JPH11269416A - Oil-base ink for ink jet process printing plate and method for forming printing plate by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-base ink improved in dispersion stability, re-dispersibility, storage stability, image reproducibility, and plate wear by selecting an ink for forming a printing plate composed of a water-resistant support and an image receptive layer formed thereon and containing zinc oxide and a binder resin, wherein the resin is prepared by polymerizing a solution containing (A) a monofunctional monomer, (MA) a monofunctional macromonomer, and (P) a dispersion stabilizing resin and granulating the polymer. SOLUTION: A printing plate is provided in which the angle of contact of the surface of an image receptive layer with water is 30 deg. or greater, and the non-image area is desensitized. The ink is prepared by dispersing resin particles in a nonaqueous carrier fluid having an electric resistance of 10<9> Ωcm or above and a permittivity of 3.5 or below. Component A is a monomer which is miscible with the carrier fluid, is soluble in a nonaqueous solution, and is insolubilized therein when polymerized, component MA is a macromonomer having a weight-average molecular weight of 2×10<4> or below and having a main chain represented by formula I (V<0> is -COO- or the like) and having a polymerizable double bond group of formula II (V<1> is -COO- or the like) at either terminal, and component P is a resin being soluble in a nonaqueous solution and containing a comonomer component of formula III (R<1> is a 10-32C alkyl or the like).

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 ink-jet plate making and a method for preparing a printing plate using the same, and more particularly, to dispersion stability, re-dispersibility, storage stability, and image reproduction. The present invention relates to an oil-based ink having excellent printing properties and printing durability, and a method for preparing a 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. Plate making, that is, a method of forming a lithographic printing plate by forming an image, 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 discharge section for discharging minute ink droplets that enables a high-resolution plate-making image is liable to occur.

In general, in the ink jet recording method, ink is ejected from a discharge portion after passing through a filter. Therefore, in this recording method, clogging of a discharge portion, clogging of a filter, flowability of ink, etc. are caused. Is likely to cause ink ejection abnormality due to various other factors such as changes over time.

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 a discharge portion 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 image formation of a lithographic printing plate, provides satisfactory printing durability due to insufficient image strength at the time of printing.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an oil-based ink for ink-jet plate making which is excellent in dispersion stability, re-dispersibility, storage stability, image reproducibility and printing durability. Another object of the present invention is to provide an ink-jet type plate-making ink in which the ink discharge is stable without causing clogging in the discharge section and the ink supply path.

Another object of the present invention is to provide a method of preparing an ink-jet printing plate for preparing a lithographic printing plate which can stably perform ink-jet recording even when used repeatedly and has excellent printing durability. . Another object of the present invention is to provide a method for producing an ink-jet printing plate capable of printing a large number of prints of a clear image.

[0016]

This and other objects are achieved by the present invention which is defined below as (1) to (6). (1) An image receiving layer of a lithographic printing plate precursor having an image receiving layer containing zinc oxide and a binder resin on a water-resistant support, and having a contact angle of 30 ° or more with water on the surface of the image receiving layer. An oil-based ink formed 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 was ejected in a droplet form thereon to form an image by an inkjet method. Thereafter, in the oil-based ink for ink-jet type plate-making used in the method of preparing an ink-jet type printing plate to desensitize the non-image portion of this image-receiving layer by a chemical reaction process to make a lithographic printing plate, the dispersed resin particles are ,
(i) at least one monofunctional monomer (A) that is soluble in a non-aqueous solvent that is at least miscible with the non-aqueous carrier liquid and becomes insoluble by polymerization; The weight of the polymer containing a repeating unit corresponding to the monomer represented by the general formula (I), in which a polymerizable double bond group represented by the following general formula (II) is bonded to only one end of the main chain. Monofunctional macromonomer having an average molecular weight of 2 × 10 ⁴ or less (M
A solution containing at least one of A) and (iii) at least one dispersion stabilizing resin (P) containing a copolymer component represented by the following general formula (III) soluble in the non-aqueous solvent is polymerized. An oil-based ink for ink-jet plate making, comprising a copolymer resin obtained by granulation.

[0017]

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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 of 8 or more atoms (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom).

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⁾ C
The O- represents (wherein D ²² represents the same content as the D ^21). A ¹ and A ² may be the same or different from each other, and each may be substituted. The following general formula (Ib)
And at least one group selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms (however, in the case of two or more groups, a combination of these groups of formula (Ib) and / or a hydrocarbon group) Represents

[0021]

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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 and n do not become 0 at the same time.

[0023]

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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

[0025]

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In the formula (III), R¹Represents a group having 10 to 32 carbon atoms.
Represents an alkyl group or an alkenyl group. d¹Is a hydrogen atom
Or an alkyl group having 1 to 4 carbon atoms. X¹And X
^TwoIs V in formula (I)⁰And the contents of the same. W is
Linking group X¹And bonding group X^TwoAt least one
One carbon atom, oxygen atom, sulfur atom, silicon atom or
Represents a nitrogen atom. e¹, E^Two, F¹and
f^TwoMay be the same or different from each other, and in the formula (I)
a ¹, A^TwoAnd the contents of the same. x and y are weights of the copolymer.
X / y is 90/10 to 99/1.
You.

(2) 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 30 ° or more with water on the surface of the image receiving layer. After the oil-based ink according to the above (1) is discharged in the form of droplets on the image receiving layer to form an image by an inkjet method,
A method for producing an ink jet printing plate in which a non-image portion of the image receiving layer is desensitized by a chemical reaction treatment to form a lithographic printing plate. (3) The method for producing an ink-jet printing plate as described in (2) above, wherein the image formation of the ink-jet method is performed by utilizing electrostatic attraction.

(4) The ink jet printing plate as described in (2) or (3) above, wherein a support having a specific electric resistance of at least 10 ¹⁰ Ωcm or less is used as the water-resistant support. How to create (5) As the water-resistant support, a support having a specific electric resistance value of 10 ¹⁰ Ωcm or less for the entire support is used (2).
Or the method for producing an ink jet printing plate according to (3). (6) The resin particles dispersed in the oil-based ink are electrostatic particles charged to a positive charge or a negative charge, according to any one of the above (2) to (5). Method of making an inkjet printing plate.

According to the present invention, an image is formed by discharging an oil-based ink by an ink-jet method on an image receiving layer of a lithographic printing plate precursor, and a non-image portion is desensitized to obtain a lithographic printing plate. The oil-based ink used is excellent in dispersion stability, re-dispersibility, and storage stability, and the obtained lithographic printing plate can print many clear images.

[0030]

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 oil-based ink according to the present invention, are prepared by adding
Dispersion stabilizing resin (P) soluble in the above non-aqueous solvent containing a polymerizable double bond group capable of copolymerizing with monofunctional monomer (A) as a copolymerization component of the random copolymer In the presence of a macromonomer (M) containing at least one monomer (A) and a repeating unit containing a specific substituent.
It has been granulated by polymerizing at least one of A).

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

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or the like. Examples thereof include aromatic hydrocarbons and halogen-substituted products thereof. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shelsol 70, Shelsol 71, AMSCO OMS, AMSCO 460 solvent and the like can be used alone or in combination.

Other organic solvents which can be used by mixing 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 the polymerization granulation. There is no problem as long as the resistance is within the range of 10 ⁹ Ωcm or more and the dielectric constant is 3.5 or less.

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

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

[0038]

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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, the phenylene group may be referred to as “—Ph—”. The phenylene group may be 1,2-, 1,3 -And 1,4-phenylene groups). Here, W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group,
2-methoxyethyl group, 3-methoxypropyl group, etc.).

D ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group,
Propyl, butyl, 2-chloroethyl, 2,2-
Dichloroethyl group, 2,2,2-trifluoroethyl group,
2-bromoethyl group, 2-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-
Carboxamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

G ¹ and g ² may be the same or different from each other, and are each a ¹ or a ² in the above-mentioned general formula (I).
And the contents of the same.

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 preferable hydrocarbon group is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, Methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl Group, 3-bromopropyl group, etc.), and optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2 -Pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.), carbon number 7-1
2 optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group and the like, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexyl) An ethyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

When V ⁰ represents -Ph- (phenylene group), the benzene ring may have a substituent. 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 directly bonded to a carbon atom or a nitrogen atom) will be described in detail.

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

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 (-Ph-), 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.

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

The simple substance 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,
Contains at least two or more specific polar groups in a unit component
More specifically, the following repeating unit is used as an example.
Can be mentioned. The following equations (1) to (19)
Here, each symbol represents the following contents.

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

[0058]

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[0059]

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[0060]

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

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

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

[0066]

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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, D ⁴⁴ are each independently a hydrogen atom, a hydrocarbon group representing same contents as the D ^11], atomic such linking group alone selected from atomic groups such as linking groups shown below Represents a single connecting group selected from or a connecting group composed of an arbitrary combination.

[0069]

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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.

Specific examples of the portion represented by the following general formula (II ') in the general formula (V) are shown below. However, the present invention is not limited to these.

[0072]

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

[0074]

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[0075]

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[0076]

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[0077]

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Further, in the polymerization component of the macromonomer (MA) used in the present invention, a repeating unit corresponding to the monomer represented by the general formula (I) and another repeating unit are contained as a copolymerization component. Is also good.

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

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

In the total of the repeating units of the macromonomer (MA), the repeating unit component 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 .

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 the 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 dispersion resin of the present invention comprises at least one kind of each of the monomer (A) and the monofunctional macromonomer (MA). Importantly, the resin synthesized from these monomers is used in a non-aqueous solvent. It is insoluble, so that a desired dispersed resin can be obtained.

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

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

Dispersion stabilizing resin (P) used in the present invention
Is a polymerizable double bond copolymerizable with the monomer (A) at least at the terminal of the side chain of the copolymerizable component (component X), which is soluble in the non-aqueous solvent, represented by the general formula (III). It is a random copolymer containing a copolymer component (Y component) containing a group and soluble in the non-aqueous solvent. General formula (II
In the component (I), the X component may be contained in the resin (P) in two or more types.

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

D ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), preferably a hydrogen atom or methyl group.

X ¹ and X ² each represent V ^{0 in} formula (I)
Represents the same content as W is a group connecting the bonding group X ¹ and the bonding group X ^2, and at least one carbon atom, oxygen atom,
Represents those consisting of sulfur, silicon or nitrogen atoms.

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

[0095]

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[R _{3 to} r ₆ each represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group) Etc.). r ₇ ~r ₉ each represents a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) and the like. r _{10 to} r ₁₁ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example,
A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a benzyl group, a phenethyl group, a phenyl group, a tolyl group, etc. or -Or ₁₂ (where r ₁₂ is the same as the hydrocarbon group in r ₁₀ ) Is shown)).

The heterocyclic group includes hetero atoms containing hetero atoms such as an oxygen atom, a sulfur atom and a nitrogen atom (for example, a thiophene ring, a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring and a piperidine ring). ,
Pyrazine ring, pyrrole ring, piperazine ring, etc.).

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

Specific examples of the repeating unit (Y component) containing a polymerizable double bond group are shown below.
It is not limited to these. In the following formula, each symbol represents the following contents.

[0100]

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[0101]

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[0102]

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

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

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

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

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

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

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

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, azobisisobutyronitrile, 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 the remaining amount together with the polymerization initiator is added to a mixed solution containing the entire amount of the dispersion stabilizing resin (P) and a part of the monomer (A) and the macromonomer (MA). A method in which the monomer (A) and the macromonomer (MA) are arbitrarily added, a mixed solution of the dispersion stabilizing resin (P), the monomer (A) and the macromonomer (MA) in a non-aqueous solvent, There is a method of arbitrarily adding it together with the polymerization initiator, and any of these methods can be used for production.

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 25 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total monomers used above.

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

When the above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination with the non-aqueous solvent used in the reaction, or when the monomer (A) to be polymerized and granulated is not used. When the reactant remains, it is preferable to remove it by heating it to a boiling point of the solvent or the monomer or higher or distilling it off under reduced pressure.

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

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

The oil-based ink of the present invention is excellent in dispersion stability, re-dispersibility and storage stability of dispersed resin particles, has good fast fixability after image formation, and maintains sufficient strength during printing. Shows high printing durability. In other words, it shows extremely stable dispersibility, and particularly in a recording apparatus, has good dispersibility even when used repeatedly for a long time, and is easy to redisperse. I can't. Further, when the ink image was formed and fixed by rapid processing such as heating after heating, a strong film was easily formed on the surface of the image receiving layer of the lithographic printing plate precursor, and good fixability was exhibited. Thereby, even in offset printing, printing of a large number of sheets (high printing durability) becomes possible.

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

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

Further, the macromonomer (MA) having a specific substituent is a monomer (A) which is insolubilized during polymerization granulation.
However, the specific substituent moiety contained in the macromonomer (MA) is designed to have good affinity with the non-aqueous solvent because the specific substituent portion forms particles by non-aqueous dispersion polymerization. By having, because the solvation with the dispersion medium is better than penetrating the inside of the particle structure,
It is oriented at the interface (surface) portion of the particle structure, and as a result, together with the dispersion stabilizing resin (P), the affinity for the dispersion medium on the particle surface is improved, and the effect of preventing aggregation between the particles is significantly enhanced. It is estimated that It is considered that these factors suppress the aggregation and precipitation of the insoluble particles, and significantly improve the redispersibility.

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

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

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

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

These pigments and dyes may be used alone or in an appropriate combination, but may be contained in the range of 0.05 to 5% by weight based on the whole ink. desirable.

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

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

[0127] The particles can be imparted with an electric detecting property by appropriately utilizing a technique of a wet type electrophotographic developer. Specifically, "Recent development and practical use of electrophotographic development systems and toner materials", pages 139 to 148, "The Basics and Applications of Electrophotographic Technology", edited by the Society of Electrophotographic Engineers, 497-505.
Page (Corona Publishing, 1988), Yuji Harasaki "Electrophotography"
16 (No. 2), p. 44 (1977) and the like.

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

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1000 parts by weight of the dispersion medium as the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electrical resistance of the oil-based ink. 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. .

The oil-based ink containing the electro-detectable resin particles of the present invention is preferably used in an electric field control type ink jet recording system utilizing an electrostatic attraction by applying an electrostatic field. In this case, the ease of discharging the oil-based ink is further improved.

A method for producing a printing plate according to the present invention will be described.

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

The image receiving layer contains zinc oxide and a binder resin, and the degree of hydrophobicity of the surface thereof is 30 degrees at a contact angle with water.
゜ or more. 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 plate at room temperature and measuring the surface contact angle (degree) after 30 seconds using a surface contact meter (CA-D, Kyowa Interface Science Co., Ltd.). )). The smaller the value, the better the wettability to water and the more hydrophilic.

When the contact angle with water is in the above range, the strength of the image portion is sufficiently maintained as described above, and a clear image is formed without disturbing the image such as fine lines, fine characters and halftone dots. Is done. In consideration of ink receptivity, it is preferably 40 ° to 130 °, more preferably 50 ° to 120 °, and particularly preferably 55 ° to 110 °.

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

In the present invention, the smoothness of the surface of the image receiving layer is preferably 30 (sec / 10 cc) or more, more preferably 45 to 300 (sec / 10 c), in Beck smoothness.
c). By using an image receiving layer having a smooth surface, a clear image without image defects is formed, and the adhesion between the image area and the image receiving layer is also improved by the effect of improving the adhesion area, and printing durability is improved. The properties are also remarkably improved to several thousand sheets or more.

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

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

That is, zinc oxide is classified according to a starting material and a production method, and includes a dry method, a French method (indirect method), an American method (direct method), and a wet method. Co., Ltd.), Sakai Chemical Co., Ltd., Hakusui Chemical Co., Ltd., Honjo Chemical Co., Ltd., Toho Zinc Co., Ltd.,
Examples include those commercially available from various companies such as Mitsui Kinzoku Kogyo.

The content of zinc oxide in the image receiving layer is preferably about 75 to 90% by weight. If the amount of zinc oxide is too small, hydrophilization of the surface of the image receiving layer by the desensitizing treatment becomes insufficient, and if it is too large, the required amount of binder resin cannot be secured, which is not preferable.

As described above, the binder resin provided for the image receiving layer of the present invention constitutes an image receiving layer together with zinc oxide, and has a hydrophobic property such that the contact angle on the surface thereof is within the above-mentioned predetermined range. Resin, and the weight average molecular weight (M
w) is preferably 10 ³ to 10 ⁶ , more preferably 5 ×
It is 10 ^{3 to} 5 × 10 ⁵ . Further, the glass transition point of this resin is preferably 0 ° C to 120 ° C, more preferably 10 ° C to 120 ° C.
90 ° C.

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

Other components that may be contained include:
There are inorganic pigments other than zinc oxide, such as, for example, kaolin, clay, calcium carbonate,
Examples include barium carbonate, calcium sulfate, 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% by weight based on 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 used.
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. The content of the resin particles is preferably 20% by weight or less based on the total composition of the image receiving layer.

When these other inorganic pigments or resin particles are used within the above-mentioned use range, the desensitization (hydrophilicity) of the non-image portion 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 more effectively exhibited, and film strength is maintained during printing or high hydrophilicity is maintained during desensitization treatment.

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

In the present invention, a reaction accelerator may be added as necessary in order 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), thiuram disulfide compounds (such as tetramethylthiuram disulfide), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride,
3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.).
When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator is used, and examples thereof include a peroxide and an azobis compound.

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

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

In the present invention, the thickness of the image receiving layer is 1 m ²
3 in terms of application amount (after drying) of the image receiving layer composition per unit
It is preferably about 30 g. This image receiving layer is usually 3 to 50 vol%, preferably 10 to 40 vol%.
It is preferable to have a porosity of the order.

The image receiving layer of the present invention is provided on a water-resistant support. Aluminum plate,
Bimetal plates such as zinc plate, copper-aluminum plate, copper-stainless plate, chrome-copper plate, etc., and tri-metal plates such as chrome-copper-aluminum plate, chrome-lead-iron plate, chromium-copper-stainless plate, etc. It is preferably 0.1 to 3 mm, particularly preferably 0.1 to 1 mm. Also, the thickness is 80μ ~
Paper subjected to a water resistance treatment of 200 μ, paper laminated with a plastic film or metal foil, plastic film, or the like is also preferably used.

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

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

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

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

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

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

Next, the conductive layer will be described.

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

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

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

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

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

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

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

As the water-resistant substrate, the above-mentioned water-resistant support can be used.

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

In the present invention, the surface of the support on the side adjacent to the image receiving layer has a Beck smoothness of 300 (seconds / 10/10).
cc) or more, and preferably adjusted to 900 to 3000 (second / 10 cc), more preferably 1,000 to 3,000.
It is preferably 3000 (sec / 10 cc). The Beck smoothness of the support surface can also be measured by the method described above.

By regulating the smoothness of the surface of the support on the side adjacent to the image receiving layer to the above value, image reproducibility and printing durability can be further improved. Such an improvement effect is obtained even if the surface smoothness of the image receiving layer itself is the same, and the adhesion of the image portion to the image receiving layer is improved by increasing the smoothness of the support surface. It is thought to be.

The highly smooth surface of the water-resistant support thus regulated refers to the surface on which the image receiving layer is directly applied. For example, the above-mentioned conductive layer, underlayer, overcoat When a coat layer is provided, it refers to the surface of the conductive layer, underlayer, and overcoat layer. As a result, the image receiving layer whose surface condition has been adjusted as described above is sufficiently retained without receiving the unevenness of the surface of the support, and the image quality can be further improved.

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

In the present invention, as described above, an under layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a curl prevention is provided on the surface of the support opposite to the image receiving layer. A backcoat layer (backside layer) can be provided for the purpose, but the backcoat layer preferably has a smoothness in the range of 150 to 700 (sec / 10 cc). Accordingly, when the printing plate is supplied to the offset printing press, the printing plate is accurately set on the printing press without causing displacement or slippage.

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

Such 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 the coating solution, or laminating the coating solution. The resin used here is appropriately selected and used. Specifically, the same resin as the resin provided for the above-described conductive layer can be used.

Examples of the pigment include clay, kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica and the like. These pigments are used to achieve the desired smoothness.
It is preferable to appropriately select and use the particle size. Since a lower smoothness is required in the back coat layer as compared with the under layer, a larger particle size, specifically, about 0.5 to 10 μm is used. Particle size pigments are preferably used. In addition, it is preferable to use the pigment as described above at a ratio of 80 to 200 parts by weight with respect to 100 parts by weight of the resin. In order to obtain excellent water resistance, the under layer and the back coat layer described above are effective to contain a water-resistant agent such as a melamine resin or a polyamide epichlorohydrin resin. The particle size can be measured by a scanning electron microscope (SEM) photograph. When the particles are not spherical, the diameter is obtained by converting the projected area into a circle.

In order to prepare a lithographic printing plate precursor used in the present invention, a solution containing an under layer component, if necessary, is applied to one surface of a support and dried to form an under layer.
Further, if necessary, a solution containing the component of the back coat layer may be applied and dried on the other surface to form a back coat layer, and then a coating solution containing the component of the image receiving layer may be applied and dried to form an image receiving layer. The application amount of the back coat layer is 1 to
30 g / m ^2, are suitable particularly 6~20g / m ^2.

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

Next, a method for 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 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 transferred from an information supply source such as the computer 3 through a transmission means such as the bus 4 to the oil-based ink. Is supplied to the ink jet recording apparatus 1 that uses. The ink jet recording head 10 of the recording apparatus 1 stores oil-based ink therein, and when the master 2 passes through the recording apparatus 1, sprays minute droplets of the ink on the master 2 according to the information. Thereby, ink adheres to the master 2 in the pattern. Thus, an image is formed on the master 2.

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

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

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

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

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

As described above, on the lithographic printing original plate,
After an image is formed by an ink jet method using an oil-based ink, the surface is treated with a desensitizing solution to desensitize the non-image portion, thereby producing a printing plate.

The desensitization of zinc oxide has been conventionally carried out as this type of desensitization treatment solution, a treatment 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 treatment solution containing a phytic acid compound include:
JP-A Nos. 53-83807, 53-83805, 53-102102, 53-109701, and 5
Nos. 3-127003, 54-2803, 54-4
No. 4901 and the like.

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

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

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

In any of the above desensitizing treatments,
The zinc oxide in the image receiving layer is ionized into zinc ions, and the ions undergo a chelation reaction with the chelating compound in the desensitizing solution to form a zinc chelate, which is deposited in the surface layer Is believed to be hydrophilized. Desensitization treatment is usually performed at room temperature (15 ° C to 3 ° C).
(About 5 ° C.) for about 2 to 60 seconds. Using this printing plate, several thousand sheets of offset printing can be performed using dampening water.

[0197]

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

Synthesis Example 1 of Dispersion Stabilizing Resin (P) 1: Resin [P-1] A mixed solution of 96 g of octadecyl methacrylate, 4 g of 4- (2-methacryloyloxyethyloxycarbonyl) butyric acid, and 200 g of toluene was placed in a nitrogen stream. Lower, temperature 75
Warmed to ° C. As an initiator, 1.5 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours. I. B. N. 0.8
g was added and the mixture was heated to a temperature of 80 ° C. and reacted for 4 hours. After cooling the reaction mixture to a temperature of 25 ° C., 6 g of allyl alcohol was added with stirring, followed by 10 g of dicyclohexyl dicarbodiimide (abbreviated as DCC), 4- (N, N
A mixed solution of 0.1 g of-(diethylamino) pyridine and 30 g of methylene chloride was added dropwise over 1 hour. Further, the reaction was continued for 3 hours to complete the reaction. Next, 10 g of 80% formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. Then, the insoluble matter was filtered off, and the solution 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 was 70 g and Mw was 5
× 10 ⁴ (polystyrene-equivalent value according to GPC; the same applies hereinafter).

[0200]

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Synthesis Example 2 of Dispersion Stabilizing Resin (P): Resin [P-2] A mixed solution of 50 g of dodecyl methacrylate, 45 g of octadecyl acrylate, 5 g of glycidyl methacrylate and 200 g of toluene was stirred at 75 ° C. under a nitrogen stream. Was heated. A. I. B. N. Was added and reacted for 4 hours. I. B. N. 0.5g
Time, and A. I. B. N. Was added and reacted for 3 hours. Next, 6 g of 3-acryloyloxypropionic acid and N, N-dimethyldodecylamine were added to the reaction solution.
0 g and t-butyl hydroquinone 0.5 g were added, 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,
g was obtained. The weight average molecular weight (Mw) of the polymer is 4 × 10 ⁴
Met.

[0202]

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Synthesis Example 3 of Dispersion Stabilizing Resin (P): Resin [P-3] A mixed solution of 96 g of tridecyl methacrylate, 4 g of 11-methacrylamidoundecanoic acid and 200 g of toluene was stirred at a temperature of 75 ° C. under a nitrogen stream. Was heated.
A. I. B. N. Was added and reacted for 4 hours. I. B. N. Was added for 3 hours, and A. I.
B. N. Was added and reacted for 3 hours. After cooling to a temperature of 40 ° C., 0.2 g of hydroquinone was added. Further, 6.9 g of vinyl acetate and 0.05 g of mercury acetate were added and reacted for 2 hours. The temperature is raised again to 70 ° C and 100% sulfuric acid 7.5
× 10 ^-3 ml was added and reacted for 6 hours. After the reaction, 0.04 g of sodium acetate trihydrate was added to the reaction solution, and the mixture was stirred well, and then poured into 4.5 liters of methanol for reprecipitation purification to obtain 75 g of a slightly brownish viscous substance. Obtained. Mw of the polymer was 5.3 × 10 ⁴ .

[0204]

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

[0206]

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Production Example 1 of Macromonomer (MA) Macromonomer (MA-1) A mixed solution of 100 g of octadecyl methacrylate, 2 g of 3-mercaptopropionic acid and 200 g of toluene was heated to 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. C. Expressed in terms of polystyrene by the method. same as below).

[0208]

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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 polymerization average molecular weight of each of the obtained macromonomers is 9 × 10 ³ to 1
× 10 ⁴ range.

[0210]

[Table 1]

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

The filtrate obtained by filtering off 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.

[0213]

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Production Examples 13 to 1 of Macromonomer (MA)
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, the macromonomers shown in Table 2 below were each produced. 60 ~
The polymerization average molecular weight of each macromonomer obtained in 70 g was in the range of 7 × 10 ^{3 to} 9 × 10 ³ .

[0215]

[Table 2]

Production Example 16 of Macromonomer (MA) Macromonomer (MA-16) A mixed solution of 100 g of 2,3-dihexanoyloxypropyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated at a temperature of 7 under a nitrogen stream.
Warmed to 5 ° C. 5.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: 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 ° 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 .

[0218]

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Production Example 1 of Resin Particles: Resin Particles [L-1] 10 g of dispersion stabilizing resin [P-1], 100 g of vinyl acetate
g, 4 g of macromonomer (MA-1) and 342 g of Isopar H were 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. I. V.
N. Was added and reacted for 2 hours. Continue to A.
I. B. N. Was added, and the temperature was raised to 80 ° C. and reacted for 3 hours. Then, the temperature was raised to 100 ° C.
The mixture was stirred at 0 mmHg for 2 hours to distill off unreacted monomers.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 98% and an average particle size of 0.40 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

A part of the white dispersion was centrifuged (rotator: 1 × 10 ⁴ rpm, rotation time: 1 hour), and the sedimented resin particles were collected and dried, and the weight average molecular weight (Mw) of the resin particles was measured. ) And the glass transition point (Tg)
Mw was 3 × 10 ⁵ (polystyrene conversion value by GPC; the same applies hereinafter), and Tg was 38 ° C.

Production Example 2 of Resin Particles: Resin Particles [L-2] Dispersion stabilizing resin [P-2] 12 g and Isopar H were mixed with 17
7 g of the mixed solution was stirred at a temperature of 60 ° C. under a nitrogen stream.
Was heated. 40 g of methyl methacrylate, 60 g of methyl acrylate, 3 g of macromonomer (MA-5), 200 g of Isopar G and A.I. I. V. N. To 1.0
g of the mixture was added dropwise over 2 hours, and the mixture was stirred for 2 hours. Further, A.I. I. V. N. 0.5 g and temperature 75
C. and stirred for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth.
Was a latex having an average particle size of 0.38 μm. The Mw of the resin particles was 1 × 10 ⁵ , and the Tg was 38 ° C.

Production Examples 3-6 of Resin Particles: Resin particles [L-
3] to [L-6] In Resin Particle Production Example 1, the dispersion stabilizing resin [P-
1] Instead of 10 g, use 11 g of resin [P-4],
Vinyl acetate (monomer A) and macromonomer (MA-
Except that each monomer (A) and macromonomer (MA) shown in Table 3 below were used in place of 1), resin particles [L-3] to [L-
6] was produced.

[0223]

[Table 3]

The degree of polymerization of each resin particle was 93 to 98%, the average particle diameter was in the range of 0.35 to 0.40 μm, and the monodispersity was good. Mw of each resin particle is 8 × 10 ⁴ or more.
It was in the range of 1 × 10 ⁵ .

Production Examples 7 to 15 of Resin Particles: Resin Particles [L
-7] to [L-15] In Resin Particle Production Example 2, the dispersion stabilizing resin [P-
2] Instead of 12 g, 11 g of resin [P-3] was used,
The present invention was carried out in the same manner as in Production Example 2 except that the compounds shown in Table 4 below were used instead of the monomer (A) (that is, methyl methacrylate and methyl acrylate) and the macromonomer (MA-5). Resin particles [L-7]
To [L-15].

[0226]

[Table 4]

The polymerization rate of each of the obtained resin particles is 95 to 99.
%, And the average particle size is in the range of 0.38 to 0.45 μm.
The monodispersibility was good. Mw of each resin particle is 8 ×
10 ^Four~ 2 × 10^FiveWas within the range.

Resin Particle Production Examples 16 to 19: Resin Particles [L-16] to [L-19] In the resin particle production example 1, the dispersion stabilizing resin [P-
1] and the macromonomer (MA-1) in place of the dispersion stabilizing resin and the macromonomer (M) shown in Table 5 below.
Resin particles [L-16] to [L-19] of the present invention were produced in exactly the same manner as in Production Example 1 except that A) was used.

[0229]

[Table 5]

The polymerization rate of each of the obtained resin particles is 97 to 98.
%, The average particle size was in the range of 0.3 to 0.4 μm, and the monodispersity was good. Mw for each resin particle is 2 × 10
^{5 to} 3 × 10 ⁵ , Tg was in the range of 37 to 38 ° C.

Production Example 20 of Resin Particles (Comparative) A resin for comparison was produced in the same manner as in Production Example 1 except that 4 g of the macromonomer (MA-1) used in Production Example 1 of the resin particles was omitted. Particles [L-20] were produced. The polymerization rate of the obtained resin particles was 95%, and the average particle size was 0.45.
μm. The Mw of the resin particles was 3 × 10 ⁵ , and the Tg was 37 ° C.

Example 1 <Preparation of planographic printing plate precursor> Dry zinc oxide (Seido Chemical Co., Ltd.)
100 g, binder resin (B-1) 3.0 having the following structure
g, binder resin (B-2) 17.0 g, benzoic acid 0.15
g and 155 g of toluene were mixed with a wet disperser homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 6.
Dispersed at ³ rpm for 8 minutes.

[0233]

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A support of ELP-1X type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing plate precursor for transfer printing (support surface smoothness 1200 (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 plate precursor. .

As described above, 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 at room temperature,
The surface contact angle (degree) after 0 seconds is measured using a surface contact angle meter (CA-
D, manufactured by Kyowa Interface Science Co., Ltd.)
It was 102 degrees.

The smoothness of the image receiving layer was determined by using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) as described above.
When the smoothness (second / 10 cc) was measured under the condition of an air volume of 10 cc, it was 220 (second / 10 cc).

<Preparation of oil-based ink (IK-1)> Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 9)
5 g (5/5 weight ratio), 10 g of alkali blue and 71 and 30 g of Shellsol were put together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of alkali blue. 50 g (as solid content) of the resin particles (L-1) of Production Example 1 of latex particles, 18 g of the above-mentioned alkali blue dispersion, and 0.09 g of octadecene-half-maleic acid octadecylamide copolymer were added to 1 liter of Isopar G. A blue oil-based ink was prepared by dilution.

A servo plotter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing output from a personal computer, using the lithographic printing original plate prepared as described above was modified, and the ink ejection head shown in FIG. ,
Printing was performed on the lithographic printing original plate placed on the counter electrode with an interval of 1.5 mm using the oil-based ink (IK-1) having the above-mentioned contents, and plate-making was performed. Continue to RICOH FUSE
Using an R model 592 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 65 ° C. and heated for 10 seconds to sufficiently fix the image area.

When the copied image of the obtained plate-making product 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 also good, and abnormalities such as bleeding, lack, and blur were recognized. No contamination was observed in the non-image area.

The above plate-making product was treated with a desensitizing solution: ELP-
It was immersed in E2 (manufactured by Fuji Photo Film Co., Ltd.) for 5 seconds to desensitize the non-image area to obtain a printing plate. This printing plate is printed with black ink for offset printing using a solution obtained by diluting the above ELP-E2 15 times with water as immersion water, and using Oliver 94 type (manufactured by Sakurai Seisakusho) as a printing material. did. As a result, more than 3,000 printed images with clear images free of background stains were obtained.

Next, an ink ejection test was performed using the above-mentioned ink jet printer. As a result, stable ink ejection was obtained even after 600 hours. The ink stored at room temperature for 6 months showed no generation of agglomerates, and stable ink ejection was obtained even when the same ejection test was performed.

Further, when the printing plate obtained under these conditions was actually printed, 3,000 or more printed matters having clear images without background smear were obtained. Further, the redispersibility of the ink was evaluated under strong printing conditions. That is, the ejection head used in the printer is filled with ink and removed.
The ink (IK-1) was left for 3 days at 3 ° C., and then immersed in the discharge head for 3 minutes in Isopar G, followed by gentle stirring.
Were all removed from within the slit. That is, it is considered that the ink (IK-1) adhering to the slit tip portion of the ejection head in a non-fluid state when left undisturbed was easily redispersed by solvation with the dispersion medium.

As described above, the oil-based ink of the present invention has good ink ejection stability, forms a clear image free of stains, and obtains a printing plate, even after continuous plate making for a long period of time. Indicates high printing durability.

Comparative Example A The operation was performed in the same manner as in Example 1 except that the oil-based ink (IKR-1) having the following content was used instead of the oil-based ink (IK-1).

<Preparation of Comparative Oil-Based Ink (IKR-1)> In the oil-based ink (IK-1), the resin particles (L-
In place of 1), 50 g of comparative resin particles (L-20)
(Ink (IK-1))
Created in the same way as

The lithographic printing plate obtained by using the oil-based ink of Comparative Example A was prepared first, and as in Example 1, 3,000 or more prints of clear images without stain were obtained. Was. However, in the ink ejection test, Comparative Example A showed 20
The ink ejection became unstable in about 0 hours. Also, 6
The ink of Comparative Example A that had been stored for months stored an aggregated precipitate and did not redisperse when shaken. Further, for Comparative Example A, a forced test of the ink redispersibility was performed under the same conditions as in Example 1. As a result, extraneous matter remained in the slits of the ejection head portion.

Example 2 <Preparation of lithographic printing original plate> In Example 1, an ELP-2X type master (Fuji Photo Film Co., Ltd.) was used instead of the ELP-1X type master support used as the water-resistant support.
A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that a PET laminated paper support [trade name of manufactured product] (support surface smoothness: 1800 (sec / 10 cc)) was used.

<Preparation of oil-based ink (IK-2)> 10 g of poly (dodecyl methacrylate) and 10 g of nigrosine
g and 30 g of Isopar H were put together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine. 50 g of resin particles (L-2) of Production Example 2 of resin particles (in terms of solid volume) 35 g of the above nigrosine dispersion and 0.10 g of [octadecyl vinyl ether-hemo maleic acid dodecylamide] copolymer were added to 1 liter of Isopar G. By dilution, a black oil-based ink was prepared.

This printing original plate and oil-based ink (IK-2)
In the same manner as in Example 1, plate making and desensitizing treatment were performed to obtain a printing plate, and offset printing was performed.

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printed matter of Example 1.
The printing durability was as good as 10,000 sheets or more. When an ink ejection test and a redispersibility compulsory test were conducted for 600 hours in the same manner as in Example 1, the performance was completely the same as that of the ink (IK-1), and was excellent.

[0251] Using the high quality paper weighing 100 g / m ² Example 3 substrate, a back layer coating the following composition on one surface of the substrate by coating using a wire bar, a dry coating amount of 12 g / m ² After the back layer was provided, calendering was performed so that the smoothness of the back layer was about 50 (second / 10 cc).

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

Next, under layer coatings A to G (detailed in Table 6) having the following composition were applied to the other surface of the substrate using a wire bar, and the under layer having a dry coating amount of 10 g / m ^{2 was} applied. Is provided, the smoothness of the under layer is 1500 (seconds / 1
Calendar processing was performed so as to be about 0 cc). As shown in Table 6, the seven types of the water-resistant supports obtained in this manner were used as support samples N according to the coating formulations A to G, respectively.
o. 01-No. 07.

[0254]

[Table 6]

<Coating for under layer> Carbon black (30% aqueous dispersion) Clay (50% aqueous dispersion) SBR latex (solid content 50%, Tg 25 ° C.) Melamine resin (solid content 80%, Sumi Let's Resin SR
-613)

The above components were mixed in the composition shown in Table 6,
Water was added so that the total solid content concentration was 25% to obtain coating liquids for underlayer coatings A to G.

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

[0258]

[Table 7]

[Preparation of Lithographic Printing Precursor] 01-No. 07, an image receiving layer was provided so that the applied amount of the dispersion of the following composition after drying was 6 g / m ² , to prepare lithographic printing original plates. The surface smoothness of each master was in the range of 200 to 230 (sec / 10 cc), and the contact angle with water was 102 degrees. 100 g of dry zinc oxide (manufactured by Seido Chemical Co., Ltd.) as in Example 1, 16 g of binder resin (B-3) having the following structure, and binder resin (B-4) 4
g, a mixture of 0.36 g of 3-propoxybenzoic acid and 155 g of toluene were dispersed at a rotation speed of 1 × 10 ⁴ rpm for 20 minutes using a wet type disperser Kedimill.

[0260]

Embedded image

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

Each lithographic printing plate was converted to a fully automatic printing machine (AM-28).
50, a product of AM Co., Ltd., trade name), as a dampening solution, a solution obtained by diluting ELP-E2 10 times with distilled water was placed in a dampening solution tray, and black ink for offset printing was used. Printing was done. The image quality of the drawn images of the plate-making product and the printed material thus obtained was evaluated as follows. The results are shown in Table-8.

[0263]

[Table 8]

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

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

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

The lithographic printing original plate sample no. 4-7
The specific electric resistance of the under layer is 10 ⁸-10^ThreeΩcm and small
It is composed of a support and has no problem with the image,
The letters are also very good. High printing durability. On the other hand,
Air resistance of 10¹²-10¹¹Lithographic printing original plate as large as Ωcm
Sample No. 1 and 2 are missing or blurred images
You. Also, the resin layer of the drawn image becomes thin as a result of bleeding
Therefore, printing durability is low. That is, the support directly below the image receiving layer
The higher the conductivity of the body under layer, the higher the plate making quality and printing
This indicates that the image quality is good.

Examples 4 to 20 Plate-making and printing were performed in the same manner as in Example 1 except that the oil-based ink (IK-1) was replaced with the oil-based ink shown in Table 9 below. The oil-based ink used was the oil-based ink (IK-1) with resin particles (L-
It was prepared in the same manner except that 50 g (as a solid content) of the resin particles (L) in Table 6 below were used instead of 1).

[0269]

[Table 9]

It was found that each plate had the same image quality as the printing plate of Example 1, and the printing durability was 3,000 or more. Further, in the same manner as in Example 1, even in the ink ejection test and the redispersibility forced test for 600 hours or more, the performance was completely equivalent to or higher than that of the ink (IK-1), and was excellent.

Example 21 [Preparation of Water-Resistant Support] A high-quality paper weighing 100 g / m ² was used as a substrate, and a coating for an underlayer 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 Beck smoothness of the under layer surface was 150 sec / 10 cc, and the Bekk smoothness was adjusted to 1500 (sec / 10 cc) by calender treatment.

<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 Beck smoothness was about 50 (second / 10 cc).

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

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

[0276]

Embedded image

<Acrylic Acid Resin Particle Dispersion> 8 g of acrylic acid, 2 g of AA-6 (trade name: a macromonomer of methyl methacrylate manufactured by Toa Gosei Chemical Co., Ltd.), 2 g of ethylene glycol dimethacrylate, 0 g of methyl 3-mercaptopropionate A mixed solution of 0.1 g and 55 g of methyl ethyl ketone was heated to a temperature of 60 ° C. under a nitrogen stream. 0.2 g of 2,2'-azobis (isovaleronitrile)
Was added and reacted for 3 hours. Further, 0.1 g of the initiator was added and reacted for 4 hours. The resulting dispersion has a conversion of 95%.
The average particle size of the dispersed resin particles was 0.20 μm and the monodispersibility was good (particle size measurement: CAPA-500 (trade name, manufactured by Horiba, Ltd.)).

The coated product was coated on a water-resistant support similar to that used in Example 1 with a wire bar so as to have a coating amount of 18 g / m ^2, and dried to obtain a lithographic printing original plate. The surface Beck smoothness of the obtained image receiving layer is 350 (sec / 10 cc).
Met.

This printing original plate was made in the same manner as in Example 1, subjected to desensitization treatment to form a printing plate, and offset printing was performed. However, the oil-based ink of Example 1 (IK-
Instead of 1), oil-based ink (IK-20) of the following content
Was used.

<Preparation of oil-based ink (IK-20)> White dispersion (L-6) obtained in Production Example 6 of latex particles
A mixture of 300 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 blue resin dispersion having an average particle size of 0.38 μm was obtained. 260 g of the above blue resin dispersion and 0.16 g of zirconium naphthenate were diluted to 1 liter of Shellsol 71 to prepare a blue oil-based ink.

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printed matter of Example 1.
The printing durability was as good as 3,000 or more. In addition, as in Example 1, the ink ejection test and redispersibility compulsory test for 600 hours showed the same performance as that of the ink (IK-1) and were excellent.

According to the present invention, a monofunctional macromonomer having a polymerizable double bond group at the terminal, a monofunctional monomer and a dispersion stabilizing resin shown in the specification are reacted in a non-aqueous solvent system to form a copolymer. Using an oil-based ink in which polymer resin particles are dispersed, an image is formed by an inkjet method on an image receiving layer made of zinc oxide and a binder resin, and a lithographic printing plate prepared by desensitizing a non-image portion is a lithographic printing plate. The plate making process is simple and the printing durability is excellent. The oil-based ink of the present invention has good storage stability and dispersibility.

[Brief description of the drawings]

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

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

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

[Explanation of symbols]

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

Claims (6)

[Claims] A zinc oxide and a binder tree on a water-resistant support
Having an image receiving layer containing fat,
An image of a lithographic printing plate with a contact angle of 30 ° or more with water
On the receiving layer, an electric resistance of 10⁹2. Ωcm or more and dielectric constant
In a non-aqueous carrier liquid of 5 or less, at least resin particles are dispersed.
Ink jet method by discharging oil-based ink composed of droplets
After forming an image by the formula, the non-image part of this image receiving layer is converted
A lithographic printing plate after desensitization by chemical reaction
Ink jet printing plate
In a jet type oil-based ink for plate making, the dispersed resin particles
Are (i) at least miscible with the non-aqueous carrier liquid.
Soluble in non-aqueous solvents, and becomes insoluble by polymerization.
At least one of the monofunctional monomers (A), (ii)
Contains a repeating unit corresponding to the monomer represented by the general formula (I)
The following general formula (II) only at one end of the main chain of the polymer
Weight-average component obtained by bonding a polymerizable double bond group represented by
Child size is 2 × 10^FourA monofunctional macromonomer that is
(MA) at least one, and (iii) the non-aqueous solvent
Containing a copolymerizable component represented by the following general formula (III)
Contains at least one kind of dispersion stabilizing resin (P)
Resin obtained by subjecting a solution to polymerization granulation
Oil-based ink-jet plate making characterized by the following
ink. Embedded imageIn the general formula (I), V⁰ Is -COO-, -OCO-,-
(CH_Two)_rCOO-,-(CH_Two)_rOCO-, -O-,-
SO_Two-, -CONHCOO-, -CONHCONH
-, -CON (D¹¹)-, -SO_Two N (D¹¹)-
Represents a phenylene group (where D¹¹Is a hydrogen atom or charcoal
Represents a hydrocarbon group having a prime number of 1 to 22, and r is an integer of 1 to 4
Shown). a¹ And a^Two Are the same but different
Each may be a hydrogen atom, a halogen atom, a cyano group,
Hydride group, -COO-D¹²Or through a hydrocarbon group
-COO-D¹²(Where D¹²Is a hydrogen atom or
Represents a hydrocarbon group which may be substituted). D⁰ Has 8 carbon atoms
To 22 hydrocarbon groups or 8 or more total atoms (however, carbon
Excluding hydrogen atom directly bonded to atom or nitrogen atom)
Represents a substituent represented by the following general formula (Ia). General formula (Ia)-(A¹ -B¹ )_m-(A^Two -B^Two )_n-D^{twenty one} In the general formula (Ia), D^{twenty one}Is a hydrogen atom or a carbon number of 1 to 22
Represents a hydrocarbon group. B¹ And B^Two Are the same as each other
May also be different, each being -O-, -CO-, -CO
_Two -, -OCO-, -SO_Two -, -N (D^{twenty two})-, -C
ON (D^{twenty two})-Or -N (D^{twenty two}) Represents CO- (here
In D^{twenty two}Is D^{twenty one}It shows the same content as). A¹ And A
^Two May be the same or different from each other,
A group represented by the following general formula (Ib) and a carbon
At least one selected from hydrocarbon groups having a prime number of 1 to 18
Are each a single group (however, when two or more groups are represented by the formula (I)
b) and / or a combination of hydrocarbon groups). Embedded imageIn the general formula (Ib), B^Three And B^Four Are the same but different
The above B¹ , B^Two Indicates the same content as
A^Four Is an optionally substituted hydrocarbon having 1 to 18 carbon atoms
A group; D^{twenty three}Is D^{twenty one}Indicates the same content as. m, n
And p may be the same or different from each other;
Represents an integer of 0 to 4; However, m and n simultaneously become 0
It will not be. Embedded imageIn the general formula (II), V¹ Is -COO-, -CONHCOO
-, -CONHCONH-, -CONH- or phenyl
Represents a len group. b¹ And b^Two Are the same but different
A in formula (I)¹ , A^Two Same contents as
Represents Embedded imageIn the formula (III), R¹Is an alkyl group having 10 to 32 carbon atoms or
Represents an alkenyl group. d¹Is a hydrogen atom or 1 carbon atom
Represents an alkyl group of 4 to 4. X¹And X^TwoIs the formula
V in (I)⁰And the contents of the same. W is a bonding group X¹When
Linking group X^TwoAnd at least one carbon atom
Atom, oxygen atom, sulfur atom, silicon atom or nitrogen atom
Represents the following. e¹, E^Two, F¹And f^TwoAre each other
May be the same or different, and a in formula (I) ¹, A^TwoSame as
Indicates the content of-. x and y represent the weight composition ratio of the copolymer.
However, x / y is 90/10 to 99/1. 2. An image of a lithographic printing plate precursor having an image receiving layer containing zinc oxide and a binder resin on a water-resistant support, and having a contact angle of 30 ° or more with water on the surface of the image receiving layer. After the oil-based ink according to claim 1 is ejected in the form of droplets on the receiving layer to form an image by an ink jet method, the non-image portion of the image receiving layer is desensitized by a chemical reaction process to perform lithographic printing. How to make an inkjet printing plate as a plate. 3. The image forming method according to claim 1, wherein:
The method for producing an ink jet printing plate according to claim 2, wherein the method is performed by utilizing electrostatic attraction. 4. The method according to claim 2, wherein at least a portion immediately below the image receiving layer has a specific electric resistance of 10 ¹⁰ Ωcm or less as the water-resistant support. 5. The method for producing an ink jet printing plate according to claim 2, wherein a support having a specific electric resistance value of 10 ¹⁰ Ωcm or less is used as the water-resistant support. 6. The method according to claim 2, wherein the resin particles dispersed in the oil-based ink are electrifying particles charged to a positive charge or a negative charge. How to make an inkjet printing plate.