate. The image 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 used in the 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 under layer 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 the unevenness of the surface of the support, and the image quality can be further improved.

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

In the present invention, as 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 way 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, a calendering process is performed once after the underlayer is formed, and a calendering process 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 in the original plate of the present invention include, for example, substrates such as wood pulp paper, synthetic pulp paper, mixed paper of wood pulp and synthetic pulp, non-woven fabric, plastic film, cloth, metal sheet, and composite sheet materials thereof. Can be used as it is. 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, an undercoat is formed on the substrate to adjust 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.

In order to prepare the lithographic printing plate precursor of the present invention, a solution containing an under layer component is coated on one side of the support, if necessary, and dried to form an under layer. A solution containing a component of a back coat layer is applied to the surface and dried to form a back coat layer, and then a coating solution containing a component of an image receiving layer is applied and dried to form an image receiving layer. 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 of forming an image on the lithographic printing original plate (hereinafter also referred to as “master”) will be described. FIG. 1 shows an example of an apparatus system for performing such a method.

The apparatus system shown in FIG. 1 has an ink jet recording apparatus 1 using oil-based ink.

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

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 structural view showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

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

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

The width of the discharge electrode 10b is preferably as narrow as possible in order to form a high quality image, for example, for printing.

For example, when 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 original plate,
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 solution of this type, a treating solution containing a cyanide compound containing ferrocyanate or ferricyanate as a main component, 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 solution,
JP-B-44-9045, JP-B-46-39403, JP-A-52-76101, JP-A-57-107889, and JP-A-57-107889.
4-117201 and the like.

Examples of the phytic acid compound-containing treating 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-41-10308.
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-56-11695.

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 performed at room temperature (15 ° C. to 35 ° C.).
) For about 2 to 60 seconds. Using this printing plate, about 5000 sheets of offset printing can be performed by using dampening water.

[0198]

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 (MA) A mixed solution of 100 g of macromonomer (MA-1) octadecyl methacrylate, 2 g of 3-mercaptopropionic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. Warmed.
2,2'-azobis (isobutyronitrile) (abbreviation A.
I. B. N. ) Was added and reacted for 4 hours.
I. B. N. Was added for 3 hours, and A. I. B.
N. Was added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 10 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. The weight average molecular weight (Mw) of the polymer was 1 × 10 ⁴ (the weight average molecular weight was
G. FIG. P. Represents the polystyrene equivalent value by the C method. same as below).

[0200]

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

[0202]

[Table 1]

Production Example 12 of Macromonomer (MA) Macromonomer (MA-12) A mixed solution of 100 g of tetradecyl methacrylate, 2 g of thioethanol and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. A. I. B. N. Was added and reacted for 4 hours. Further, A.I. I. B. N.
Was added for 3 hours, and then A. I. B. N.
Was added and reacted for 3 hours. The reaction solution was cooled to room temperature, 8 g of 2-carboxyethyl acrylate was added, and dicyclohexylcarbodiimide (abbreviated as D.I.
C. C. ) And 60 g of methylene chloride were added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred as it was for 4 hours.

The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was collected by decantation, dissolved in 150 ml of methylene chloride and reprecipitated in 1 liter of methanol. The oil was collected and dried under reduced pressure to give a yield of 60 g and a Mw of 8 ×.
To obtain a 10 ³ polymer.

[0205]

Embedded image

Production Examples of Macromonomer (MA) 13-1
5: Macromonomer (MA-13) to (MA-15) In Production Example 12 of macromonomer (MA), methacrylate monomer (corresponding to tetradecyl methacrylate) and unsaturated carboxylic acid (corresponding to 2-carboxyethyl acrylate) were used. In the same manner as in Production Example 12, each of the macromonomers in Table 2 below was produced. The yield was 60 to 70 g, and the weight average molecular weight of each macromonomer was in the range of 7 × 10 ^{3 to} 9 × 10 ³ .

[0207]

[Table 2]

Production Example 16 of Macromonomer (MA) Macromonomer (MA-16) A mixed solution of 100 g of 2,3-diheptanoyloxypropyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated at a temperature of 7 under a nitrogen stream.
Warmed to 5 ° C. 5.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) was added and reacted for 5 hours. C. V. Was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liters of methanol, and the oil was collected by decantation and dried under reduced pressure. The yield was 85 g.

50 g of this oil, 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine
g, 1.0 g of 2,2'-methylenebis (6-t-butyl-p-cresol) and 100 g of toluene were stirred at a temperature of 100 DEG C. for 15 hours. After cooling, the reaction solution was reprecipitated in 1 liter of petroleum ether to obtain 63 g of a white powder. The weight average molecular weight was 7 × 10 ³ .

[0210]

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Production Example 1 of Dispersion Stabilizing Resin (P) 1: Resin (P-1) 100 g of octadecyl methacrylate, 3 g of thioglycolic acid, 5.0 g of divinylbenzene and toluene 20
0 g of the mixed solution was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 1,1′-azobis (cyclohexane-1-
0.8 g of carbonitrile) (abbreviated as ACNH)
The reaction was performed for 4 hours. Further, A. C. H. N. To 0.4
g. and reacted for 2 hours. C. H. N. Was added and reacted for 2 hours. After cooling, 10 g of allyl alcohol was added and the temperature was set at 25 ° C. To this solution, a mixed solution of 16 g of dicyclohexyldicarbodiimide (abbreviated as DCC), 0.2 g of 4- (N, N-diethylamino) pyridine and 40 g of methylene chloride was added dropwise with stirring for 1 hour. Further, the reaction was continued for 3 hours to complete the reaction. Next, 80%
After adding 10 g of formic acid and stirring for 1 hour, the insoluble matter was filtered off,
The filtrate was reprecipitated in 2.5 liters of methanol. After collecting the precipitate by filtration, the precipitate was dissolved again in 200 g of toluene, the insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol.
The precipitate was collected by filtration and dried. The yield of the obtained polymer is 7
At 0 g, the Mw was 4.5 × 10 ⁴ . (GPC.
Polystyrene conversion value. Hereinafter the same)

Production Examples 2 to 10 of Dispersion Stabilizing Resin (P):
Resins (P-2) to (P-10) In Production Example 1 of dispersion stabilizing resin (P), instead of octadecyl methacrylate and divinylbenzene,
Each dispersion stabilizing resin was produced in exactly the same manner as in Production Example 1 except that the monomers and polyfunctional monomers shown in Table 3 below were used. Mw of each resin (P) was in the range of 4 × 10 ^{4 to} 6 × 10 ⁴ .

[0213]

[Table 3]

Production Examples 11 to 1 of Dispersion Stabilizing Resin (P)
4: Resins (P-11) to (P-14) Production Example 1 was the same as Production Example 1 of the dispersion stabilizing resin (P) except that the mercapto compound in Table 4 below was used instead of 3 g of thioglycolic acid. In the same manner as in the above, dispersion stabilizing resins (P-11) to (P-14) were produced.

[0215]

[Table 4]

Production Example 15 of Dispersion Stabilizing Resin (P): Resin (P-15) A mixed solution of 100 g of octadecyl methacrylate, 3 g of 2-mercaptoethanol, 4.5 g of divinylbenzene, 150 g of toluene and 50 g of ethanol was placed in a nitrogen stream. Was heated to a temperature of 60 ° C. 0.5 g of 2,2'-azobis (isobutyronitrile) (abbreviated as AIBN) was added, and the mixture was reacted for 5 hours. I. B. N. Was added and reacted for 3 hours. I. B. N.
Was added and reacted for 3 hours.

Next, the reaction mixture was cooled to 25 ° C.
To this, 8 g of vinyl acetic acid was added, and D.I. C. C.
, A mixed solution of 0.4 g of 4- (N, N-diethylamino) pyridine and 30 g of methylene chloride was added dropwise over 1 hour, and the mixture was further stirred for 4 hours.

Next, 5 g of a 30% ethanol solution of hydrogen chloride was added.
And 5 g of water were added, followed by stirring 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 × 10 ⁴ .

Production Examples 16 to 2 of Dispersion Stabilizing Resin (P)
3: Resins (P-16) to (P-23) Production Example 15 of Production Example 15 of Dispersion Stabilizing Resin (P), except that polymerizable group-containing carboxylic acid compound of Table 5 below was used instead of vinyl acetic acid. Each dispersion stabilizing resin was manufactured in exactly the same manner as in No. 15. The Mw of each of the obtained resins was about 5 × 10 ⁴ .

[0220]

[Table 5]

Production Example 24 of Resin for Stabilizing Dispersion (P): Resin (P-24) 100 g of octadecyl acrylate, 1.1 g of ethylene glycol diacrylate and tetrahydrofuran 2
While stirring under a nitrogen stream, 00 g of the mixed solution was heated at a temperature of 7 g.
Warmed to 0 ° C. 6 g of 4,4'-azobis (4-cyanopentanol) was added and reacted for 5 hours. Further, 1.0 g of the above azobis compound was added and reacted for 5 hours. The reaction mixture was cooled to a temperature of 20 ° C. in a water bath, and 3.2 g of pyridine and 1.0 g of 2,2′-methylenebis- (6-t-butyl-p-cresol) were added thereto, followed by stirring. To this mixed solution, 4.2 g of methacrylic acid chloride was added dropwise over 30 minutes so that the reaction temperature did not exceed 25 ° C. The mixture was stirred at a temperature of 20 ° C to 25 ° C for 4 hours. Next, the reaction product was reprecipitated in a mixture of 1.5 liter of methanol / 0.5 liter of water, and a white powder was collected by filtration and dried. The yield was 82 g and the weight average molecular weight was 7.5 × 10 ⁴ .

Production Example of Latex Particle 1: Latex Particle (D-1) 6 g of dispersion stabilizing resin (P-1), 100 g of vinyl acetate,
A mixed solution of 0.8 g of the macromonomer (MA-1) and 392 g of Isopar H was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 2,2'-azobis (isovaleronitrile) (abbreviated as AIVIN) as a polymerization initiator
Was added and reacted for 3 hours. Further, the initiator A.
I. B. N. 0.8 g was added, and the mixture was heated to a temperature of 80 ° C. and reacted for 4 hours. Subsequently, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 98% and an average particle size of 0.22 μm.
The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

A part of the white dispersion was centrifuged (rotated
Number 1 × 10^Four r. p. m. , Rotation time 1 hour)
The precipitated resin particles are collected and dried, and the weight of the resin particles is determined.
Measure the weight average molecular weight (Mw) and glass transition point (Tg)
As a result, Mw is 2 × 10 ^Five , Glass transition point: Tg
38 ° C.

Preparation Example 2 of Latex Particles: Latex Particles (D-2) Dispersion stabilizing resin (P-17) (8 g) and Isopar H were mixed with 17
7 g of the mixed solution was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 25 g of methyl methacrylate, 75 g of methyl acrylate, 1.5 g of macromonomer (MA-12)
200 g of Isopar G and A. I. V. N. Was added dropwise over 2 hours, followed by stirring for 2 hours. Further, A. I. 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 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 100% and an average particle size of 0.22 μm. The Mw of the resin particles was 2 × 10 ⁵ , and the Tg was 26 ° C.

Latex Particle Production Examples 3 to 12: Latex Particles (D-3) to (D-12) The dispersion stabilizing resin (P-1) and the macromonomer (MA-MA) used in Latex Particle Production Example 1 were used. Latex particles were produced in the same manner as in Production Example 1 except that the compounds shown in Table 6 below were used instead of 1).

The polymerization rate of each of the obtained latex particles was 95.
９８98%, the average particle diameter was in the range of 0.18-0.23 μm, and the monodispersity was good. Mw for each resin particle
Was in the range of 1 × 10 ^{5 to} 3 × 10 ⁵ .

[0227]

[Table 6]

Latex Particle Production Examples 13 to 21: Latex Particles (D-13) to (D-21) Monomer (A) used in Latex Particle Production Example 2
Same as in Production Example 2 except that the compounds shown in Table 7 below were used instead of (that is, methyl methacrylate and methyl acrylate), macromonomer (MA-12) and dispersion stabilizing resin (P-17). To produce latex particles.

The polymerization rate of each of the obtained latex particles was 95.
-100%, the average particle size was in the range of 0.18 to 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 .

[0230]

[Table 7]

Production Example 22 of Latex Particles: Latex Particles (D-22) [Comparative Example A] In Production Example 1 of latex particles, instead of 8 g of the dispersion stabilizing resin (P-1), a conventionally known structure having the following structure was used. Production Example 1 except that 10 g of dispersion stabilizing resin (RP-1) was used.
A white dispersion was synthesized in exactly the same manner as described above. Degree of polymerization 95
% Of latex particles having an average particle size of 0.21 μm. The Mw of the resin particles was 1 × 10 ⁵ , and the Tg was 38 ° C.

[0232]

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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.).

[0234]

Embedded image

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

The contact angle of the image receiving layer with water was determined by placing 2 μl of distilled water on the surface of the printing original plate, and measuring the surface contact angle (degree) after 30 seconds using a surface contact angle meter (CA-D, Kyowa Interface). As a result of measurement using Scientific Co., Ltd., it was 102 ° (the lower the value, the better the wettability to water and the more hydrophilic).

The smoothness of the image receiving layer was measured by using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air volume of 10 cc and measuring the smoothness (second / 10 cc) of the printing original plate. , 220 (sec / 10 cc). In addition, the smoothness of the support shown above was also measured in the same manner.

<Preparation of oil-based ink (IK-1)> Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 9
10 g of a 5/5 (weight ratio), 10 g of alkali blue, and 30 g of Shellsol 71 were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of alkali blue. . 50 g of resin particles (D-1) produced in Production Example 1 of latex particles
(As solids content), 1
8 g, 30 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol) and 0.08 g of octadecene-half-maleic acid octadecylamide copolymer were diluted to 1 liter of Isopar G to obtain a blue oily ink. .

Using the lithographic printing original plate prepared as described above, a servoproter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing output from a personal computer, 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-making product (that is, printing plate) was visually observed with an optical microscope at a magnification of 200 times, there was no problem in the copied image, fine lines and fine characters were good, and bleeding, chipping, and blurring were observed. No abnormalities were observed, and no contamination was observed in the non-image area.

Next, after the plate making as described above, a desensitizing solution (ELP-E2, trade name, manufactured by Fuji Photo Film Co., Ltd.) was applied to a fully automatic printing machine (AM-2850, manufactured by Am Co., Ltd.). The solution was prepared by diluting the desensitizing solution (ELP-E2) four times with distilled water as the dampening solution into the dampening solution tray, and then using the black ink for offset printing. Printing was performed through a plate-making product using a printing machine. As a result, more than 3,000 printed images with clear images free of background stains were obtained.

Next, when an ink ejection test was performed using the above-mentioned ink jet printer, stable ink ejection was obtained even for 800 hours. The ink stored at room temperature for 6 months showed no generation of aggregates, and stable ink ejection was obtained even when the same ejection test was performed. Further, when the plate-making printing plate under these conditions was actually printed, 3,000 or more printed matters having clear images without background smear were obtained.

Further, the evaluation was performed under the forced redispersibility condition of the ink. That is, the ejection head used in the printer is filled with ink, removed, left at 35 ° C. for 3 days, then the ejection head is immersed in Isopar G for 30 minutes, and then lightly stirred, the ink (IK-1) is slit. Everything was removed from within. That is, the ink (IK-1) adhering to the tip of the slit of the ejection head in a non-fluid state when left undisturbed is solvated with the dispersion medium.
This is probably due to easy re-dispersion.

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

<Preparation of Comparative Oil-Based Ink (IKR-1)> In oil-based ink (IK-1), resin particles (D-
In place of 1), 50 g of comparative resin particles (D-22)
(Ink (IK-1))
Created in the same way as

The oil-based ink of Comparative Example A (IKR-
As for the lithographic printing plate obtained by using the method 1), 3,000 or more printed matters having clear images without stains were obtained in the same manner as in Example 1 for the first printing. However, in the ink ejection test,
In Comparative Example A, ink ejection became unstable after about 200 hours. In the ink of Comparative Example A stored for 6 months, a coagulated precipitate was deposited and did not redisperse even after shaking.

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

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

Example 2 <Preparation of a lithographic printing original plate> In Example 1, an ELP-IIX type master (Fuji Photo Film Co., Ltd.) was used instead of the ELP-1 type master support used as a water-resistant support.
A lithographic printing plate precursor was obtained in the same manner as in Example 1, except that the laminated paper support [the smoothness of the support underlayer was 1800 (sec / 10 cc)] used in the trade name 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. 50 g (as solid content) of resin particles (D-2) of Production Example 2 of latex particles 35 g of the above nigrosine dispersion, 40 g of isostearyl alcohol and 0.12 g of [octadecyl vinyl ether-dodecylamide hemimaleate] copolymer were mixed with isopar. G was diluted to 1 liter to produce a black oil-based ink.

Using this printing original plate and the oil-based ink (IK-2), plate-making was performed in the same manner as in Example 1 to obtain a printing plate.
Offset printing was performed. The obtained printed matter was obtained in Example 1.
As in the case of the printing plate of No. 1, the image quality was clear with no stain on the non-image area, and the printing durability was as good as 10,000 sheets or more.

Further, when an ink ejection test was performed for 800 hours in the same manner as in Example 1, the ink ejection was stable even after 800 hours. Also in the redispersibility compulsory test,
The performance was exactly the same as that of the ink (IK-1), and was excellent.

Examples 3 to 8 Plate making and printing were performed in the same manner as in Example 1, except that the oil ink shown in Table 8 below was used instead of the oil ink (IK-1). Each oil-based ink used is
In the oil-based ink (IK-1), latex particles (D
It was prepared in the same manner except that 45 g (as solid content) of the resin particles shown in Table 8 below were used instead of -1).

[0254]

[Table 8]

It can be seen that each plate had the same image quality as that of the printing plate of Example 1, and was clear with no stain on the non-image area and excellent in printing durability of 3,000 sheets or more. Met. In the same manner as in Example 1, the ink (IK-1) was used in the 800-hour ink ejection test and the redispersibility compulsory test.
The performance was exactly the same as that of the above, and was excellent.

Examples 9 to 22 Plate making and printing were carried out in the same manner as in Example 2 except that the oil-based ink (IK-2) was replaced with the oil-based ink shown in Table 9 below. The oil-based ink used was a latex particle (D-
It was prepared in the same manner except that 45 g (as solid content) of the resin particles shown in Table 9 below were used instead of 2).

[0257]

[Table 9]

It can be seen that each plate had the same image quality as the printing plate of Example 2 and was clear, with no non-image portions stained, and excellent in printing durability of 10,000 sheets or more. Met. In the same manner as in Example 1, the ink (IK-1) was used in the 800-hour ink ejection test and the redispersibility compulsory test.
The performance was exactly the same as that of the above, and 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.

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

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

<Coating for Back Coat Layer> 200 parts kaolin (50% aqueous dispersion) 60 parts polyvinyl alcohol aqueous solution (10%) 60 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> 100 g of dry zinc oxide (manufactured by Seido Chemical Co., Ltd.) as in Example 1, 16 g of a binder resin (B-3) having the following structure, and a binder resin (B-4) ) 4
g, a mixture of 0.36 g of 3-propoxybenzoic acid [A-12] and 155 g of toluene were dispersed at a rotation speed of 1 × 10 ⁴ rpm for 20 minutes using a wet dispersing machine Kedimill.

[0264]

Embedded image

The dispersion is placed on the above-mentioned water-resistant support and
12 g / m application amount using ear bar ^Two So that
Cloth and dry, flatness of surface smoothness 150 (sec / 10cc)
A printing plate precursor was created. The contact angle of the surface with water is 10
It was twice.

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 (IK-
Instead of 1), the following oil-based ink (IK-23)
Was used.

<Preparation of oil-based ink (IK-23)> White dispersion (D-4) 5 obtained in Production Example 4 of resin particle particles
00g and Sumicaron Black 7.5g
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, thereby obtaining a black resin dispersion having an average particle size of 0.22 μm. 250 g of the above black resin dispersion, 0.10 g of a charge control material (CD-3) having the following structure, FOC-16
00 (Hexadecyl alcohol manufactured by Nissan Chemical Co., Ltd.) 3
By diluting 5 g to 1 liter of Isopar G, a black oil-based ink was prepared.

[0268]

Embedded image

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 2.
The printing durability was as good as 10,000 sheets or more. Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 800 hours showed the same performance as that of the ink (IK-1) and was excellent.

Example 24 <Preparation of a lithographic printing plate precursor> 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.

[0271]

Embedded image

<Preparation of Acrylic Resin Particle Dispersion> Acrylic acid 8 g, AA-6 [trade name, manufactured by Toa Gosei Chemical Co., Ltd .:
Macromonomer of methyl methacrylate] 2 g, ethylene glycol dimethacrylate 2 g, methyl 3-mercaptopropionate 0.1 g and methyl ethyl ketone 5
5 g of the mixed solution was heated to a temperature of 60 ° C. under a nitrogen stream. Add 2,2'-azobis (isovaleronitrile)
0.2 g was added and reacted for 3 hours.
g was added and reacted for 4 hours. The resulting dispersion had a conversion of 95%, and the dispersed resin particles had an average particle size of 0.20 μm and a good monodispersibility (particle size measurement: CAPA-50).
0 (trade name, manufactured by Horiba, Ltd.).

This dispersion was coated on a water-resistant support similar to that used in Example 2 with a wire bar so as to have a coating amount of 20 g / m ² and dried to obtain a lithographic printing plate precursor.

The surface Beck smoothness of the obtained image receiving layer was 350 (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 2.
The plate was made and desensitized to form a printing plate, and offset printing was performed. However, the oil-based ink of Example 2 (IK-2)
Was replaced by an oil-based ink (IK-24) having the following content.

<Preparation of Oil-Based Ink (IK-24)> The white dispersion (D-21) 3 obtained in Production Example 21 of resin particles
A mixture of 00 g and Victoria Blue B, 5 g, was heated to a temperature of 100 ° C. and heated and stirred for 4 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, whereby a black resin dispersion having an average particle size of 0.23 μm was obtained. A blue oil-based ink was prepared by diluting 260 g of the above black resin dispersion, 0.09 g of zirconium naphthenate, and 50 g of FOC-1600 (manufactured by Nissan Chemical Co., Ltd., hexadecyl alcohol) into 1 liter of Shellsol 71. .

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 2.
The printing durability was as good as 10,000 sheets or more. Also, as in Example 1, the ink ejection test and the redispersibility compulsory test for 800 hours showed the same performance as that of the ink (IK-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 (6)

[Claims] 1. A lithographic printing plate precursor having an image receiving layer containing zinc oxide and a binder resin on a water-resistant support, wherein the contact angle of water on the surface of the image receiving layer is 50 ° or more. 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 forming an image by the method, the non-image part of this image receiving layer is desensitized by a chemical reaction treatment to make a lithographic printing plate. In the oil-based ink, the dispersed resin particles are (i) a monofunctional monomer that is soluble in a non-aqueous solvent that is at least miscible with the non-aqueous carrier liquid, and becomes insoluble by polymerization. At least one of A), (ii) below A polymer containing a repeating unit corresponding to a monomer represented by the general formula (I), wherein a polymerizable double bond group represented by the following general formula (II) is bonded to only one terminal of the main chain. Weight average molecular weight of 1 × 10 ³ or more
At least one monofunctional macromonomer (MA) having 2 × 10 ⁴ , and (iii) at least one of the following general formula (II)
A polymer containing a repeating unit represented by I),
A part thereof is cross-linked, and is soluble in the non-aqueous solvent, wherein a polymerizable double bond group copolymerizable with the monomer (A) is bonded to only one end of at least one polymer main chain. An oil-based ink for an ink-jet type plate-making printing plate, which is a copolymer resin obtained by polymerizing a solution containing at least one kind of the dispersion stabilizing resin (P). Embedded image In the general formula (I), V ⁰ is -COO-, -OCO-,-
(CH ₂ ) _r COO-,-(CH ₂ ) _r OCO-, -O-,-
SO _2- , -CONHCOO-, -CONHCONH
—, —CON (D ¹¹ ) —, —SO ₂ N (D ¹¹ ) —, or a phenylene group (where D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents 1 to 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 has 8 carbon atoms
To 22 hydrocarbon groups or a total of 8 or more atoms (excluding hydrogen atoms bonded to carbon and nitrogen) represented by the following general formula (I
represents a substituent represented by a). Formula ^{(Ia) - (A 1 -B} 1) m - (A 2 -B 2) in _n -D ²¹ formula (Ia), D ²¹ 1 to 22 hydrogen atoms or carbon atoms
Represents a hydrocarbon group. B ¹ and B ² may be the same or different from each other, and are each -O-, -CO-, -CO
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - C
ON (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^21). A ¹ and A
² is the same or different, and each may be substituted; at least one group selected from a group represented by the following general formula (Ib) and a hydrocarbon group having 1 to 18 carbon atoms (However, in the case of two or more, these formulas (I
b) a bond of a group and / or a hydrocarbon group). Embedded image In the general formula (Ib), 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. Embedded image 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). Embedded image In the general formula (III), X ¹ represents -COO-, -OCO-, -C
_{H 2 OCO -, - CH 2} COO -, - O- or -SO ₂
Represents-. Y ¹ represents an aliphatic group having 8 to 32 carbon atoms. d
¹ and d ² may be the same or different from each other,
Each represents the same content as a ¹ and a ^{2 in} the formula (I). 2. An ink-jet plate making method, wherein an image of the oil-based ink according to claim 1 is formed on a lithographic printing plate having a hydrophilic surface capable of lithographic printing by an ink-jet method to form a lithographic printing plate. How to make a printing plate. 3. The image forming method according to claim 1, wherein:
3. The method according to claim 2, wherein the oil-based ink is discharged using an electrostatic field. 4. The lithographic printing plate precursor is provided with an image receiving layer having a lithographically printable hydrophilic surface on a water-resistant support, and as the water-resistant support, at least immediately below the image receiving layer. 4. The method for preparing an ink-jet type plate making printing plate according to claim 2, wherein a support having a specific electric resistance value of 10 ¹⁰ Ωcm or less is used. 5. The water-resistant support is a support having a specific electric resistance of 10 ¹⁰ Ωcm or less for the whole support.
5. The method for producing an ink-jet type plate-making printing plate according to any one of items 1 to 4. 6. The ink-jet ink according to claim 2, wherein the resin particles dispersed in the oil-based ink are oil-based inks that are positively or negatively charged. How to make a formula plate printing plate.