JPH10306244A - Oily ink for ink-jet type graphic art printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject ink capable of showing redispersibility, shelf stability and printing resistance and printing a large number of sheets of printed paper having a clear image, by dispersing specific polymer resin particles into a prescribed nonaqueous carrier liquid. SOLUTION: This ink is used for injecting the ink in a droplet state from a nozzle on a water-resistant substrate having a hydrophilic surface printable by lithography and forming an image by an ink-jet method to form a lithographic printing block. The ink is obtained by dispersing polymer resin particles prepared by polymerizing a mixture containing each at least one of a monofunctional monomer which is soluble in a nonaqueous solvent but is made insoluble by polymerization and one specific resin for dispersion stability into a nonaqueous carrier liquid having >=10<9> Ωcm electric resistance and <=3.5 dielectric constant. The resin for dispersion stability is composed of a block A containing a polymer component corresponding to the monofunctional monomer and a polar group-containing polymer component and a block B of the formula [X<1> is COO, etc.; Y<1> is an >=8C aliphatic group; a<1> and a<2> are each H, cyano, etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based ink used for an ink-jet type plate-making printing plate.
The present invention relates to an oil-based ink having excellent redispersibility, storage properties, image reproducibility and printability.

[0002]

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

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

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

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

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

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

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

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

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

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

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

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

[0014]

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

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

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

[0017]

The above object is achieved by the following constitution. (1) An oil-based ink in which at least resin particles are dispersed in a non-aqueous carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less on a lithographically printable water-resistant support having a hydrophilic surface. In the oil-based ink for an ink-jet type plate-making printing plate, which is ejected in a droplet form from a nozzle to form an image by an ink-jet method to form a lithographic printing plate, the dispersed resin particles are soluble in the non-aqueous solvent. A polymer obtained by polymerizing a mixture containing at least one monofunctional monomer (A) which becomes insoluble by polymerization and at least one dispersion stabilizing resin [P]. The combined resin particles, wherein the dispersion stabilizing resin [P]
Is that at least three AB type block polymer chains composed of blocks A and B are bonded to organic molecules, and each AB type block polymer chain is a polymer main chain of block A. Is a star-type copolymer bonded to the organic molecule at one end opposite to the end bonded to the block B, and the weight-average molecular weight of the star-type copolymer is 2 × 1
0 ⁴ a to 1 × 10 ^6, wherein the block A is a polymer component corresponding to the monofunctional monomer (A), a phosphono group,
Carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, -P (= O) (OH) R ¹ group, [R ¹ is-
Represents an R ² group or an —OR ² group, wherein R ² represents a hydrocarbon group], a —CONR ³ R ⁴ group, a —SO ₂ NR ³ R ⁴ group (R ³ and R ⁴ are each independently a hydrogen atom Or a hydrocarbon group] and a polymer component containing at least one polar group selected from cyclic anhydride-containing groups, and the block B is represented by the following general formula (I) An oil-based ink for an ink-jet type plate-making printing plate, comprising at least one polymer component represented by the formula:

[0018]

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In the general formula (I), X ¹ is -COO-, -O
_{CO -, - (CH 2)} x COO -, - (CH 2) x OCO-
[Where x represents an integer of 1 to 3], or -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. a ¹ and a
² may be the same or different, and each is a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-
Z ¹ or —COO—Z ¹ via a hydrocarbon group (here, Z ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted). (2) In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 50/9.
The oil-based ink for an ink-jet type plate-making printing plate of the above (1), which has a weight ratio of 9 to 50. (3) The resin particles are represented by the following general formula (II) copolymerizable with the monomer (A) together with the monofunctional monomer (A) and the dispersion stabilizing resin particles [P]. Monomer (B)
(However, the amount of the monomer (B) used is 0.1 to 15% by weight with respect to the monofunctional monomer (A)). An oil-based ink for an ink-jet type plate-making printing plate according to the above (1) or (2), which is the obtained copolymer.

[0020]

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In the general formula (II), E ¹ represents an aliphatic group having 8 or more carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0022]

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In the general formula (III), R ²¹ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. K ¹ And K ²
May be the same or different from each other, and are each -O-,
-S -, - CO -, - CO 2 -, - OCO -, - SO 2
^{-, - N (R 22)} -, - CON (R 22) -, - N
^{(R 22) CO -, -} N (R 22) SO 2 -, SO 2 N (R
²²⁾ -, - NHCO ₂ - or an -NHCONH- (wherein R ²² is as defined in the above R ^21). L ¹ And L ² May be the same or different, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following general formula (IIIa) intervening in the bond of the main chain.

[0024]

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In the above general formula (IIIa), K ³ And K ⁴
May be the same or different from each other, and the above K ¹ , K ²
Represent the same contents as, L ⁴ Is an optionally substituted carbon number 1 to
And R ²³ is the same as R ²¹ described above. m, n and p may be the same or different, and each represents an integer of 0-4. However, m + n + p = 0
Will not be. In the formula (II), U ¹ is -COO-,-
^{CONH -, - CON (E 2} ) - [wherein, E ² represents a substituent represented by the aliphatic group or the general formula (II)], -OCO -, - CONHCOO -, - CH 2 CO
O—, — (CH ₂ ) _S OCO—, wherein s is 1 to 4
It represents an integer], -O- or -C ₆ H ₄ - represents a. b
¹ and b ² may be the same or different from each other,
Each has the same meaning as a ¹ and a ² in the formula (I).

[0026]

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

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

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

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. Group hydrocarbons and their halogen-substituted products. For example, octane, isooctane, decane, isodecane, decalin, nonane,
Dodecane, isododecane, isoper E, isoper G, isoper H, isoper L, shersol 70,
Shellsol 71, AMSCO OMS, AMSCO 460 solvent and the like are used alone or in combination.

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

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

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

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

[0034]

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

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

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

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

Next, the monomer (B) containing a specific substituent represented by the general formula (II) and used in the present invention, which is mentioned as a preferred embodiment, will be further described.

[0040]

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In the general formula (II), E ¹ represents an aliphatic group having 8 or more carbon atoms or a substituent selected from the substituents represented by the following general formula (III).

[0042]

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In the general formula (III), R ²¹ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. K ₁ and K ₂
May be the same or different from each other, and are each -O-,
-S -, - CO -, - CO 2 -, - OCO -, - SO 2
^{-, - N (R 22)} -, - CON (R 22) -, - N
^{(R 22) CO -, -} N (R 22) SO 2 -, SO 2 N (R
²²⁾ -, - NHCO ₂ - or an -NHCONH- (wherein R ²² is as defined in the above R ^21). L ¹ And L ² May be the same or different, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following general formula (IIIa) intervening in the bond of the main chain.

[0044]

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In the above general formula (IIIa), K ³ And K ⁴
May be the same or different from each other, and the above K ¹ , K ²
Represent the same contents as, L ⁴ Is an optionally substituted carbon number 1 to
And R ²³ is the same as R ²¹ described above.

M, n and p are the same or different and each represents an integer of 0-4. However, m + n +
p = 0 never occurs.

In the formula (II), U ¹ is -COO-, -CON
^{H -, - CON (E 2} ) - [wherein, E ² represents a substituent represented by the aliphatic group or the general formula (III)], -OCO -, - CONHCOO -, - CH 2 CO
O—, — (CH ₂ ) _S OCO—, wherein s is 1 to 4
It represents an integer], -O- or -C ₆ H ₄ - represents a.

B ¹ and b ² may be the same or different from each other, and have the same meanings as a ¹ and a ^{2 in} the general formula (I), respectively.

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

In the general formula (II), E ¹ preferably represents an alkyl group having 10 or more carbon atoms which may be substituted or an alkenyl group having 10 or more carbon atoms.

U ¹ is -COO-, -CONH-, -CO
N (E ² )-[where E ² preferably has 1 to 3 carbon atoms
2 represents an aliphatic group (for example, an aliphatic group represents an alkyl group, an alkenyl group or an aralkyl group);
OCO -, - represents a CH ₂ OCO- or -O-.

More preferably, in formula (II), U ¹
Is -COO -, - CONH-, or -CON (E ²⁾
And b ¹ and b ² may be the same or different and represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or a methyl group, and E ¹ has the same contents as described above.

In the monomer (B) represented by the above general formula (II), when E ¹ represents an aliphatic group having 8 or more carbon atoms, specific examples thereof include a total of 10 to 32 carbon atoms. An aliphatic group (an aliphatic group may contain a substituent such as a halogen atom, a hydroxyl group, an amino group, an alkoxy group, or a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, A carbon-carbon bond may be mediated)
Esters of unsaturated carboxylic acids such as acrylic acid, α-fluoroacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid (e.g. decyl as an aliphatic group) Group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, dodecenyl group, hexadecenyl group, oleyl group, linoleyl group,
Amides of the above-mentioned unsaturated carboxylic acids (aliphatic groups are the same as those shown for esters); vinyl esters or allyl esters of higher fatty acids (for higher fatty acids, for example, lauric acid , Myristic acid, stearic acid, oleic acid, linoleic acid,
Behenic acid or the like); or vinyl ethers substituted with an aliphatic group having a total of 10 to 32 carbon atoms (the aliphatic group represents the same range as the aliphatic group of the unsaturated carboxylic acid).

The case where E ¹ in the monomer (B) represented by the general formula (II) represents a substituent represented by the general formula (III) will be described in detail.

L ¹ And L ² For further specific examples of these, these are -C (R ²⁴ ) (R ²⁵ )-[R ²⁴ , R ²⁵
Represents a hydrogen atom, an alkyl group, a halogen atom, etc.],-
(CH = CH) -, a cyclohexylene group [hereinafter, a cyclohexylene group - expressed in, "" -C ₆ H ₁₀ "- C ₆ H ₁₀
-"Includes a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group], and an arbitrary combination of atomic groups such as the general formula (IIIa). Is what is done.

Further, a bonding group in the general formula (II): -U ^1- (L ¹ −K ¹ ) _M - (L ² −K ² ) In _n -R ^21, from U ¹ R ²¹ (i.e., U ^1, L ¹ ,
K ¹ , L ² , K ² , R ²¹ ) preferably has a total number of atoms of 8 or more. Here, U ¹ represents —CON (E ² ) —, and E ² represents a substituent represented by the general formula (III), ie, — (L ¹
−K ¹ ) _M - (L ² −K ² ) When it represents an _n -R ^21], linked backbone consists of E ² are also included in the connecting backbone. Furthermore, L ¹ , L ² Is a hydrocarbon group which makes the above-mentioned general formula (IIa) intervene in the bond of the main chain, -K ³ − (L
^Four −K ⁴ ) _P -R ²³ is also included in the connecting backbone. As the number of atoms in the connecting main chain, for example, when U ¹ represents —COO— or —CONH—, an oxo group (＝ O group) and a hydrogen atom are not included in the number of atoms, and carbon atoms constituting the connecting main chain are not included. Atoms, ether-type oxygen atoms, and nitrogen atoms are included in the number of atoms. Therefore, -COO- and -CONH- are counted as 2 atoms. At the same time, when R ²¹ represents —C ₉ H ₁₉ , the number of hydrogen atoms is not included, and the number of carbon atoms is included. Therefore, in this case, it is counted as 9 atoms.

In the monomer (B) represented by the above general formula (II), when E ¹ represents a substituent represented by the above general formula (III), that is, it contains a specific polar group. In the case of a monomer, more specifically, the following compounds can be exemplified.

The following formulas (b-1) to (b-19)
Here, each symbol represents the following contents. r1: -H, -CH _3, -Cl or -CN, r2: -H or -CH ₃ l: 2 to 10 integer, p: 2 to 6 integer, q: 2 to 4 integer, m: 1 An integer from 1 to 12, n: an integer from 4 to 18,

[0059]

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[0060]

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[0061]

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The dispersing resin of the present invention comprises at least one kind of each of the monomer (A) and further the monomer (B),
Importantly, if the resin synthesized from these monomers is insoluble in a non-aqueous solvent, a desired dispersed resin can be obtained.

More specifically, the monomer (A) to be insolubilized
With the monomer (B) represented by the general formula (II) in 0.1.
It is preferably used in an amount of 1 to 10% by weight, and more preferably 0.1 to 10% by weight.
It is preferable to use 3 to 8% by weight.

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

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

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

The solution-free polymer produced by polymerizing the monomer (A) and, if necessary, the monomer (B) in a non-aqueous solvent is used to form a stable resin dispersion. The dispersion stabilizing resin [P] of the present invention has a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁴ comprising at least three polymer chains of an AB type block copolymer component bonded to an organic molecule. ^{6 is} a star copolymer.

One block (block A) bonded to the organic molecule is a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group,
(＝ O) (OH) R ¹ group (R ¹ represents a —R ² group or —OR ² group, and R ² represents a hydrocarbon group), —CONR ³ R
^Four, -SO ₂ NR ³ R ⁴ [R ³ and R ⁴ are each independently
Represents a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from cyclic acid anhydride-containing groups and / or a polymer corresponding to the monofunctional monomer (A). It is constituted by containing at least one kind of coalescence component.

The other block (block B) comprises at least one polymer component comprising a repeating unit represented by the above general formula (I).

Here, the sequence of the blocks A and B in the polymer chain is such that one end of the polymer main chain of the block A opposite to the end where the block B is bonded is bound to the organic molecule. The resin [P] is schematically represented by the following formula (V). Equation (V)

[0071]

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In the above formula (V), X represents an organic molecule, [A] represents a block A, [B] represents a block B, and [A]-[B] represents a polymer chain. Also, such A
The upper limit of the number of -B type block polymer chains contained in the organic molecule is at most 15, usually about 10.

Block A in the star type copolymer
And the weight composition ratio of each co-polymerized composition of block B is 1/50 /
99 to 50, preferably 5 to 40/95 to 60.

The specific polar group-containing polymer component contained in the block A is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the dispersion stabilizing resin [P]. It is. When no specific polar group-containing polymer component is present in the block A, the polymer component corresponding to the functional monomer (A) is preferably contained in 100 parts by weight of the dispersion stabilizing resin [P]. It is 5 to 50 parts by weight, more preferably 10 to 40 parts by weight.

The polymer component represented by the general formula (I) contained in the block B is preferably 50 to 99 parts by weight, more preferably 60 to 99 parts by weight, per 100 parts by weight of the dispersion stabilizing resin [P]. 95 parts by weight.

In the dispersion stabilizing resin [P], the predetermined abundance (that is, the abundance of the block A and the block B and the polymer component represented by the general formula (I) contained in the block B) ), The redispersion stability of the dispersed resin particles obtained by polymerizing the monofunctional monomer (A) and the monomer (B) decreases. On the other hand, if it exceeds the predetermined abundance, the average particle size of the dispersed resin particles obtained by the polymerization reaction with the monofunctional monomer (A) and the monomer (B) is increased, and the particle distribution of the particles is increased. Lowers the monodispersity.

The resin for dispersion stabilization [P] used in the present invention
May be soluble in an organic solvent, specifically, at least 5 parts by weight or more of a dispersion stabilizing resin at 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 2 × 10 ⁴ to 1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 × 10 ⁵ .

Next, block A of dispersion stabilizing resin [P]
Will be described in detail.

The block A is composed of a polymer component corresponding to the monofunctional monomer (A) and / or a polymer component containing the above-mentioned specific polar group. Monofunctional monomer (A)
Examples of the polymer component corresponding to the above include those having the same contents as described above in the insoluble monomer (A). Preferably, it is composed of the same monomer as the monofunctional monomer (A) serving as the dispersion stabilizing resin.

In a specific polar group, -P (＝ O) (OH) R
^{In one} group, R ¹ represents a —R ² group or an —OR ² group;
² represents a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group for R ^2, an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a butenyl group, a pentenyl group, A hexenyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, and the like; Xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In the specific polar groups, R ³ and R ⁴ in —CONR ³ R ⁴ group and —SO ₂ NR ³ R ⁴ group are
Each independently represents a hydrogen atom or a hydrocarbon group (having 1 to 1 carbon atoms);
0, preferably an optionally substituted hydrocarbon group having 1 to 8 carbon atoms). Specific examples of the hydrocarbon group represented by R ³ and R ⁴ are the same as the hydrocarbon group represented by R ² .

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

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

Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylic anhydride, and thiophenedicarboxylic anhydride. Dicarboxylic anhydrides include, for example, chlorine atoms, halogen atoms such as bromine atoms, alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, hydroxyl groups, cyano groups, nitro groups, alkoxycarbonyl groups (as alkoxy groups) , For example, a methoxy group, an ethoxy group, etc.).

In a more specific polar group, the amino group is represented by -N
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ and R ⁶ are
Represents a hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms. More preferably represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, the same hydrocarbon group represented by R ² are exemplified.

The hydrocarbon group of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is even more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted, a benzyl group which may be substituted, And a phenyl group which may be substituted.

The monomer corresponding to the polymer component containing the specific polar group may be any monofunctional monomer containing at least one specific polar group.
For example, it is described in “Polymer Data Handbook, Basic Edition”, edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-form)
Bromo form, α-fluoro form, α-tributylsilyl form, α
-Cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, Crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid,
-Ethyl-2-octenoic acid), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzene carboxylic acid, vinylbenzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, vinyl group or allyl group of dicarboxylic acids Examples thereof include half ester derivatives, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituents of the amide derivatives.

The following are specific examples of these compounds. However, in each of the following examples, e is-
_{H, -CH 3, -Cl, -Br} , -CN, -CH 2 COO
Represents CH ₃ , f represents —H or —CH ₃ , and n represents 2 to
Represents an integer of 10; m represents an integer of 1 to 10;
Represents an integer of from 4 to 4. X ³ is -COOH, -OP (=
_{O) (OH) 2, -SO} 3 H, -OH, -NR a R b, -C
HO or -OP (= O) (OH) _Ra is represented. Here, R _a and R _b represent an alkyl group having 1 to 4 carbon atoms. X ⁴
Represents -COOH or -OH.

[0089]

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[0090]

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[0091]

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Next, the block B of the dispersion stabilizing resin [P] is used.
The repeating unit represented by the general formula (I) constituting the formula (I) will be described in detail.

In the general formula (I), X ¹ preferably represents -COO-, -OCO- or -O-.

Y ¹ preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel 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 or a bromine atom), a cyano group, or an alkyl group having 1 to 3 carbon atoms (eg, Methyl group, ethyl group, propyl group, etc.), -COO-Z ¹ or -CH ₂ COO-Z ¹ [Z
¹ represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.)].

Specifically, Z ¹ is, in addition to a hydrogen atom, a preferred hydrocarbon atom such as an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group and a butyl group). , Heptyl group, hexyl group, octyl group, nonyl group, 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 and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1 -A 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
To 12 optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group , A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
And an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, Ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, A propioamidophenyl group, a dodecylylamidophenyl group, etc.).

In the block B of the dispersion stabilizing resin used in the present invention, other repeating units may be contained as a copolymer component together with the repeating units represented by the general formula (I). Other copolymer components include those represented by the general formula (I)
Any compound may be used as long as it is composed of a monomer copolymerizable with a monomer corresponding to the repeating unit (1).
However, it is preferable that no other monomer be contained, and it is used in an amount not exceeding 20 parts by weight in the block B at most. If the amount exceeds 20 parts by weight, the dispersibility of the dispersed resin particles deteriorates. In the block B, two or more kinds of the repeating units represented by the general formula (I) may be used in combination.

On the other hand, according to the present invention, the organic molecule formed by bonding at least three polymer chains is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. Examples include the trivalent hydrocarbon residues described below.

[0099]

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[Here, r ^{3 to} r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, at least one of r ³ and r ⁴
And at least one of r ⁵ and r ⁶ are each linked to a polymer chain. ]

These organic residues have a constitution of a single compound or an arbitrary combination thereof. In the case of a combination, -O-, -S-, -N (r ⁹ )-, -COO-,-
^{CON (r 9) -, -} SO 2 -, - SO 2 N (r 9) - ( wherein r ⁹ represents a hydrogen atom or a hydrocarbon group), - NH
COO-, -NHCONH-, oxygen atom, sulfur atom,
Hetero atom-containing heterocycle of nitrogen atom (for example, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring,
And a combination of bonding units such as a pyrrole ring and a piperazine ring.

Examples of other organic molecules that bind the polymer chains include those composed of a combination of the following and the above-mentioned binding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0103]

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The star-type copolymer [P] of the present invention can be synthesized by using a conventionally known method for synthesizing a star-type monomer having a polar group and having a polymerizable double bond. Can be. For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morto
n, TE Helminiak et al "J. Polym. Sci." 57, 471
(1962), B. Gordon III, M, Blumenthal, JE Loftus
et al "Polym. Bull." 11,349 (1984), RB Bates, WA
It can be synthesized according to the method described in Beavers et al "J. Org. Chem." 44, 3800 (1979).

However, when this reaction is used, the “specific polar group” of the present invention is used as a protected functional group, polymerized, and then the protective group is eliminated. The protection of the specific polar group of the present invention by the protective group and the elimination of the protective group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references. Further, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977), TW Green "Pr
otective Groups in Organic Synthesis "(John Wiley &
Sons, 1981), JFW McOmic "Protective Groups
in Organic Chemistry "(Plenum Press, 1973) and the like.

As another method, a monomer having a specific functional group of the present invention which is not protected is used, and a compound containing a disiocarbament group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu “Polymer”
37, 248 (1988), Shunichi Himori, Ryuichi Otsu "polym. Rep. Ja
p. "37, 3508 (1988), JP-A-64-11, JP-A-64-26619, Nobuyuki Higashi, etc." Polymer Preprin
ts, Japan "36 (6), 1511 (1987), M. Niwa, N. Higash
i et al "J. Macromol. Sci. Cem." A24 (5), 567 (198
It can be synthesized according to the synthesis method described in 7).

In order to produce the dispersed resin particles (latex particles) used in the present invention, generally, the dispersion stabilizing resin [P], the monofunctional monomer (A) and the monomer (A) are used. B) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution containing the dispersion stabilizing resin [P], the monomer (A) and the monomer (B), In the dissolved solution, the monomer (A)
Further, a method in which the monomer (B) is added dropwise together with the polymerization initiator, the polymerization is carried out in a solution containing the entire amount of the dispersion stabilizing resin [P] and the monomer (A) and a part of the monomer (B). A method in which the remaining monomer (A) and the monomer (B) are optionally added together with the initiator, or the dispersion stabilizing resin [P], the monomer (A) and the monomer There is a method in which the mixed solution of (B) is arbitrarily added together with the polymerization initiator, and any method can be used for the production.

The total amount of the monomers (A) and (B) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The soluble resin as the dispersion stabilizing resin [P] is used in an amount of 1 to 100 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total monomers used above. The amount of the polymerization initiator is suitably from 0.1 to 5% by weight of the total monomers. The polymerization temperature is about 50 to 180 ° C., preferably 60 to 12 ° C.
0 ° C. The reaction time is preferably 1 to 15 hours.

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

As described above, the non-aqueous dispersed resin particles produced according to the present invention exist as fine particles having a uniform particle size distribution. Its average particle size is 0.08-0.8
μm, and preferably 0.1 to 0.5 μm. The particle size can be determined using CAPA-500 (trade name, manufactured by Horiba, Ltd.) or the like. At the same time, it shows extremely stable dispersibility, and especially in a recording apparatus, has good dispersibility even when used repeatedly for a long time, and is easy to re-disperse. Not at all.

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

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

The remarkable performance-improving effect of the present invention is attributable to the star-type copolymer [P] comprising a specific block used together with the insolubilizing monomer (A) and the monomer (B) used together. It depends on.

That is, the dispersion stabilizing resin of the present invention [P]
Is a block B composed of a linear aliphatic group-containing polymer component having a high affinity for the non-aqueous solvent, and a monomer (A) having a low affinity for the non-aqueous solvent and being insolubilized. It is a star-type copolymer in which at least three or more polymer chains of an AB type block in which a block A composed of a polymer component having an affinity is bonded to at least three or more organic molecules. And Thereby, the block A portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the block B portion having a high affinity for the non-aqueous dispersion medium is sufficiently adsorbed to the solvent. 3 or more polymer chains that are solvated with water and have a sufficient three-dimensional repulsion effect (so-called tail adsorption), so that the adsorption effect and the three-dimensional repulsion effect can be sufficiently efficiently exhibited. It is presumed that the effects of the present invention were exhibited.

On the other hand, in the conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, the component serving as the adsorbed portion is constituted by a component that solvates. Adhesion to the dispersed resin particles is not sufficient because they are randomly bonded in the polymer chain, and furthermore, the adsorption pattern becomes loop-shaped, which hinders the steric repulsion effect, and the dispersion stability is sufficient. Was not.

Further, together with the polymer (A) which is polymerized and insolubilized, the monomer (B) copolymerizable with the monomer (A) is added in a small amount (0%) to the monomer (A). .1 to 10
% By weight), and the dispersed resin particles of the present invention obtained by polymerization and granulation in the same time are insolubilized and dispersed at the particle interface of the resin.
The soluble component contained in the monomer (B) is present, the surface of the particles is improved in some way, the affinity with the dispersion medium is improved, the solvation with the dispersion medium is further enhanced, and the resin particles are improved. It is considered that aggregation between them is prevented.

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

As described above, when the dispersion stabilizing resin [P] of the present invention is used, the dispersion stability is improved, and when the oil-based ink is repeatedly used for a long time, the oil-based ink is concentrated in the ink. The concerns that caused the problem have been improved.

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

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

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

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

These pigments and dyes may be used alone or in appropriate combination, but may be contained in an amount of 0.01 to 5% by weight based on the whole ink. desirable.

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

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

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

[0127] The particles can be imparted with an electric detecting property by appropriately utilizing a technique of a wet type electrophotographic developer. Specifically, the above-mentioned “Recent development and practical use of electrophotographic development systems and toner materials”, pp. 139-148,
The Society of Electrophotography, "Basics and Application of Electrophotographic Technology" 497-
505 (Corona Co., 1988), Yuji Harasaki "Electrophotography" 16 (No. 2), page 44 (1977), and the like, using an electric test material and other additives.

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

The charge 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. That is, if the electric resistance of the ink from which the dispersed particles are removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, it is necessary to control the amount of each additive within this limit. It is.

The water-resistant support having a lithographically printable hydrophilic surface used in the present invention may be any as long as it provides a hydrophilic surface suitable for lithographic printing. The body can be used as is.

Preferably, the surface of the image receiving layer for receiving the ink image has a contact angle with water, preferably 5 degrees or less,
More preferably, it has a hydrophilic surface at 0 °, and a printed matter free from ink stains on non-image areas is obtained as offset printing.

The smoothness of the surface of the image receiving layer is preferably 50 (sec / 10 cc) or more, more preferably 80 (sec / 10 cc) or more in terms of Beck smoothness.

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

When the Beck smoothness is 50 or more, the loss or blurring of the formed ink image due to the size of the unevenness of the image receiving layer is suppressed.

As a preferred embodiment, a water-resistant substrate is
A water-resistant support provided with an image-receiving layer having a lithographically printable hydrophilic surface (also referred to as a lithographic printing original plate) is exemplified.

The water-resistant substrate has a thickness of 80 to 200.
Paper, plastic film or metal film-laminated paper or plastic film which has been subjected to a water-proof treatment of μm, and the like can be used.

The image-receiving layer on the hydrophilic surface provided on the water-resistant support is a hydrophilic layer having an inorganic pigment and a binder, and the thickness of the image-receiving layer is suitably in the range of 5 to 50 μm. It is.

As the inorganic pigment used in the hydrophilic image receiving layer, clay, kaolin, talc, silica, calcium carbonate, zinc oxide, aluminum oxide, barium sulfate and the like can be used. As the binder, hydrophilic binders such as polyvinyl alcohol, starch, carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, polyacrylate, polyvinylpyrrolidone, and polymethylether / maleic anhydride copolymer can be used. . If necessary, a melamine formalin resin, a urea formalin resin, and other crosslinking agents are added to impart water resistance.

Next, a method of forming an image on the lithographic printing plate precursor (hereinafter also referred to as “master”) will be described. FIG. 1 shows an example of an apparatus system for performing such a method.

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

As shown in FIG. 1, first, pattern information of an image (figure or text) to be formed on the master 2 is transmitted from an information source such as a computer 3 through a transmission means such as a bus 4 to an oil-based ink. Is supplied to the ink jet recording apparatus 1 that uses. The ink jet recording head 10 of the recording apparatus 1 stores oil-based ink therein, and when the master 2 passes through the recording apparatus 1, ejects minute droplets of the ink to the master 2 according to the information. Thereby, ink adheres to the master 2 in the pattern.

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

FIGS. 2 and 3 show examples of the configuration of an ink jet recording apparatus as in the apparatus system of FIG. 2 and 3, members common to FIG. 1 are denoted by common reference numerals.

FIG. 2 is a schematic structural view showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

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

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

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

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

[0149]

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

Synthesis Example 1 of Dispersion Stabilizing Resin [P] Resin [P-1] 50 g of methyl methacrylate, 50 g of methyl acrylate
g, a mixture of 7.8 g of an initiator [I-1] having the following structure and 100 g of tetrahydrofuran at a temperature of 50 under a nitrogen stream.
Warmed to ° C. The solution was added to the solution with a 400 W high-pressure mercury lamp.
Light irradiation photopolymerization was performed for 8 hours through a glass filter from a distance of cm. The polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried.

[0151]

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Next, a mixed solution of 30 g of the above polymer, 70 g of stearyl methacrylate and 100 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream.
Next, after performing light irradiation for 16 hours in the same manner as above,
The obtained reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried. The yield was 80 g and the weight average molecular weight [Mw: Mw was determined by the GPC method in terms of polystyrene (GPC: size exclusion chromatography). Value by graphy)
Gave a polymer [P-1] of 6 × 10 ^{4 having} the following structure.

[0153]

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Synthesis Examples 2 to 14 of Dispersion Stabilizing Resin [P]:
Resins [P-2] to [P-14] In Synthesis Example 1 of dispersion stabilizing resin, initiator [I-1]
In place of the initiator [I-2 to 14] described in Table A below.
A polymer was synthesized in the same manner as in Synthesis Example 1 except that 0.011 mol was used. The Mw of each polymer obtained was 4 × 10 ⁴
６6 × 10 ⁴ .

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

[Table 3]

[0158]

[Table 4]

Synthesis Examples 15 and 2 of Dispersion Stabilizing Resin [P]
8: Resins [P-15] to [P-28] Each monomer corresponding to the polymer component of block A shown in Table B below, starting at 0.01 mol based on all monomers used. A mixture of the agent [I-7] and 100 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. This solution was irradiated with light for 12 hours in the same manner as in Synthesis Example 1 to perform a polymerization reaction.

Next, each of the obtained polymers was mixed with a predetermined amount (x: as solid content) shown in Table B and each monomer corresponding to the polymer component of block B shown in Table B below. Using a predetermined amount shown in Table-B (y: as solid content) and adding a mixed solution of tetrahydrofuran so that the concentration of all compounds becomes 60% by weight, the mixture was again heated to 55 ° C. under a nitrogen stream.
Was heated. Next, after performing light irradiation for 16 hours in the same manner as described above, the obtained reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried. Yield 60 ~
80 g of each polymer having Mw of 3 × 10 ^{4 to} 6 × 10 ⁴ was obtained.

[0161]

[Table 5]

[0162]

[Table 6]

[0163]

[Table 7]

[0164]

[Table 8]

[Production Example of Resin Particle 1: Resin Particle D-1]
16 g of dispersion stabilizing resin [P-17], vinyl acetate 10
A mixed solution of 0 g and 384 g of Isopar H was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. As a polymerization initiator, 1.0 g of 2,2'-azobis (isovaleronitrile) (abbreviated as AIVN) was added and reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Next, 0.8 g of an initiator was added, and 2
After reacting for an hour, 0.5 g of an initiator was further added and reacted for 3 hours. Next, raise the temperature to 100 ° C.
After stirring for an hour, unreacted vinyl acetate was distilled off. 20 after cooling
After passing through a 0-mesh nylon cloth, the resulting white dispersion was a latex having a conversion of 98% and an average particle size of 0.22 μm. The particle size is CAPA-500 (manufactured by Horiba, Ltd.)
Was measured.

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour), and the sedimented resin particles were collected and dried, and the weight average molecular weight of the resin particles was measured. Mw) and the glass transition point (Tg) were measured.
Mw was 2 × 10 ⁵ (polystyrene conversion value by GPC, the same applies hereinafter), and Tg was 39 ° C.

[Production Example 2 of Resin Particles: Resin Particles D-2]
14 g of dispersion stabilizing resin [P-18], vinyl acetate 10
A mixed solution of 0 g, 4.0 g of octadecyl methacrylate and 385 g of Isopar H was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 2,2 'as a polymerization initiator
-Azobis (isovaleronitrile) (abbreviated as A.I.V.
N. ) Was added and reacted for 4 hours. In addition,
2'-azobis (isobutyronitrile) (abbreviated as A.I.
B. N. ) Was added, and the mixture was heated to a temperature of 80 ° C. and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. Thereafter, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour to remove unreacted vinyl acetate.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 98% and an average particle size of 0.20 μm. Mw of resin particles is 2.5 × 10 ⁵ ,
Tg was 38 ° C.

[Production Examples 3-9 of Resin Particles: Resin Particles D-
3-9] In Resin Particle Production Example 2, in place of 14 g of the dispersion stabilizing resin [P-18] and 4.0 g of octadecyl methacrylate, the dispersion stabilizing resin [P] and the monomer (B) shown in Table 1 below were used. ) Except that 0.01 mole was used
Resin particles D-3 of the present invention in exactly the same manner as in the above Production Examples
D-9 was produced.

The polymerization rate of each of the obtained resin particles is 95 to 10
At 0%, the average particle size was in the range of 0.18 to 0.25 µm and the monodispersity was good. Mw of each resin particle is 8
× 10 ^{4 to} 2 × 10 ⁵ and Tg were in the range of 36 to 39 ° C.

[0170]

[Table 9]

[Production Example 10 of Resin Particles: Resin Particles D-1]
0] 20 g of dispersion stabilizing resin [P-1] and Isopar H
Was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 2. 40 g of methyl methacrylate, 60 g of methyl acrylate, octadecyl acrylate
5 g, 200 g of Isopar G and A. I. V. N.
Was added dropwise over 2 hours, followed by stirring for 2 hours. Further, A.I. I. V. N. Add 0.5g and add 3
Stirred for hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was obtained at a conversion of 99% and an average particle size of 0.1%.
It was a 23 μm latex. The Mw of each resin particle was 2 × 10 ⁵ , and the Tg was 34 ° C.

[Production Examples 11 to 21 of Resin Particles: Resin Particles D-11 to 21] The monomers (A) (namely, methyl methacrylate and methyl acrylate) and monomer B used in Production Example 10 of the resin particles were used. (Ie, octadecyl acrylate), and the compounds shown in Table 2 below were used instead of the dispersion stabilizing resin [P-1], respectively.
Resin particles D- of the present invention in exactly the same manner as in Production Example 10 above.
11 to D-21 were produced. The polymerization rate of each of the obtained resin particles is 92 to 99%, and the average particle size is 0.15 to 0.25.
The monodispersity was good in the range of μm. Mw of each resin particle was in the range of 8 × 10 ⁴ to 2 × 10 ⁵ .

[0173]

[Table 10]

[Production Example 22 of Resin Particles: D-22 (Comparative Example A)] In Production Example 1 of resin particles, instead of 16 g of the dispersion stabilizing resin [P-17], a resin [RP-
1] Except for using 16 g, the polymerization rate was 97% and the average particle size was 0.35 μm in the same manner as in Production Example 1 of the resin particles.
A white dispersion as latex particles of m was obtained. Comparative dispersion stabilizing resin [RP-1]

[0175]

Embedded image

[Production Example 23 of Resin Particles: D-23 (Comparative Example B)] In Production Example 1 of resin particles, instead of 16 g of the dispersion stabilizing resin [P-17], a resin [RP-
2] Except for using 18 g, the polymerization rate was 90% and the average particle size was 0.30 in the same manner as in Production Example 1 of the resin particles.
A white dispersion as μm latex particles was obtained. Comparative dispersion stabilizing resin [RP-2]

[0177]

Embedded image

Example 1 <Preparation of a lithographic printing plate precursor> A composition 1 having the following contents was mixed with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.).
, And dispersed for 60 minutes, and then the glass beads are filtered off.
A dispersion was obtained.

(Composition 1) Gelatin 20 g Silica: Sylysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 8 g Colloidal silica 20% solution Snowtec C (manufactured by Nissan Chemical Industries, Ltd.) 38 g Fluoroalkyl ester: FC430 (3M) 0.8 g Hardening compound 0.24 g [CH ₂ ＣＨCHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH ＣＨCH ₂ ] Water 54 g

A support of ELP-1 type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing plate for light printing was used, and the above composition was coated on the support using a wire bar. The resultant was dried at 100 ° C. for 10 minutes to form an image receiving layer having a coating amount of 18 g / m ² , thereby obtaining a lithographic printing original plate. The Beck smoothness of the surface of the image receiving layer of this master was 250 (sec / 10 cc), and the contact angle with water on the surface was 0.
Degree.

<Preparation of Oil Ink (IK-1)> Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 9)
(5/5 weight ratio), 10 g of alkali blue, and 30 g of Shellsol 71 were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of alkali blue. Was.

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

Using the lithographic printing original plate prepared as described above, a servoproter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing an output from a personal computer, was modified, and the ink ejection head shown in FIG. , 1.5
Printing was performed on the lithographic printing original plate placed on the counter electrode spaced at a distance of mm using the oil-based ink (IK-1) described above. Subsequently, using an RICOH FUSER model 592 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 70 ° C. and heated for 20 seconds to sufficiently fix the image area.

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

This printing plate was used as immersion water for SLM-O
Using a solution obtained by diluting D (manufactured by Mitsubishi Paper Mills) eight times with water, printing was performed with black ink for offset printing using Oliver 94 type (manufactured by Sakurai Seisakusho) as a printing material.

As a result, 2,000 or more printed matters were obtained in a clear image with no background smear.

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

Further, when the plate-making printing plate was actually printed under these conditions, 2,000 or more printed matters having clear images without background smear were obtained.

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

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

<Comparative oil-based ink IKR-1> In the oil-based ink IK-1, instead of the resin particles (D-1),
50 g of resin particles for comparison (D-22) (as solid content)
Was prepared in the same manner as the ink IK-1 except that the ink was used.

[Comparative Example B] In Example 1, instead of the oil-based ink IK-1, the following oil-based ink IKR-
Except for using No. 2, the same procedure as in Example 1 was performed.

<Comparative oil-based ink IKR-2> In the oil-based ink IK-1, instead of the resin particles (D-1),
50 g of resin particles for comparison (D-23) (as solid content)
Was prepared in the same manner as the ink IK-1 except that the ink was used.

The lithographic printing plates obtained using the oil-based inks of Comparative Examples A and B described above were printed first, and as in Example 1, the printed matter of clear image without stain was 2,000. More than one sheet was obtained. However, in the ink ejection test, the ink ejection became unstable after about 200 hours in Comparative Example A and about 350 hours in Comparative Example B. In the ink of the comparative example stored for 6 months, a coagulated sediment was deposited and did not redisperse even after shaking.

Further, for Comparative Examples A and B,
When a forced test of the ink re-dispersibility was performed under the same conditions as in Example 1, deposits remained in the slits of the ejection head portion.

As described above, the oil-based ink of the present invention has good ink ejection stability, forms a clear image with no background smear, and can be used as a printing plate even after a long period of continuous plate making. However, it shows high printing durability.

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

(Composition 2) Gelatin 20 g Silica: Sylysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 8 g Alumina sol 200 10% solution (manufactured by Nissan Chemical Industries, Ltd.) 50.3 g Fluorinated alkyl ester: FC430 (3M Company) 0.8 g Hardening compound 0.30 g [CH ₂ ＣＨCHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH ＣＨCH ₂ ] Water 54 g

A support of ELP-II type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing was used, and the above composition was coated on the support using a wire bar. The resultant was dried at 100 ° C. for 10 minutes to form an image receiving layer having a coating amount of 22 g / m ² , thereby obtaining a lithographic printing plate precursor. The Beck smoothness of the surface of the image receiving layer of this master was 200 (sec / 10 cc), and the contact angle with water on the surface was 0.
Degree.

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

Resin Particles of Production Example 2 of Resin Particles (D-2)
50g (as solid content) Nigrosine dispersion 35 above
g, 70 g of isostearyl alcohol and 0.60 g of [octadecylvinyl ether-hemo maleic acid dodecylamide] copolymer were diluted to 1 liter of Isopar G to prepare a black oil-based ink.

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

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 4,000 sheets or more.

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

Examples 3 to 8 Plate making and printing were carried out in the same manner as in Example 1, except that the oil ink shown in Table 3 below was used in place of the oil ink (IK-1). The oil-based ink used was prepared in the same manner as in the oil-based ink (IK-1) except that 45 g (as a solid content) of the resin particles of Table 3 below were used instead of the resin particles (D-1).

[0206]

[Table 11]

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 2,000 or more.

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

Examples 9 to 22 Plate making and printing were performed in the same manner as in Example 1 except that the oil-based ink (IK-2) was replaced with the oil-based ink shown in Table 4 below. The oil-based ink used was prepared in the same manner as in the oil-based ink (IK-2) except that 45 g (as a solid content) of resin particles shown in Table 4 below were used instead of the resin particles (D-2).

[0210]

[Table 12]

[0211] The obtained printed matter was of a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 2.
The printing durability was as good as 4,000 sheets or more.

In the same manner as in Example 1, the ink IK test was performed in the 800-hour ink ejection test and the redispersibility compulsory test.
The performance was exactly the same as -2, which was excellent.

Example 23 Plate making and printing were performed in the same manner as in Example 2 except that the oil ink (IK-23) having the following content was used instead of the oil ink (IK-2).

<Oil-based Ink IK-23> A mixture of 500 g of the white dispersion (D-21) obtained in Production Example 22 of resin particles and 7.5 g of Sumicaron Black was heated at a temperature of 100 g.
C. and heated and stirred for 6 hours. 200 after cooling to room temperature
The residual dye was removed through a mesh nylon cloth to obtain a black resin dispersion having an average particle size of 0.22 μm.

250 g of the above black resin dispersion, 0.12 g of a charge control material (CD-3) having the following structure, FOC-160
0 (hexadecyl alcohol manufactured by Nissan Chemical Co., Ltd.) 40
g to 1 liter of Isopar G,
A black oil-based ink was prepared.

[0216]

Embedded image

The obtained printed matter has a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 4,000 sheets or more.

Also, in the same manner as in Example 1, 800
In the time ink ejection test and the redispersibility compulsory test, the performance was completely equivalent to that of the ink IK-1 and was excellent.

Example 24 <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 smoothness of the under layer surface was 150 (sec / 10 cc), and the smoothness was adjusted to 1500 (sec / 10 cc) by calendering.

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

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

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

<Preparation of lithographic printing plate precursor> Composition 3 having the following contents was put into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) together with glass beads, and dispersed for 80 minutes. I got

(Composition 3) Silica: Silicia 445 (manufactured by Fuji Silysia Chemical Ltd.) 40 g Colloidal silica 20% solution Snowtec CR503 (manufactured by Nissan Chemical Industries, Ltd.) 200 g Clay 50% dispersion 40 g polyvinyl alcohol: PVA-11710% solution (manufactured by Kuraray Co., Ltd.) 120 g Melamine resin 2.0 g Ammonium chloride 0.2 g Water 50 g

This dispersion was coated on the above-mentioned water-resistant support using a wire bar, dried and dried to obtain a coating amount of 20 g /
to form an image-receiving layer of m ^2, and to obtain a lithographic printing plate precursor. The Beck smoothness of the image receiving layer surface of this master was 150 (seconds / 10
cc), the contact angle of the surface with water was 0 degree.

This printing original plate was prepared in the same manner as in Example 1.
Plate making was performed, and offset printing was performed as a printing plate. However, instead of the oil-based ink (IK-1) used in Example 1, the following oil-based ink (IK-24) was used.

<Oil-based ink IK-24> White dispersion (L-20) 5 obtained in Production Example 20 of latex particle particles
00g and 7.5 g of Sumikaron Black
The mixture was heated to a temperature of 100 ° C. and stirred for 6 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, thereby obtaining a black resin dispersion having an average particle size of 0.20 μm.

250 g of the above black resin dispersion, 0.10 g of the charge control material (CD-3) having the above structure, FOC-160
0 (Nissan Chemical Co., Ltd., hexadecyl alcohol) 50
g to 1 liter of Isopar G,
A black oil-based ink was prepared.

[0229] The obtained printed matter has clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1.
The printing durability was as good as 3,000 sheets or more.

In the same manner as in Example 1, in the ink ejection test for 800 hours and the forced redispersibility test, the ink IK
The performance was equal to or higher than -1 and was good.

[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 (3)

[Claims] At least resin particles are dispersed in a non-aqueous carrier liquid having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5 on a water-resistant support having a lithographically printable hydrophilic surface. An oil-based ink for a plate-making printing plate for ink-jet printing, in which the oil-based ink is ejected in the form of droplets from a nozzle to form an image by an ink-jet method to form a lithographic printing plate, wherein the dispersed resin particles are soluble in the non-aqueous solvent. A mixture containing at least one monofunctional monomer (A) which is soluble and becomes insoluble by polymerization and at least one dispersion stabilizing resin [P] is obtained by polymerization reaction. Wherein the dispersion stabilizing resin [P] comprises a block A and a block B.
At least three of the AB type block polymer chains composed of the following are bonded to an organic molecule, and each AB type block polymer chain has a terminal bonded to the block B of the polymer main chain of the block A. Is a star-type copolymer bonded to the organic molecule at one end opposite to the above, and the weight-average molecular weight of the star-type copolymer is 2 × 10 ⁴ to 1 × 10 ⁶ , and the block A Represents a polymer component corresponding to the monofunctional monomer (A), a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, —P (（O) (OH) R ¹
A group [R ¹ represents a —R ² group or an —OR ² group, and R ² represents a hydrocarbon group], a —CONR ³ R ⁴ group, and a —SO ₂ NR ³ R ⁴
At least one polymer component containing at least one polar group selected from a group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group] and a cyclic anhydride-containing group. An oil-based ink for an ink-jet type plate-making printing plate, wherein the block B contains at least one polymer component represented by the following general formula (I). Embedded image In the general formula (I), X ¹ is -COO-, -OCO-,-
(CH ₂ ) _x COO-,-(CH ₂ ) _x OCO- [where x
Represents an integer of 1 to 3], or represents -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. a ¹ and a ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-Z ¹ , or —COO-Z ¹ via a hydrocarbon group (here, Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 2. In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 5.
2. The oil-based ink for an ink-jet type plate-making printing plate according to claim 1, which has a weight ratio of 0/99 to 50. 3. A resin represented by the following general formula (II), which is copolymerizable with the monomer (A) together with the monofunctional monomer (A) and the dispersion-stabilizing resin particles [P]. At least one of the monomers (B) to be used (however, the amount of the monomer (B) used is 0.1 to 15% by weight based on the monofunctional monomer (A)).
The oil-based ink for an ink-jet type plate-making printing plate according to claim 1 or 2, which is a copolymer obtained by copolymerizing and polymerizing and granulating. Embedded image In the general formula (II), E ¹ is an aliphatic group having 8 or more carbon atoms;
Alternatively, it represents a substituent selected from the substituents represented by the following general formula (III). Embedded image In the above general formula (III), R ²¹ is a hydrogen atom or a carbon atom 1
To 18 aliphatic groups. K ¹ And K ² May be the same or different from each other, and are each -O-, -S-, -C
_{O -, - CO 2 -,} - OCO -, - SO 2 -, - N (R
^{22) -, - CON (R} 22) -, - N (R 22) CO -, -
_{^{N (R 22) SO 2 -}} , SO 2 N (R 22) -, - NHCO
₂ - or an -NHCONH- (wherein R ²² is as defined in the above R ^21). L ¹ And L ² May be the same or different, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following general formula (IIIa) intervening in the bond of the main chain. Embedded image In the above general formula (IIIa), K ³ And K ⁴ May be the same or different from each other, and the above K ¹ , K ² Represent the same contents as, L ⁴ Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ²³ has the same contents as R ²¹ described above. m, n
And p may be the same or different, and each represents an integer of 0 to 4. However, there is no possibility that m + n + p = 0. In the formula (II), U ¹ represents —COO—, —CONH—,
-CON (E ² )-[where E ² represents an aliphatic group or a substituent represented by the general formula (II)], -OC
O -, - CONHCOO -, - CH 2 COO -, - (C
H _{2) S} OCO-, [wherein, s represents an integer of 1 to 4], -O- or -C ₆ H ₄ - represents a. b ¹ and b
² may be the same or different, and have the same meaning as a ¹ and a ² in the formula (I), respectively.