JP2000238452A - Lithographic printing block material, lithographic printing block using the material and manufactured of printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a lithographic printing block material developed by a damping water or an ink on a printer and provided with superior sensitivity, resistance to printing and resistance to chemicals and also provide a manufacturing method for a printer matter using the material. SOLUTION: An image recording layer containing micro-gels having a group to be decomposed by light or heat on their surfaces and an infrared ray absorbent on a hydrophilic substrate. An image forming recording layer containing thermoplastic polymer particles fusion bonded on the substrate by heat energy, a compound generating the chemical reaction under the presence of a compound absorbing light energy of wavelength longer than 500 nm and an infrared ray absorbent is formed on an aqueous substrate. Light or heat is imparted into the image shape by using the lithographic printing block material, and then the image recording layer on a non-image section is eluted by a development solution composed substantially of water in the manufacture of the lithographic printing block.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate having a layer which can be developed with water or a fountain solution on a printing machine by applying light or heat energy imagewise on a hydrophilic support. The present invention relates to a plate material and a method for producing a lithographic printing plate and a printed matter using the material.

[0002]

2. Description of the Related Art A lithographic printing plate material capable of obtaining a lithographic printing plate by a development process using fresh water after image exposure or a simple developing process of developing with a fountain solution on a printing machine and a lithographic printing plate manufacturing technology using the same. Are known.

As this kind of technology, Japanese Patent Application Laid-Open No. Hei 8-3141 is known.
In JP-A-57-57, an image-forming element having a photosensitive layer containing thermoplastic polymer particles which are fused by heat and a photosensitive diazo compound on a hydrophilic support is image-exposed, and the photosensitive layer in the non-exposed area is exposed. A method for preparing a lithographic printing plate which is subjected to heat treatment after removal with fresh water is disclosed. However, this technique has the problem that the imaging element is not substantially sensitive to infrared lasers.

[0004] Japanese Patent Application Laid-Open No. 9-12387 discloses thermoplastic polymer particles dispersed on a hydrophilic support and dispersed by a thermal energy, and a compound capable of converting light into heat. A method is disclosed in which an image forming element having an image recording layer to be image-exposed is exposed to light and developed on a printing press with a dampening solution or ink to form a lithographic printing plate. However, this technique has problems in printing durability and chemical resistance.

JP-A-9-127683 discloses a lithographic printing plate in which a self-water-dispersible thermoplastic resin particle layer which can be made lipophilic by heat is formed on the surface of a hydrophilic substrate. A method is disclosed in which energy is applied to make the particles lipophilic to form a heat-sealed image, and the heat-sealed image is filled with ink using immersion water, transferred to a recording medium, and printed. However, this technique has problems in printing durability and chemical resistance.

The present inventors have proposed a photosensitive composition containing a photosensitive microgel chemically modified with diazo as a photosensitive composition applicable to a negative photosensitive layer or the like of a photosensitive lithographic printing plate (Japanese Patent Application Laid-Open No. H10-163,837). Hei 4-317351). According to this technique, development with water is possible, but there is a problem that the photosensitive layer according to this technique has substantially no sensitivity to an infrared laser.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a lithographic printing plate material which is capable of simple development as described above, is excellent in environmental suitability and workability. It is an object of the present invention to provide a lithographic printing plate material excellent in sensitivity, printing strength and chemical resistance, and a method for producing a lithographic printing plate and printed matter using the material.

[0008]

The constitution of the present invention for solving the above-mentioned problems is as follows.

(1) An image recording layer containing a microgel having a group which is decomposed by at least one of light and heat energies on its surface and an infrared light absorbing agent is formed on a hydrophilic support. And planographic printing plate material.

(2) On a hydrophilic support, an image recording layer containing a microgel having on its surface a polymer containing a group decomposable by the energy of at least one of light and heat and an image recording layer containing an infrared light absorbing agent are formed. A lithographic printing plate material characterized in that:

(3) Thermoplastic polymer particles fused on a hydrophilic support by thermal energy, a compound that induces a chemical reaction in the presence of a compound that absorbs light energy having a wavelength longer than 500 nm, and infrared light A lithographic printing plate material comprising an image recording layer containing an absorbent.

(4) Using the lithographic printing plate material as described in (1) to (3) above, at least one of light and heat energy is applied in the form of an image, and then a developer substantially consisting of water is used. A method for producing a lithographic printing plate, comprising eluting an image recording layer corresponding to a non-image portion.

(5) Production of printed matter characterized by producing a printed matter by using the lithographic printing plate material described in the above (1) to (3) by any of the following procedures (a) and (b). Method.

(A) Applying at least one of light and heat energy to the image recording layer of the lithographic printing plate material in an image form, placing the lithographic printing plate material on a printing cylinder of a printing machine, Alternatively, ink is supplied to the image recording layer of the lithographic printing plate material to perform printing.

(B) placing the lithographic printing plate material on a printing cylinder of a printing machine, applying at least one of energy of light and heat to the image recording layer of the lithographic printing plate material in an image form, Alternatively, ink is supplied to the image recording layer of the lithographic printing plate material to perform printing.

The inventor of the present invention has proposed a method for producing a photosensitive microgel or anionic microgel chemically modified with diazo having a photosensitive layer having a photosensitive microgel in which the counter ion is an onium salt or an iron-arene complex, A photosensitive lithographic printing plate having excellent printing durability and chemical resistance was proposed (Japanese Patent Application No. 4-317351). Claim 1 or 2
Is based on the finding that image exposure with infrared light is possible by using an infrared light absorber together with the microgel.

The invention according to claim 3 is disclosed in Japanese Patent Application Laid-Open No. 8-314.
It is an unexpected effect that the use of an infrared light absorber in combination with the image forming element described in JP-A-157-157 makes it possible to form an image with infrared light, and that the printing durability and chemical resistance are remarkably improved. Met.

Hereinafter, the present invention will be described in detail.

According to one embodiment, the hydrophilic support of the lithographic printing plate material of the present invention may be anodized aluminum. Particularly preferred hydrophilic supports are electrochemically granulated and anodized aluminum supports. The anodized aluminum support may be treated to improve the hydrophilic property of its surface by the method described in JP-A-9-12387. For example, the aluminum support may be silicate treated by treating the surface of the aluminum support with a sodium silicate solution at an elevated temperature, such as 95 ° C. Alternatively, a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution which may further contain inorganic fluoride. Further, the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be performed at room temperature or about 30
It can also be carried out at slightly elevated temperatures of 〜50 ° C. A further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution. It has also been demonstrated that one or more of these post-treatments can be performed alone in combination.

According to another embodiment of the hydrophilic support of the lithographic printing plate material according to the invention, the hydrophilic support comprises a flexible support provided with a cross-linked hydrophilic layer, such as paper or plastic film. Comprising. Particularly suitable cross-linked hydrophilic layers are obtained from hydrophilic binders cross-linked with a cross-linking agent such as, for example, formaldehyde, glyoxal, polyisocyanate or hydrolyzed tetra-alkyl orthosilicate. . The latter is particularly preferred.

As the hydrophilic binder, hydrophilic (co) polymers such as vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide,
Homopolymers and copolymers of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride / vinyl methyl ether copolymer can be used. The (co) polymer or (co) polymer mixture used preferably has a hydrophilicity of at least 60.
By weight, preferably equal to or higher than the hydrophilicity of the hydrolyzed polyvinyl acetate to the extent of 80% by weight.

The amount of the crosslinking agent, especially the tetraalkyl orthosilicate, is at least 0.2 part by weight, preferably between 0.5 and 5 parts by weight, more preferably 1 part by weight, per part by weight of hydrophilic binder. 0.0 parts by weight to 3 parts by weight.

The crosslinked hydrophilic layer in the hydrophilic support used as the hydrophilic support of the lithographic printing plate material according to the invention preferably also contains substances which increase the mechanical strength and the porosity of the layer. . Colloidal silica can be used for this purpose. The colloidal silica used may be in the form of a commercially available water-dispersion of colloidal silica having an average particle size of, for example, up to 40 nm, for example 20 nm. In addition, inert particles of a size larger than colloidal silica, such as those described in Colloid a
nd Interface Sci. , Vol. 26,
1968, pages 62-69.
at least 100 particles of silica or titanium dioxide or other heavy metal oxide produced by Eber
Particles having an average diameter of nm can also be added.
The addition of these particles gives the surface of the cross-linked hydrophilic layer a uniform rough texture consisting of microscopic asperities, which act as storage for water in the background.

The thickness of the crosslinked hydrophilic layer in the lithographic base according to this embodiment can vary from 0.2 to 25 μm and is preferably from 1 to 10 μm.

A specific example of a cross-linked hydrophilic layer suitable as a hydrophilic support for the lithographic printing plate material of the present invention is EP
-A 601240, British Patent 1,419,512
No. 2,300,354, U.S. Pat. No. 3,971,660, U.S. Pat. No. 4,284,705
And EP-A 514 490.

As the flexible support of the hydrophilic support according to this embodiment, it is particularly preferable to use a plastic film, for example, a polyethylene terephthalate film, a cellulose acetate film, a polystyrene film, a polycarbonate film or the like to be used as a substrate. The plastic film support may be opaque or transparent.

It is particularly preferred to use a polyester film support provided with an adhesion improving layer. Adhesion improving layers which are particularly suitable as a hydrophilic support for the lithographic printing plate material of the present invention are EP-A 615 524, EP-A 6205.
No. 02 and EP-A 6195525, hydrophilic binders and colloidal silica. Preferably,
The amount of silica in the adhesion improving layer was 200 mg / m ²
750 mg / m ² . Further, the ratio of silica to hydrophilic binder is preferably greater than 1 and the surface area of the colloidal silica is preferably at least 300 m ² per gram, more preferably 500 m ² per gram.

The microgel having a surface having a group decomposed by at least one of light and heat energy used in the image recording layer of the planographic printing plate material according to the first to third aspects of the present invention will be described.

Examples of the group capable of decomposing by at least one of light and heat energy include JP-A-2-263805,
JP-A-3-64755, JP-A-3-75750, JP-A-3-76704, JP-A-5-45877, JP-A-5-97915, JP-A-5-178946, JP-A-5-249674, Examples include the groups of known microgels (microgels) described in JP-A-6-118463, JP-A-7-261384, and the like. Examples thereof include butoxycarbonyl groups and azide groups; quinonediazides, diazonium salts, and ammonium salts. And a group comprising a phosphonium salt, an iodonium salt, a sulfonium salt, a polymerizable double bond, a counter salt of a dye, and phenylmaleimide.

In the present invention, the term "microgel" refers to small spherical gel particles in which a polymer is bonded in a three-dimensional network, and the microgel particles are smaller than latex, have a charge, have a spread soft structure, It refers to swellable gel particles formed during emulsion polymerization.

The microgel having a group which is decomposed by at least one of light and heat energy used in the present invention (hereinafter also referred to as "microgel of the present invention") is a group which is decomposed by at least one of light and heat energy. Is a microgel having on its surface a polymer containing
As the microgel of the present invention, for example, the following (1) to (1)
2). Preferred are microgels having onium bases described in (1) and (2) below.

(1) Photosensitive microgel chemically modified with diazo, and photosensitive microgel in which the counter cation of an anionic microgel is an onium salt or an iron-arene complex The photosensitive microgel chemically modified with diazo is a diazo group. (Hereinafter referred to as “diazo compound”) and a microgel are bonded by ionic bond or covalent bond.

Compounds in which a diazo compound and a microgel are bonded by an ionic bond. A compound in which the counter anion of a cationic microgel is a diazo compound having an anionic group, and an anionic microgel in which a counter anion of a diazonium salt is an anion.

(-1) Microgel in which the counter anion of the cationic microgel is a diazo compound having an anionic group The cationic microgel is a latex polymer having a quaternary nitrogen atom, that is, dispersed in water or a polar solvent. Granular polymers are used. The cationic latex polymer preferably contains a quaternary nitrogen atom in the side chain of the latex polymer. Representative examples of the monomer units forming such a latex polymer include those represented by the following general formulas [1] to [5].

[0035]

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[0036]

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In the general formulas [1] to [5], X ⁻ represents an anion. That is, halogen ions, sulfate ions,
Phosphate ion, sulfonate ion, acetate ion and the like. The Rs bonded to N ⁺ may be the same or different, and each R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl) , Decyl), an alkenyl group (eg, propenyl, butynyl), or an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl), an aralkyl group (eg, benzyl, phenethyl, Represents each group of naphthylmethyl) or an alkaryl group (for example, each group of tolyl and xylyl). Z represents a group of nonmetal atoms necessary for forming an unsaturated heterocyclic ring, and is preferably an imidazole, pyridine, piperidine, pyrrole or morpholine ring. n represents an integer.

The above-mentioned cationic monomer forming a cationic latex polymer preferably forms a copolymer with a non-cationic monomer in order to control water solubility.
Such non-cationic monomers include acrylic acid, esters of methacrylic acid, styrene, alkylene,
Ether, vinyl acetate, acrylonitrile and the like can be mentioned. In the present invention, the cationic latex polymer is preferably cross-linked by a monomer having two or more functional groups such as divinylbenzene and dimethacrylate,
It is desirably produced by emulsion polymerization.

When the copolymer is formed, the cationic latex polymer contains 5 to 95 cationic monomers.
%, More preferably 25 to 6% by polymerization.
It is contained in the range of 5% by weight. Further, the non-cationic monomer preferably contains 5 to 95% by weight of the cationic latex polymer, and among them, the crosslinkable monomer preferably contains 0.1 to 8% by weight.

As an example of synthesizing a cationic latex polymer, as described in Examples of JP-A-51-73440, vinylbenzyl chloride is emulsion-polymerized with other monomers, and thereafter, tertiary amine is used. A quaternization technique is known.

Particularly preferred cationic latex polymers are latex polymers produced by quaternizing a tertiary amine-containing latex polymer obtained by emulsion polymerization with a quaternizing agent. As an example of this synthesis, there is a technique described in JP-A-55-22766.

Another particularly preferred cationic latex polymer having a quaternary nitrogen atom is a latex polymer produced by emulsion-polymerizing a quaternary nitrogen-containing monomer with a lipophilic monomer. The synthesis method is selected from various known methods and used. One example is described in JP-A-56-17352.

An image recording layer formed by applying a photosensitive composition containing a photosensitive microgel chemically modified with diazo,
In the exposed portion, the resin is cured by the reaction of the diazo resin cation, loses hydrophilicity, and becomes water repellent.

However, when a large amount of cations are present inside the latex particles, the cations remain in the particles even after exposure, the hydrophilicity is maintained, the penetration of the aqueous developer cannot be prevented, and swelling occurs during development. It becomes easy to cause a decrease in film strength.

From the above, the cationic latex polymer in the photosensitive composition containing the photosensitive microgel chemically modified with diazo is produced by a synthesis method in which the cations are more oriented on the surface of the latex particles. Are particularly desirable. As for the manufacturing method,
The most suitable method is to synthesize a latex polymer having an amine by emulsion polymerization, and then quaternize with a quaternizing agent.

Another useful method for synthesizing a cationic latex polymer is a method for producing a quaternary nitrogen atom-containing monomer by emulsion polymerization with a suitable lipophilic monomer. This synthesis method is based on cationic latex polymer,
Ratio of small amount of cationic monomer units (preferably 5 to 5)
30% by weight).

In the photocuring reaction of an image recording layer formed by coating a photosensitive composition containing a photosensitive microgel chemically modified with diazo, the cationic group in the cationic latex polymer plays an important role. ing. Although the reaction mechanism is not clear, the cationic latex polymer having a useful cationic group is selected from those having a quaternary nitrogen atom as described above.

Specific examples of the cationic latex polymer include the following compounds. (Specific examples of the molar ratio are shown in parentheses.)

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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Examples of the diazo compound having an anionic group include Japanese Patent Publication No. 47778/1990 and Japanese Patent Application Laid-Open No. 4-1723.
Compounds in which an anionic group is further introduced into the diazo compounds described in JP-A-53-53 and JP-B-57-43890 can be used. As a specific example, for example, 4-
Sodium diazostilbene-2-sulfonate, sodium 4-diazo-1-phenylamino-2-sulfonate, sodium 4,4'-diadiastilbene-2-sulfonate, sodium 4-diazobenzophenone-4'-carboxylate , 1-diazopyrene-6-sodium sulfonate, 4,4'-diadiazophenylazonaphthalene-
Examples thereof include sodium 5-sulfonate, sodium diazonaphthalene-4-sulfonate, and sodium diazobenzene-m-carboxylate.

To synthesize a microgel in which the counter anion of the cationic microgel is a diazo compound having an anionic group, an aqueous solution of the diazo compound having an anionic group is mixed with the aqueous dispersion of the cationic microgel. The resulting precipitate is collected by suction filtration and washed with water to obtain the desired product.

(-2) The microgel diazonium salt in which the counter anion of the diazonium salt is an anionic microgel is a negative photosensitive lithographic printing plate (P
A photosensitive diazo compound commonly used as a photosensitive component in the photosensitive layer of the (S plate) is used. In general, such diazo compounds are diazo-aromatics, more particularly diazo-arylamines, preferably p-diazo-diphenylamine and its derivatives, which can be substituted on the aromatic nucleus or on the amino-nitrogen. For example, aldehydes and their condensation products with organic condensing agents containing reactive carbonyl groups such as acetal, in particular condensates with compounds such as formaldehyde zinc chloride and paraformaldehyde. The preparation of such highly suitable condensation products is described in U.S. Pat. Nos. 2,922,715 and 2,946,683.
No.

As the anionic microgel, those having an acrylic group or a methacrylic group and having a carboxylic acid group, a sulfonic acid group and a phosphonic acid group as monomer units of the latex polymer are used. Specific examples include the compounds shown below.

[0058]

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[0059]

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It is preferable that the component composed of the above monomer is contained in the microgel in an amount of 0.5 to 50% by weight, particularly 2 to 30% by weight.

The microgel-containing latex polymer can be synthesized by copolymerizing the above monomer with a non-anionic monomer. Examples of the non-anionic monomer used include acrylic acid, methacrylic acid ester, and the like. Examples include styrene, alkylene, ether, vinyl acetate, acrylonitrile and the like, which are preferably crosslinked with a monomer having two or more functional groups such as divinylbenzene and dimethacrylate. Such a non-ionic monomer is present in the photosensitive composition in an amount of from 5 to 95%.
%, And a monomer such as divinylbenzene dimethacrylate is preferably contained in the composition in an amount of 0.1 to 10%.
% By weight.

The latex polymer is described in, for example,
It can be synthesized according to the emulsion polymerization method described in JP-A-1-73440 and JP-A-55-22766.

As a method for synthesizing a microgel in which the counter anion of the diazonium salt is an anionic microgel, a precipitate obtained by mixing the aqueous solution of the diazonium salt and the aqueous dispersion of the anionic microgel is subjected to suction filtration. It can be collected and washed with water to obtain the desired product.

Compound in which diazo compound and microgel are bonded by covalent bond The amino group of the microgel having an amino group on the particle surface is diazotized with sodium nitrite under acidic conditions.

A microgel having an amino group is usually produced by emulsion polymerization using a monomer having an amino group. Generally, microgels have a polymer content of 99-99.
It is formed from 5% by weight and 10 to 0.5% by weight of a crosslinking agent. The polymer components can be varied in the course of polymerization to produce core and shell microgels with different compositions on the inside and the outside. When a polymeric binder is used, the weight ratio of microgel to binder is from 1:20 to 1:
It can be changed widely within the range of 1.

Microgels can be made from a variety of starting materials. Usually, monomers having one ethylenically unsaturated bond are used to make up most of the microgels, but the crosslinking agent has at least two double bonds.

Examples of the monomer having an amino group include acrylamide, methacrylamide, 2-aminoethyl vinyl ether, p-aminostyrene and the like.

Preferred monomers copolymerized with these are methyl methacrylate, ethyl acrylate,
Methacrylic acid, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, styrene and allyl methacrylate; other useful monomers include acrylonitrile, methacrylonitrile,
Acrylic acid, methacrylic acid and 2-methyl-hexyl acrylate are included.

The preferred crosslinking agent is butanediol diacrylate, but others include ethylene glycol dimethacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, methylene bisacrylamide. , Methylenebismethacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, glycerin trimethacrylate, pentaerythritol tetramethacrylate, triallyl cyanurate, divinyl acetylene, divinyl ethane, divinyl Sulfide, divinyl sulfone, hexatriene, triethylene glycol dimethacrylate, Arirushianamido, glycol diacrylate, ethylene glycol divinyl ether,
Diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether and the like.

In the preparation of microgels, one or several monomers and a crosslinking agent are usually dispersed in water together with a suitable emulsifier and initiator. Usually anionic,
A cationic or nonionic emulsifier and a water-soluble initiator are used. Examples of emulsifiers are sodium lauryl sulfate,
Lauryl pyridine chloride, polyoxyethylene, polyoxypropylene, colloidal silica, anionic organic phosphate, magnesium montmorillonite, reaction product of 1 mol of octylphenol with 12 to 13 mol of ethylene oxide, sodium dialkyl sulfate and the like And the like. Examples of initiators are potassium persulfate, sodium persulfate, ammonium persulfate, t-butyl hydroperoxide, hydrogen peroxide, azobis (isobutyronitrile), azobis (isobutyromidine hydrochloride), hydrogen peroxide-sulfuric acid Various redox (oxidation-reduction) systems such as ferrous iron and the well-known persulfate-bisulfite combination.
0.05 based on the weight of monomers normally copolymerized
５5% by weight of initiator is used.

Another method for introducing a hydroxyl group or an amino group into the particle surface is described in, for example, "Chemical Reaction of Polymer (above)".
(Below) "(Nobuo Ogawara, Kagaku Doujin, 1972)," Polymer Fine Chemicals "(Ryohei Oda, Kodansha, 197)
6), a method based on a polymer reaction described in “Reactive polymer” (Keita Kurita, Yoshio Iwakura, Kodansha, 1977) can also be used. For example, a compound having an amino group after synthesizing a microgel having a reactive group A method of chemically modifying a reactive group with the above or graft-polymerizing a reactive group as a starting point with a polymerizable monomer having an amino group is used.

In order to synthesize a compound in which the diazo compound and the microgel are bonded by a covalent bond, the aqueous dispersion of the microgel having an amino group is made acidic with sulfuric acid, hydrochloric acid, or the like, cooled to about 0 ° C., and mixed with stirring. A concentrated aqueous solution of sodium nitrate is added dropwise, and after the addition, it is confirmed that the solution is acidic. Then, the mixture is stirred for 30 minutes to complete diazotization. If a salt of a desired counter anion (for example, zinc chloride or ammonium hexafluorophosphate) is added to this solution and shaken well and allowed to stand, a microgel having a diazo group precipitates.

Next, a photosensitive composition containing a photosensitive microgel in which the counter cation of the anionic microgel is at least one selected from an onium salt and an iron-arene complex will be described.

As the onium salt, a compound represented by the following general formula [6] or [7] is used.

[0075]

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In the general formulas [6] and [7], Ar ¹
And Ar ² may be the same or different and represent a substituted or unsubstituted aryl group. Preferred substituents are alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxy, alkoxycarbonyl, hydroxy, mercapto groups and halogen atoms,
More preferably, an alkyl group having 1 to 8 carbon atoms, 1 carbon atom
８8 alkoxy groups, nitro groups and chlorine atoms.

R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms and an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof.

Preferred substituents are alkoxy having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms, nitro, carboxy, hydroxy group and halogen atom for the aryl group. Is an alkoxy, carboxy, or alkoxycarbonyl group having 1 to 8 carbon atoms.

Further, two of R ⁴ , R ⁵ and R ⁶ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

X ^- represents an anion (counter ion). Specific examples include halogen atom anions, BF ₄ ⁻ , BC
l ₄ ⁻ , ZrCl ₅ ⁻ , SbCl ₆ ⁻ , FeCl ₄ ⁻ , GaCl _{4
^{-, GaBr 4 -, AlI 4}} -, AlCl 4 -, SbF 6 -, C
F ₃ SO ₃ ⁻ , PF ₆ ⁻ , BPh ₄ ⁻ , condensed polynuclear aromatic sulfonic acid anions such as naphthalene-1-sulfonic acid, anthracene-1-sulfonic acid, anthraquinonesulfonic acid anion, anthracenesulfonic acid anion, sulfonic acid group Dyes and the like are included, but are not limited thereto.

Specific examples of the compound represented by the general formula [6] are shown below.

[0082]

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[0083]

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[0084]

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[0085]

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Specific examples of the compound represented by the general formula [7] used in the present invention are shown below.

[0087]

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[0088]

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The amount of the onium compound used is in the range of 0.01 to 50 parts by weight, particularly preferably 0.1 to 20 parts by weight, based on 100 parts of the photosensitive composition.

The compounds represented by the general formulas [6] and [7] are described, for example, in J. Am. W. Knappzyk et al. A
m. Chem. Soc. 91, p. 145 (19
69), A. L. Myacock et al. Org.
Chem. 35, 2532 (1970),
E. FIG. Goethals et al., Bull. Soc. Che
m. Belg. 73, p. 546 (1964).
Year), H. M. Leicester, J.A. Am. Ch
em. Soc. 51, p. 3587 (1929).
Year), J.M. V. Crivello et al. Poly
m. Soc. Polym. Chem. Ed. , 18th
2677 (1980), U.S. Pat.
7,648 and 4,247,473;
M. Beringer et al. Am. Chem. So
c. 75, p. 2705 (1953), JP-A-53-101331, and the like.

As the anionic microgel, the anionic microgel described in the above (-2) can be used.

In order to synthesize a photosensitive microgel in which the counter cation of the anionic microgel is an onium salt from the onium salt and the anionic microgel, the aqueous solution of the onium salt and / or the polar solvent solution and the aqueous dispersion of the anionic microgel are used. The precipitate obtained by mixing with the liquid is collected by suction filtration and washed with water to obtain the desired product.

The photosensitive microgel in which the counter cation of the anionic microgel is an iron-arene complex is iron-arene complex.
The precipitate obtained by mixing the aqueous solution of the arene complex and / or the polar solvent solution with the aqueous dispersion of the anionic microgel is collected by suction filtration, and washed with water to obtain the desired product. As the anionic microgel, those described above can be used.

The iron-arene complex is represented by the following general formula [8].

[0095]

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In the general formula [8], R ¹ and R ² are C ₁ to
Alkyl C _12, alkenyl group of C ₂ ~C _12, C ₂ ~C
₁₂ alkynyl groups, C ₁ -C ₈ alkoxy groups, cyano groups, alkylthio groups, phenoxy groups, C ₂ -C ₆ monocarboxylic acids and esters and amide groups, phenyl groups, C ₂
Alkanoyl group, an ammonium group -C _5, a pyridinium group, a nitro group, an alkylsulfinyl group, selected from alkylsulfonyloxy groups and sulfamoyl groups.

The iron-arene complex represented by the general formula [8] is described in Chemiker-Zeitung, 108
(II) 345-354 (1984) describe many compounds.

Specifically, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II) -hexafluorophosphate, (η ⁶ -toluene) (η ⁵ -cyclopentadienyl) iron (II) Hexafluorophosphate, (η ⁶ -cumene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluoroarsenate , (Η ⁶ -benzene) (η ⁵ -cyclopentadienyl)
Iron (II) tetrafluoroborate, (η ⁶ -naphthalene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -anthracene) (η ⁵ -cyclopentadienyl) iron (II) Hexafluorophosphate, (η ⁶ -pyrene) (η ⁵ -cyclopentadienyl)
Iron (II) hexafluorophosphate, (η ⁶ -benzene) (η ⁵ -cyanocyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -toluene) (η ^5-
Acetylcyclopentadienyl) iron (II) hexafluorophosphate, (η ⁶ -cumene) (η ⁵ -chlorocyclopentadienyl) iron (II) tetrafluoroborate,
(Η ⁶ -benzene) (η ⁵ -carbethoxycyclohexadienyl) iron (II) hexafluorophosphate, (η
⁶ - benzene) (eta ^{5-1,3-dichloroethylene} cyclohexadienyl) iron (II) hexafluorophosphate, (eta ⁶
-Cyanobenzene) (η ⁵ -cyclohexadienyl) iron (II) hexafluorophosphate, (η ⁶ -acetophenone) (η ⁵ -cyclohexadienyl) iron (II) hexafluorophosphate, (η ⁶ -methylbenzoate) ( eta ⁵ - cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - benzenesulfonamide) (eta ⁵ - cyclopentadienyl) iron (II) tetrafluoroborate, (eta ⁶ - benzenesulfonamide)
(Eta ⁵ - cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - cyano benzene) (eta ⁵ - cyano cyclopentadienyl) iron (II) hexafluorophosphate, (eta ⁶ - chloronaphthalene) ( η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate,
(Η ⁶ -anthracene) (η ⁵ -cyanocyclopentadienyl) iron (II) hexafluorophosphate. These compounds are described in Dokl. Akd. Nau
k SSSR 149 615 (1963).

The photosensitive microgel has a particle size of 0.005.
１1 μm, the inside of the particles has a crosslinked structure, is insoluble in solvents, dispersible in water or organic solvents, and is microscopically nonuniform even if it is visually transparent when the film is formed. It is a gel.

For the method for synthesizing the photosensitive microgel, reference can be made to JP-A-6-161101.

(2) Microgel having a quaternary nitrogen atom in the molecule The quaternary nitrogen atom is preferably contained in a side chain of a polymer molecule constituting the microgel.

A typical example of the monomer unit constituting such a polymer is represented by the following general formula:

[9] to [13] are exemplified.

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[0104]

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General formula

In [9] to [13], X ⁻ represents an anion. That is, halogen ions, sulfate ions,
BF ₄ ⁻ , PF ₆ ⁻ , SiF ₆ ²⁻ , Sb containing phosphate ion, sulfonate ion, acetate ion and other fluorine
Anions such as F ₆ ⁻ and BeF ₄ ²⁻ are included.

The Rs bonded to N ⁺ may be the same or different, and each R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, pentyl, hexyl) , Heptyl, decyl), an alkenyl group (eg, propenyl, butynyl), or an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl), an aralkyl group (eg, benzyl, Phenethyl, naphthyl, methyl groups) or alkaryl groups (for example, tolyl,
Each group of xylyl). Further, those having a polymerizable unsaturated ethylene group are also preferable. This is when the above-mentioned photopolymerization of the ethylenically unsaturated compound having a polymerizable group in the molecule,
This is because they polymerize with these to form a chemical bond. Z represents a group of nonmetal atoms necessary for forming an unsaturated heterocyclic ring, and is preferably an imidazole, pyridine, piperidine, pyrrole or morpholine ring. n represents an integer.

A latex polymer constituting a microgel having a cationic group, which is represented by the general formula

Those having the monomer units represented by [9] to [13] have hydrophobicity without a polar group because the main chain is a CC bond, and thus contribute to the hydrophobicity when the photosensitive layer is formed. For example, when the latex polymer is an aqueous latex polymer, it may have a water-soluble group that can be dispersed in water, so that a relatively large number of hydrophobic groups can be introduced into the polymer molecule, so that the hydrophilic property is reduced. It is advantageous in that it can be applied and that the dispersion containing the same has a low viscosity for the resin concentration, so that the coating properties when forming the photosensitive layer are good and the dried film can be made thick. In order to adjust the water solubility by introducing a hydrophobic group into the latex polymer, a non-cationic monomer may be copolymerized with the above-mentioned cationic monomer. Examples of the non-cationic monomer include acrylate, methacrylic acid and the like. Esters, styrene, alkylene, vinyl acetate,
Acrylonitrile and the like. The latex polymer is preferably crosslinked with a monomer having two or more unsaturated groups, such as divinylbenzene and dimethacrylate, and is preferably produced by emulsion polymerization. This is because the hydrophilicity of the monomer is reduced, and emulsion polymerization can be performed effectively, and as a result, the film strength is improved.

In order to produce a copolymer of the above cationic monomer and a non-cationic monomer, the cationic monomer in the latex polymer having a cationic group contains 5 to 5 cationic monomers.
It is preferably contained in an amount of 95% by weight, more preferably 25% by weight.
~ 65% by weight. The non-cationic monomer is 5 to
The content is preferably 95%, of which 0.1 to 8% by weight of the crosslinking monomer such as divinylbenzene is preferred.

As an example of synthesizing the latex polymer having a cationic group, vinylbenzyl chloride is emulsion-polymerized with another monomer as described in Examples of JP-A-51-73440, and then A method of quaternizing with a tertiary amine can be employed. Another preferred synthesis method is the method described in JP-A-55-22766. Another preferred synthesis method is disclosed in JP-A-56-1735.
This is a method described in Japanese Patent Publication No.

The latex polymer having a cationic group is a polymer having substantially a quaternary nitrogen atom in the cationic group in the composition, and an amine, particularly a tertiary amine, in the molecule is used in an aqueous solvent. The case where a cationic group having a quaternary nitrogen atom as a result of dispersion is included is also included.

The microgel has a particle size of 10 to 200 n.
m is preferable, and if it is smaller than 10 nm, it is difficult to manufacture and is not practical. On the other hand, when it is larger than 200 nm, the resolution of an image is deteriorated when an image portion after exposure of the photosensitive layer is formed.

Specific examples of the polymer having a cationic group include (1) to (18) which are the specific examples of the cationic latex polymer in the microgel of the above (1) and the following compounds. Note that the values in parentheses are molar ratios.

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(3) Reactive microgel described in JP-A-2-263805 (4) Microgel described in JP-A-3-64755 (5) Page 2 of JP-A-3-75750 Microgel described in line 1 from the upper right column to line 8 in the lower right column on page 3 (6) Upper right column 10 on page 2 of JP-A-3-76704
(7) Microgel of a salt of a cationic latex having a quaternary nitrogen atom or a quaternary phosphorus atom and an anionic dye disclosed in JP-A-5-45877 (8) ) Reactive microgel described in JP-A-5-97915 (9) Photosensitive microgel described in JP-A-5-178946 (1) (10) JP-A-5-249675 4
Microgel of Salt of Cationic Latex Having Grade Nitrogen or Phosphorus Atom and Anionic Compound Having Photo-Crosslinking Group (11) o described in JP-A-6-118463
-A microgel whose surface is chemically modified with a quinonediazide group. (12) A microgel introduced with, for example, a butoxycarbonyl group which is released by an acid described in JP-A-7-261384. The absorption wavelength of the infrared light absorbing agent to be contained in the layer is not important as long as it is within the wavelength range of the light source used for image exposure of the image recording layer containing the infrared light absorbing agent. Particularly useful infrared light absorbers are, for example, dyes and especially infrared dyes, carbon black, metal carbides, borides, nitrides, carbonitrides (carbon).
oxides, which are structurally related to the bronze-structured oxides and bronze family, but do not contain the A component, for example WO _2.9 . Conductive polymer dispersions, such as those based on polypyrrole or polyaniline, can also be used. The lithographic performance obtained, and especially the print resistance, depends on the heat sensitivity of the imaging element. In this regard, carbon black gives very good and favorable results.

The image recording layer according to the first or second aspect of the present invention contains at least the microgel of the present invention and an infrared light absorbing agent. The content of the microgel of the present invention in the image recording layer is preferably from 100 to 90 wt%, and the content of the infrared light absorber is preferably from 0.1 to 30 wt%.

The image recording layer of the invention according to claim 1 or 2 can contain a binder resin or the like as a binder in addition to the above. As the binder resin, for example, a synthetic homo- or copolymer such as polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylamide, hydroxyethyl poly (meth) acrylate, polyvinyl methyl ether or a natural binder such as gelatin, Polysaccharide,
For example, hydrophilic binders such as dextran, burlan, cellulose, gum arabic, and alginic acid can be mentioned. The content of the binder resin is preferably in the range of 0 to 10 wt%.

The image recording layer according to the first or second aspect of the present invention comprises an embodiment in which the above components are formed as a single layer, an infrared absorbing layer (containing an infrared absorbing agent and a binder resin) and a photosensitive layer (the present invention). There is an embodiment in which a layer containing the microgel of the invention is formed in this order on a support.

The thermoplastic polymer particles to be fused by thermal energy contained in the image recording layer according to the third aspect of the present invention preferably have a solidification temperature of 35 ° C. or more, and more preferably 50 ° C. or more. Solidification may result from the softening or melting of the thermoplastic polymer particles under the influence of heat. There is no particular upper limit on the solidification temperature of the thermoplastic hydrophobic polymer particles, but this temperature must be well below the decomposition point of the polymer particles. Suitably the coagulation temperature is at least 10 ° C below the temperature at which the decomposition of the polymer particles takes place. When the polymer particles are exposed to temperatures above the coagulation temperature, they coagulate to form a hydrophobic agglomerate in the hydrophilic layer, so that in these parts the hydrophilic layer is Insoluble in

Specific examples of hydrophobic polymer particles for use in connection with the present invention include, for example, polyethylene, polyvinyl chloride, poly (methyl meth) acrylate, poly (ethyl meth) acrylate, polyvinylidene chloride, poly (vinylidene chloride), and the like. Acrylonitrile, polyvinyl carbazole and the like or a copolymer thereof. Polyethylene is most preferably used.

The weight average molecular weight of the polymer is from 5,000 to
It may be in the range of 1,000,000 g / mol.

The hydrophobic particles may have a particle size between 0.01 and 50 μm, more preferably between 0.05 and 10 μm and most preferably between 0.05 and 2 μm.

The polymer particles are present as a dispersion in the aqueous coating solution of the imaging layer and are disclosed in US Pat.
476,937. Other methods particularly suitable for preparing aqueous dispersions of thermoplastic polymer particles include: dissolving a hydrophobic thermoplastic polymer in an organic, water-immiscible solvent; and dissolving the resulting solution in water or aqueous. Dispersing in a medium and removing the organic solvent by evaporation.

The amount of hydrophobic thermoplastic polymer particles contained in the imaging layer is preferably between 20 and 65% by weight and more preferably between 25 and 55% by weight and most preferably between 3 and 55% by weight.
Between 0 and 45% by weight.

The compound which induces a chemical reaction in the presence of a compound absorbing light energy having a wavelength longer than 500 nm contained in the image recording layer of the invention according to claim 3 is described in US Pat. No. 3,048,120. There are esters of naphthoquinone- (1,2) -diazide- (2) -sulfonic acid chloride and phenol or cresol formaldehyde resin described therein. Other useful o-naphthoquinonediazide compounds include, for example, pyrogallol- described in US Pat. No. 3,635,709.
Esters of acetone resin and o-naphthoquinonediazidesulfonic acid chloride, JP-A-55-76343,
Esters of polyhydroxyphenyl resin and o-naphthoquinonediazidosulfonic acid chloride described in JP-A-6-1044 and JP-A-56-1045;
No. 13305, obtained by subjecting a homopolymer of p-hydroxystyrene or a copolymer thereof to a copolymerizable monomer with o-naphthoquinonediazide sulfonic acid chloride to an ester reaction.
And a reaction product of a polymer product of a styrene monomer and a phenol derivative and o-quinonediazidesulfonic acid described in US Pat. No. 17,481, and an ester of polyhydroxybenzophenone and o-naphthoquinonediazidesulfonic acid chloride.

A photosensitive composition containing such a quinonediazide-type positive photosensitive substance may optionally contain a binder. For example, a preferable one is a novolak resin soluble in an aqueous alkali solution. Examples of such novolak resins include phenol-formaldehyde resin, cresol-formaldehyde resin, p-formaldehyde resin.
tert-butylphenol-formaldehyde resin,
A typical example is a phenol-modified xylene resin. The amount of the quinonediazide compound in the photosensitive composition is from 10 to 50% by weight, more preferably from 20 to 50% by weight.
40% by weight. The amount of the binder is 45 to 80% by weight of the photosensitive composition, preferably 50 to 7%.
0% by weight.

As the photosensitive substance, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde is also used.

Particularly preferred are salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, for example the reaction of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with said condensates. Examples thereof include a diazo resin inorganic salt which is a product, and a diazo resin organic salt which is a reaction product of the condensate and a sulfonic acid as described in US Pat. No. 3,300,309. Furthermore, diazo resins are preferably used with binders. As such a binder, various polymer compounds can be used.
No. 98613, a monomer having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl)
A copolymer of acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate with another monomer; US Patent 4,
A polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit as described in JP-A-123,276;
Phthalization of natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins described in US Pat. No. 3,751,257, linear polyurethane resins described in US Pat. No. 3,660,097, and polyvinyl alcohol Resin, epoxy resin condensed from bisphenol A and epichlorohydrin, cellulose acetate,
Cellulose such as cellulose acetate phthalate is included.

Further, there may be mentioned those containing as a main component a photosensitive polymer such as polyesters, polyamides and polycarbonates containing —CH ＝ CH—CO— as a photosensitive group in the polymer main chain or side chain. For example, a photosensitive polyester obtained by condensation of phenylenediethyl acrylate with hydrogenated bisphenol A and triethylene glycol as described in JP-A-55-40415, U.S. Pat.
No. 956,878, photosensitive polyesters derived from (2-properidene) malonic acid compounds such as cinnamylidenemalonic acid and difunctional glycols.

Further, an aromatic azide compound in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group is also included. For example, US Pat.
No. 6,311, polyazide styrene, polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, azidoarylsulfanyl chloride described in JP-B-45-9613, and unsaturated hydrocarbons Reaction product with polymer, and JP-B-43-21
Polymers having sulfonyl azide or carbonyl azide as described in JP-A Nos. 067, 44-229, 44-22954 and 45-24915 can be mentioned.

Further, a photopolymerizable composition comprising an addition-polymerizable unsaturated compound is also included.

The content of the infrared light absorbing agent in the image recording layer of the invention according to claim 3 is preferably in the range of 0.1 to 30% by weight.

The image recording layer according to the third aspect of the invention can contain a binder resin or the like. Examples of the binder resin include a binder resin in the image recording layer according to the first and second aspects of the present invention.

In the invention according to claim 4, the image exposure is preferably performed by using a laser or an L.P. E. FIG. D. Scanning exposure involving the use of For the present invention, it emits in the infrared (IR) and / or near infrared region, ie, 700-1500
It is highly preferred to use a laser which emits in the wavelength range of nm. Laser diodes emitting in the near infrared range are particularly preferred for use in connection with the present invention.

Suitable imaging devices suitable for scanning exposure are preferably applied directly to the imaging element surface via a lens or other light-guiding component, or use a fiber optic cable to provide a blank image from a remote laser. Includes laser power that can be transmitted to the surface of the forming element. An adjuster and associated positioning hardware keep the beam output in the correct orientation relative to the imaging element surface, scan the output over the surface, and operate the laser at an adjacent selected point or portion of the imaging element. . The controller responds on the imaging element to an input image signal corresponding to the original document and / or picture to be copied to form an accurate negative or positive image of the original. These image signals are stored in a computer as a bitmap data file. Such a file may be created by a laser image processor (RIP) or other suitable means. For example, a RIP can accept input data in a page-description language or as a combination of a page-description language and one or more image data files that define all the features required to be transferred onto an imaging element. A bitmap is created to define the tone and screen frequency and angle in the case of amplification adjustment screening. However, the invention relates, for example, to EP-A 571 010, EP
Particularly suitable for use in combination with the frequency-regulated screening disclosed in EP-A-620677 and EP-A-620674.

The apparatus for forming an image may be provided with an image forming apparatus having an image forming function by itself, separately from the printing machine, and may form an image with the apparatus, or may have a means for supplying a dampening solution. It can also be added directly into the lithographic printing press. In the latter case, printing may start immediately after image-wise exposure and development, thereby significantly reducing press set-up time. The image forming device can be configured as a flatbed recorder or as a drum recorder having a lithographic blank located on the inner and outer cylindrical surfaces of the drum. Obviously, an external drum design is more suitable for use on a lithographic printing press in situ, in which case the printing cylinder itself constitutes the drum part of the recorder or plotter.

In a preferred drum configuration, the drum (and the imaging element mounted thereon) is rotated about its axis and a light beam parallel to the axis of rotation is moved, thereby moving the imaging element in a circumferential direction. To "grow" the image in the axial direction to provide the necessary relative motion between the laser beam and the imaging element. Alternatively, the beam may be moved parallel to the drum axis and the image may be "grown" circumferentially on the imaging element at increasing angles after each pass over the imaging element. In both cases, after complete scanning and development by the light beam, an image corresponding to the original will have been applied to the surface of the imaging element. In the flatbed structure,
Rays are drawn along either axis of the imaging element and are designated along the other axis after each pass.
Of course, the necessary relative movement between the light beam and the imaging element may be caused by the movement of the imaging element rather than (or in addition to) the movement of the light beam.

Regardless of how the light beam is scanned, it is generally preferred (for speed reasons) to use multiple lasers and to direct their output to a single writing array.
After the completion of each pass over or along the imaging element, a writing array is then specified, where the distance is determined by the number of rays emanating from the array and the desired resolution (ie, the number of image points per unit length). Number).

The thermal energy source according to the first to fifth aspects of the present invention is preferable because a laser and a thermal head can be heated to a fine pattern, and a laser is preferable because a non-contact and high-resolution heating can be performed.

According to a fourth aspect of the present invention, the image recording layer of the lithographic printing plate material according to the first to third aspects is provided with at least one of light and heat energies in the form of an image, and then exposed to an aqueous developing solution. It elutes the image recording layer corresponding to the image area.

The aqueous developer means a developer in which 90% by weight or more of the solvent is water. As the aqueous developer, a known aqueous developer containing an alkali, an acid, a surfactant, an organic solvent and the like can be used, but water is preferable.

The invention according to claim 5 is a method for producing a printed matter, wherein the printed matter is produced by using the lithographic printing plate material according to any one of claims 1 to 3 in one of the procedures (a) and (b). . (A) is an image exposure of a lithographic printing plate material, the lithographic printing plate material is set on a printing cylinder of a printing press, and dampening water and / or ink is supplied to an image recording layer of the lithographic printing plate to form an image. The printing is performed by removing the recording layer in an image-like manner to form a plate surface of a lithographic printing plate, and (b) performing image exposure after placing the lithographic printing plate material on a printing cylinder of a printing press. Same as (a).

In the above-mentioned production method, known ones can be applied as the fountain solution, the ink and the receiving element (substrate to be printed such as paper).
The method described in JP-A-123387 can be applied.

[0143]

EXAMPLE 1 An aluminum plate having a thickness of 0.24 mm was immersed in an aqueous solution containing 5 g / l of sodium hydroxide at 50 ° C.
Degreased by rinsing with deionized water. The aluminum plate is then electrochemically polished in an aqueous solution containing 4 g / l hydrochloric acid, 4 g / l boric acid and 5 g / l aluminum ions using an alternating current at a temperature of 35 ° C. and a current density of 1200 A / m ^2. To form a surface topology with an average centerline roughness of 0.5 μm. After rinsing with deionized water, the aluminum plate was then etched with an aqueous solution containing 300 g / l sulfuric acid at 60 ° C. for 180 seconds and rinsed with deionized water at 25 ° C. for 30 seconds.
The aluminum is then placed in an aqueous solution containing 200 g / l sulfuric acid at a temperature of 45 ° C., a voltage of about 10 V and 150 A
Anodized at a current density of about 300 s / m ² for about 300 seconds to form an anodized layer of 3.00 g / m ² Al ₂ O ₃ , then rinsed with deionized water, containing 20 g / l sodium bicarbonate The solution was worked up at 40 ° C. for 30 seconds, followed by rinsing with deionized water at 20 ° C. for 120 seconds and drying. The polished, anodized lithographic base is then submerged in an aqueous solution containing 5% by weight citric acid for 60 seconds, brought to pH 7 with an aqueous solution of 2N sodium hydroxide for 60 seconds, rinsed with deionized water and at 25 ° C. Dry,
A hydrophilic support for a printing plate was obtained. An image recording layer coating solution having the following composition is applied to the hydrophilic support using a wire bar so that the dry film thickness becomes 1.0 g / m ² , and dried at 40 ° C. for 3 minutes to perform image recording. The layers were applied to obtain a lithographic printing plate material.

Image recording layer coating solution Infrared light absorbing dye (CY10; Nippon Kayaku Co., Ltd.) 0.9 parts by weight Microgel A 9.0 parts by weight Ethylene glycol monomethyl ether 90.0 parts by weight

[0145]

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After fixing the lithographic printing plate material to the cylinder of the printing press, the semiconductor laser light source (semiconductor laser output: 100 W, emission wavelength: 830 nm, 2.2 m / sec.
After performing image exposure using a spot size of 10 μm for 2 seconds, ink supply and fountain solution supply were performed, and normal printing was performed. Good prints were obtained from the tenth printing.
Table 1 shows the evaluation results of the sensitivity, printing durability, and chemical resistance of the lithographic printing plate material. Further, after the lithographic printing plate material was subjected to image exposure using an exposure machine (Trend Setter 3244; semiconductor laser output 10 W, 240 channel machine) manufactured by Creo Products, the plate surface was sponged while washing with tap water at 20 ° C. When rubbed, the unexposed recording layer was removed, and a printing plate was obtained. When this plate was attached to the cylinder of the printing press and printing was performed in the same manner, a good printed matter was obtained, and almost the same performance as that of the printing plate subjected to development processing on the printing press was exhibited.

Example 2 The same procedure as in Example 1 was carried out except that a support prepared by the following method was used as a hydrophilic support for a printing plate, and good prints and the results shown in Table 1 were obtained.

Preparation of Hydrophilic Support The following hydrophilic layer coating solution was applied to a corona-treated polyethylene terephthalate film having a thickness of 175 μm so that the film thickness after drying became 2 μm, and dried at 110 ° C. for 10 minutes. .

Hydrophilic coating liquid Colloidal silica (Snowtex OL; 20% aqueous dispersion; manufactured by Nissan Chemical Industries, Ltd.) 25 parts by weight Porous silica (Syloid 435; manufactured by Grace Japan) 4 parts by weight Polyvinyl alcohol (KL05; Japan) 1 part by weight Pure water 70 parts by weight Example 3 A 175 μm-thick polyethylene terephthalate film subjected to corona treatment was coated with the following hydrophilic layer coating solution so that the film thickness after drying was 2 μm, After drying at 110 ° C. for 10 minutes, a hydrophilic support was prepared.

Hydrophilic coating solution Colloidal silica (Snowtex OL; 20% aqueous dispersion; manufactured by Nissan Chemical Industries, Ltd.) 25 parts by weight Porous silica (Syloid 435; manufactured by Grace Japan) 4 parts by weight Polyvinyl alcohol (KL05; Japan) 1 part by weight SD9020 (aqueous dispersion of carbon black; manufactured by Dainippon Ink and Chemicals, Inc.) 1 part by weight Pure water 70 parts by weight Next, an image recording layer coating solution having the following composition was coated on the hydrophilic support. Using a wire bar, the dry film thickness is 1.0 g /
m ² , and dried at 40 ° C. for 3 minutes to apply an image recording layer to obtain a lithographic printing plate material.

Image recording layer coating solution Microgel B 9.0 parts by weight Ethylene glycol monomethyl ether 90.0 parts by weight

[0152]

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After fixing the lithographic printing plate material to a cylinder of a printing press, a semiconductor laser light source (emission wavelength: 830 nm, 2.2 m / sec, spot size: 10 μm,
After image exposure using an energy of 300 mJ / cm ^{2 on the} image surface, ink supply and dampening water supply were performed, and normal printing was performed. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the sensitivity, printing durability, and chemical resistance of the lithographic printing plate material. Also, the lithographic printing plate material was exposed to an exposure machine (Trendsetter 3244; semiconductor laser output 10 W, 240
After performing image exposure with a channel machine, the plate surface was rubbed with a sponge while washing with tap water at 20 ° C., whereby the recording layer in the unexposed portions was removed, and a printing plate was obtained. When this plate was attached to the cylinder of the printing press and printing was performed in the same manner, a good printed matter was obtained, and almost the same performance as that of the printing plate subjected to development processing on the printing press was exhibited.

Example 4 An image recording layer coating solution having the following composition was applied on a hydrophilic aluminum support for a printing plate prepared in Example 1 using a wire bar to a dry film thickness of 1.0 g / m ² . And apply
After drying at 40 ° C. for 3 minutes, the image recording layer was applied to obtain a lithographic printing plate material.

Image recording layer coating solution Infrared light absorbing dye (CY17; Nippon Kayaku Co., Ltd.) 0.9 parts by weight Thermoplastic polymer particles (Iodozol GD87B; 50% aqueous dispersion; Nippon NSC) 20.0 parts by weight Part Polyvinyl alcohol (KL05; Nippon Gohsei) 2.0 parts by weight Polyethylene ethylene glycol diacrylate (KS-PEG400DA; Nippon Kayaku) 2.0 parts by weight Water-soluble polymerization initiator (KAYACURE QTX; Nippon Kayaku) 0.2 parts by weight Pure water 90.0 parts by weight The above lithographic printing plate material was exposed to an exposure machine manufactured by Creo Products (Trendsetter 3244; semiconductor laser output 10).
(W, 240 channel machine), the lithographic printing plate material was fixed to a cylinder of the printing press, ink was supplied and dampening water was supplied, and normal printing was performed. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the sensitivity, printing durability, and chemical resistance of the lithographic printing plate material.

Example 5 A dry film thickness of 1.0 was applied on the hydrophilic support prepared in Example 2 by using a wire bar of an image recording layer coating solution having the following composition.
g / m ² and dried at 40 ° C. for 3 minutes.
An image recording layer was applied to obtain a lithographic printing plate material.

Image recording layer coating solution SD9020 (aqueous carbon black dispersion; manufactured by Dainippon Ink and Chemicals, Inc.) 0.9 parts by weight Thermoplastic polymer particles (6040; 50% aqueous dispersion; manufactured by JSR Corporation) 20.0 parts by weight Polyvinyl alcohol (KL05; manufactured by Nippon Gohsei) 2.0 parts by weight Melamine resin (MW100LM; manufactured by Sanwa Chemical Co.) 2.0 parts by weight Water-soluble acid generator (WS Triazine; manufactured by Sanwa Chemical Co., Ltd.) 0.2 90.0 parts by weight of pure water 90.0 parts by weight of the above lithographic printing plate material was exposed to an exposure machine manufactured by Creo Products (Trendsetter 3244; semiconductor laser output 10).
(W, 240 channel machine), the lithographic printing plate material was fixed to a cylinder of a printing machine, ink was supplied and dampening water was supplied, and normal printing was performed. Good prints were obtained from the tenth printing. Table 1 summarizes the evaluation results of the sensitivity, printing strength, and chemical resistance of the lithographic printing plate material.

Example 6 An image recording layer coating solution having the following composition was applied to the hydrophilic support prepared in Example 3 using a wire bar so that the dry film thickness became 1.0 g / m ^2. After drying at 40 ° C. for 3 minutes, an image recording layer was applied to obtain a lithographic printing plate material.

Image recording layer coating solution Thermoplastic polymer particles (6040; 50% aqueous dispersion; manufactured by JSR Corporation) 20.0 parts by weight Polyvinyl alcohol (KL05; manufactured by Nippon Synthetic Chemical Company) 2.0 parts by weight Diazo resin (diazo resin) Diphenylamine-formalin condensation resin sulfonic acid / zinc chloride double salt) 0.2 parts by weight Pure water 90.0 parts by weight The above lithographic printing plate material was subjected to an exposure machine (Trendsetter 3244; semiconductor laser output 10) manufactured by Cleo Products Co., Ltd.
(W, 240 channel machine), the lithographic printing plate material was fixed to a cylinder of a printing machine, ink was supplied and dampening water was supplied, and normal printing was performed. Good prints were obtained from the tenth printing.

The sensitivity of the lithographic printing plate material, the printing durability and the chemical resistance of the resulting printing plate were measured by the following methods. The results are shown in Table 1 below.

Sensitivity: The minimum energy required for the image recording layer to gel by exposure, and the energy required to form a gel image equivalent to the laser spot diameter was measured.

Printing durability: The maximum number of printed sheets at which the density of printed matter did not decrease was examined.

Chemical resistance: The sample was immersed in a UPC (ultra plate cleaner) used at the time of printing at 25 ° C., and the maximum time during which the image was not damaged was measured.

[0164]

[Table 1]

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that the following image recording layer coating solution was used in place of the image recording layer coating solution, and the exposed portion was also eluted. No printed matter was obtained.

Image recording layer coating solution Infrared light absorbing dye (CY10; Nippon Kayaku Co., Ltd.) 0.9 parts by weight Microgel A 1.1 parts by weight Polyvinyl alcohol (KL05; Nippon Synthetic Chemical Co., Ltd.) 11.0 parts by weight 90.0 parts by weight of ethylene glycol monomethyl ether Comparative Example 2 The same experiment as in Example 1 was performed except that the following coating solution for image recording layer was used in place of the coating solution for image recording layer in Example 1, and exposure was performed. The prints were not obtained.

Image recording layer coating solution Infrared light absorbing dye (CY17; manufactured by Nippon Kayaku Co., Ltd.) 0.9 parts by weight Polymethyl methyl methacrylate (90 nm average particle diameter) 9.0 parts by weight Pure water 90.0 parts by weight Part Comparative Example 3 A lithographic printing plate material was produced based on the example of JP-A-8-314157. When an experiment similar to that of Example 1 was performed using this material, the exposed portion was also eluted, and no printed matter was obtained.

[0168]

According to the present invention, a lithographic printing plate material excellent in environmental suitability and workability, that is, development using water after image exposure or simple development using a dampening solution or ink on a printing press, is used. A lithographic printing plate material which is possible and has excellent sensitivity, printing strength and chemical resistance, and a method for producing a printed matter using the material are provided.

Continued on the front page F term (reference) 2H025 AA00 AA01 AA06 AA07 AA08 AA12 AB03 AC08 AD01 AD03 BA03 BE01 BH03 CC20 EA01 FA03 FA10 FA17 2H096 AA07 AA08 BA16 BA20 CA03 EA04 GA08 2H113 AA03 AA04 BA05 EA06 A04 A04 A04 A04 A03 A04 GA27

Claims (5)

[Claims] 1. An image recording layer containing a microgel having a group decomposed by at least one of light and heat energies on its surface and an infrared light absorber is formed on a hydrophilic support. Lithographic printing plate material. 2. An image recording layer containing a microgel having on its surface a polymer containing a group capable of decomposing by at least one of light and heat energies and an infrared light absorbing agent is formed on a hydrophilic support. A lithographic printing plate material characterized in that: 3. A compound which induces a chemical reaction in the presence of a thermoplastic polymer particle which is fused by thermal energy on a hydrophilic support, a compound which absorbs light energy having a wavelength longer than 500 nm, and an infrared light absorber. A lithographic printing plate material comprising an image recording layer containing: 4. A lithographic printing plate material according to claim 1, wherein at least one of light and heat energy is applied in the form of an image, and then a developer substantially consisting of water corresponds to a non-image portion. A method for producing a lithographic printing plate, comprising eluting an image recording layer to be formed. 5. A method for producing a printed matter, comprising using the lithographic printing plate material according to claim 1 to produce a printed matter according to one of the following procedures (a) and (b). (A) applying energy of at least one of light and heat to the image recording layer of the lithographic printing plate material in an image form, placing the lithographic printing plate material on a printing cylinder of a printing machine, and removing fountain solution and / or ink. The lithographic printing plate material is supplied to the image recording layer and printing is performed. (B) placing the lithographic printing plate material on a printing cylinder of a printing press, applying at least one of energy of light and heat to the image recording layer of the lithographic printing plate material in an image form, and supplying fountain solution and / or ink; The lithographic printing plate material is supplied to the image recording layer and printing is performed.