JP2001133966A - Negative type image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative type image recording material capable of direct recording from digital data with an IR emitting laser and capable of forming a clear image without carrying out heat treatment in image formation. SOLUTION: The negative type image recording material capable of recording by irradiation with IR contains (A) an IR absorber, (B) an N-nitrosamine compound, (C) a radical polymerizable compound and (D) a binder polymer. The N-nitrosamine compound is represented by formula I, wherein R11 is a hydrocarbon group; R12 is an oxygen anion or a hydrocarbon group, when R12 is an oxygen anion, a hydrogen cation, an ammonium cation, a tetraalkylammonium cation or a metal cation may be used as a counter cation; and X11 is a single bond, -CO-, -SO2- or -COO-.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate material, a color proof, an image recording material which can be used as a photoresist and a color filter. In particular, the present invention relates to an image recording material that can be directly made by scanning an infrared laser based on a digital signal from a computer or the like and that can be used as a so-called direct plate making lithographic printing plate material.

[0002]

2. Description of the Related Art Heretofore, as a system for directly making a plate from digital data of a computer, an electrophotographic system, a photopolymerization system for exposing with a laser emitting blue or green light, and a silver salt on a photosensitive resin are known. Laminated ones, silver salt diffusion transfer methods, and the like have been proposed.

However, in the case of using the electrophotographic method, the processes of image formation such as charging, exposure, and development are complicated, and the apparatus is complicated and large. In the case of the photopolymerization system, since a plate material having high sensitivity to blue or green light is used, handling in a bright room becomes difficult. The methods (1) and (2) have drawbacks in that processing such as development becomes complicated because silver salts are used, and silver is contained in the processing waste liquid.

On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers that emit infrared light having a wavelength of 760 nm to 1200 nm have become easily available with high output and small size. These lasers are very useful as a recording light source when making a plate directly from digital data of a computer or the like. However, many photosensitive recording materials that are practically useful have a photosensitive wavelength in the visible light range of 760 nm or less, and therefore cannot record images with these infrared lasers. Therefore, a material that can be recorded by an infrared laser is desired.

As an image recording material recordable by such an infrared laser, there is a recording material comprising an onium salt, a phenol resin and a spectral sensitizer described in US Pat. No. 4,708,925. This image recording material is a positive type image recording material utilizing the effect of suppressing dissolution in a developer, which is exhibited by an onium salt and a phenol resin, and is not a negative type as in the present invention. On the other hand, as a negative type image recording material, a recording material comprising an infrared absorber, an acid generator, a resol resin and a novolak resin is disclosed in US Pat.
0,699. However, such a negative-type image recording material requires heat treatment after laser exposure for image formation, and therefore, a negative-type image recording material that does not require heat treatment after exposure is desired. I was Examples of negative recording materials that do not require heat treatment after exposure include, for example, a photothermal conversion substance, a thermopolymerizable resin, and a thermopolymerization initiator on a support described in JP-A-8-108621. And an image recording medium having a thermopolymerizable recording layer containing However, such an image recording medium lacks sensitivity, and it is necessary to heat simultaneously with exposure in order to obtain sufficient sensitivity.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to record directly using digital data from a computer or the like by recording using a solid-state laser or a semiconductor laser that emits infrared light. An object of the present invention is to provide a negative type image recording material capable of forming a clear image without performing a heat treatment.

[0007]

Means for Solving the Problems The present inventor paid attention to the constituent components of the negative type image recording material, and as a result of intensive studies, as a result, using a compound having an N-nitrosamine structure as a radical polymerization initiator, gave the above object. Have been achieved, and the present invention has been completed. That is, the negative-type image recording material of the present invention comprises (A) an infrared absorber and (B) N
-A nitrosamine-based compound, (C) a radical polymerizable compound, and (D) a binder polymer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

[(B) N-Nitrosamine Compound] The present invention is characterized in that an N-nitrosamine compound is used as a radical polymerization initiator. First, a description will be given. N preferably used in the present invention
As the nitrosamine-based compound, the following general formula (I)
The compound shown by these is mentioned.

[0010]

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In the formula, R ¹¹ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, a hydroxyl group, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, or a 12-carbon atom.
Or less carbamoyl groups. R ¹² is an oxygen anion or an optionally substituted carbon atom having 2 carbon atoms.
Indicates 0 or less hydrocarbon groups. Preferred substituents include a halogen atom, a nitro group, a hydroxyl group, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and a carbamoyl group having 12 or less carbon atoms. . When R ¹² is an oxygen anion, a hydrogen cation, an ammonium cation, a tetraalkylammonium cation, and a metal cation can be used as counter cations. X ¹¹ represents a single bond, a —CO— group, a —SO ₂ — group, or a —COO— group. Usually, N-nitrosamine refers to a compound in which X ¹¹ is a single bond and R ¹² is a hydrocarbon group. In the present invention, X ¹¹ is a —CO— group, a —SO ₂ — group, a —COO group.
All the compounds represented by the general formula (I), including the compounds that are -groups, are included in the N-nitrosamine-based compounds.

In the present invention, the compound represented by the general formula (I) which can be suitably used includes, for example, N
-Nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodiethanolamine, N-nitroso-
tert-butylethylamine, N-nitrosodi-n-
Butylamine, N-nitroso-n-butyl-4-butanolamine, 1-nitrosopyrrolidine, N-nitrosomorpholine, N-nitroso-N-methylaniline, N-
Nitroso-N-methyl-p-toluenesulfonamide,
N-nitroso-N-methylurethane, N-nitrosodiphenylamine, ammonium salt of N-nitroso-N-phenylhydroxylamine, aluminum salt of N-nitroso-N-phenylhydroxylamine, N-nitroso-N- (1-naphthyl ) Ammonium salts of hydroxylamine.

These N-nitrosamine compounds are
It can be added to the image recording material at a ratio of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight based on the total solid content of the image recording material.
If the amount is less than 0.1% by weight, the sensitivity is lowered, and if it exceeds 50% by weight, the non-image area is stained during printing. These N-nitrosamine compounds may be used alone or in combination of two or more. Also,
These N-nitrosamine-based compounds may be added to the same layer as other components, or another layer may be provided and added thereto. In the present invention, the N-nitrosamine-based compound is used as a radical polymerization initiator. In the image recording material of the present invention, a known radical polymerization initiator such as a diazonium salt or an iodonium salt may be used. Can be used together as long as is not impaired.

Since these N-nitrosamines have conventionally been used as inhibitors of radical polymerization, they are used as initiators of radical polymerization for curing the recording layer in image recording materials as in the present invention. What can be used is surprising.

[(A) Infrared ray absorbing agent]
Image recording with a laser that emits infrared light. To this end, it is essential to use an infrared absorber. The infrared absorbent has a function of converting the absorbed infrared light into heat. Due to the heat generated at this time, the radical polymerization initiator (B) N-nitrosamine-based compound is decomposed,
Radicals are generated, and the radicals polymerize and cure the (C) radically polymerizable compound in the infrared laser exposure portion to form an image. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm.

As the dye, commercially available dyes and known dyes described in literatures such as “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned.

Preferred dyes include, for example, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875 and the like can be mentioned.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranyl compounds, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used.

Further, as another preferred example of the dye, US Pat. No. 4,756,993 discloses a compound represented by the formula (I):
Near-infrared absorbing dyes described as (II) can be mentioned.

Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes. Further, a cyanine dye is preferable, and a cyanine dye represented by the following general formula (II) is most preferable.

[0021]

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In the general formula (II), X ¹ is a halogen atom,
Or an X ² -L ^1. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms. R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. The storage stability of the recording layer coating liquid, R ¹ and R ² are preferably a hydrocarbon group having two or more carbon atoms, further, R ¹ and R ²
And particularly preferably combine with each other to form a 5- or 6-membered ring. Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Preferred examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same or different and each have a sulfur atom or 12 carbon atoms.
Represents up to dialkylmethylene groups. R ³ and R ⁴ may be the same or different, and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group, and a sulfo group.
R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the viewpoint of availability of raw materials, a hydrogen atom is preferable. Z ^1- represents a counter anion. However,
When any of R ^{1 to} R ⁸ is substituted with a sulfo group, Z ^1- is not required. Preferred Z ¹⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion from the storage stability of the recording layer coating solution, and particularly preferably a perchlorate ion. Hexafluorophosphate ion and arylsulfonate ion.

In the present invention, specific examples of the cyanine dye represented by formula (II) ([I
R-1] to [IR-12]) are shown below, but the present invention is not limited thereto.

[0024]

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[0025]

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[0026]

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As the pigment used in the infrared absorber in the present invention, commercially available pigments and Color Index (CI) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment" Application Technology ”(CMC
Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984) can be used.

The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments,
Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferable in terms of stability in the coating solution for the image recording layer, and when it exceeds 10 μm, it is not preferable in terms of uniformity of the image recording layer.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

These infrared absorbers are used in an amount of 0.01 to 50% by weight, preferably 0.1% by weight, based on the total solid content of the image recording material.
It can be added to the image recording material at a ratio of from 20 to 20% by weight, particularly preferably from 1 to 10% by weight. The amount added is 0.
If the amount is less than 01% by weight, the sensitivity will be low, and if it exceeds 50% by weight, the non-image portion will be stained during printing. Also,
When a recording material is prepared using an infrared absorbing agent, the optical density at the absorption maximum in the infrared region is preferably between 0.1 and 3.0. Outside of this range, the sensitivity will be low. Since the optical density is determined by the amount of the infrared absorbing agent added and the thickness of the recording layer, a predetermined optical density can be obtained by controlling both conditions. The optical density of the recording layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a coating layer after drying is formed to a recording layer having a thickness appropriately determined in a range necessary for a lithographic printing plate, and a transmission type optical densitometer is used. Examples include a method of measuring, a method of forming a recording layer on a reflective support such as aluminum, and measuring a reflection density. These infrared absorbers may be used alone or in combination of two or more. In addition, these infrared absorbers may be added to the same layer as other components, or may be added to another layer provided.

[(C) Radical polymerizable compound] The radical polymerizable compound used in the present invention is a radical polymerizable compound having at least one ethylenically unsaturated double bond, and has a terminal ethylenically unsaturated bond. At least one
, Preferably two or more compounds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These have chemical forms such as, for example, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and are preferred. As the ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene or the like.

Specific examples of the radical polymerizable compound which is an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butane. Diol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, penta Risuri toll triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate,
Examples include sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334 and JP-A-57-196231, and JP-A-59-5240 and JP-A-59-5240. 59-524
1, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule and a hydroxyl-containing vinyl monomer represented by the following formula (III) added to one molecule. And vinyl urethane compounds containing at least two polymerizable vinyl groups.

Formula (III) CH ₂ C (R ⁴¹ ) COOCH ₂ CH (R ⁴² ) OH (where R ⁴¹ and R ⁴² represent H or CH ₃ )

Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and JP-B-58-167.
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909 and JP-A-1-105238 may be used. good.

Another example is disclosed in JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

With respect to these radically polymerizable compounds,
Details of the method of use, such as what kind of structure is used, whether it is used alone or in combination, and how much is added, can be arbitrarily set in accordance with the final performance design of the recording material. For example, it is selected from the following viewpoints. In terms of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable,
In many cases, more than one function is preferred. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functional groups are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic ester, methacrylic ester,
It is also effective to control both the photosensitivity and the strength by using a styrene compound in combination. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in sensitivity and film strength, but may not be preferable in terms of development speed and precipitation in a developer. In addition, the selection and use of the radical polymer compound is also an important factor for the compatibility and dispersibility with other components (for example, a binder polymer, an initiator, a colorant, and the like) in the photosensitive layer. The compatibility may be improved by using a low-purity compound or by using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, the overcoat layer, and the like. Regarding the compounding ratio of the radical polymerizable compound in the image recording layer, a higher ratio is advantageous in sensitivity, but if the ratio is too large, undesired phase separation occurs or the production process due to the stickiness of the image recording layer. (For example, poor production resulting from transfer of recording layer components and adhesion) and problems such as precipitation from a developer. From these viewpoints, the preferred compounding ratio is often 5 to 8 based on all components of the composition.
0% by weight, preferably 20-75% by weight. Also,
These may be used alone or in combination of two or more. In addition, the method of using the radical polymerizable compound can be arbitrarily selected from the viewpoint of the degree of inhibition of polymerization with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, etc. Depending on the case, a layer structure and a coating method such as undercoating and overcoating may be performed.

[(D) Binder polymer] In the present invention, a binder polymer is further used. It is preferable to use a linear organic polymer as the binder. Any of such “linear organic polymers” may be used. Preferably, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is selected to enable development with water or weakly alkaline water. The linear organic polymer is selected and used not only as a film forming agent of an image recording material but also as a developer for water, weakly alkaline water or an organic solvent. For example,
Use of a water-soluble organic polymer enables water development.
Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44.
No. 615, JP-B-54-34327, JP-B-58-1
2577, JP-B-54-25957, JP-A-54-1979
No. 92723, JP-A-59-53836, JP-A-59-53836
No. 71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer Etc. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.

Among these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxyl group in the side chain is particularly preferred because it has an excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-12004,
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength, and therefore is advantageous in terms of printing durability and low exposure suitability.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the polymer used in the present invention is preferably at least 5,000, more preferably 10,000 to 300,000, and the number average molecular weight is preferably at least 1,000, more preferably Is in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

These polymers are random polymers,
Any of a block polymer and a graft polymer may be used, but a random polymer is preferable.

The polymer used in the present invention can be synthesized by a conventionally known method. As a solvent used in the synthesis, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy -2-propanol, 1-methoxy-2-propyl acetate, N, N-
Dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate,
Dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.

As the radical polymerization initiator used when synthesizing the polymer used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used.

The binder polymer used in the present invention may be used alone or as a mixture. These polymers are added to the image recording material in a proportion of 20 to 95% by weight, preferably 30 to 90% by weight, based on the total solid content of the image recording material. When the addition amount is less than 20% by weight, the strength of the image portion is insufficient when an image is formed. When the amount exceeds 95% by weight, no image is formed. The weight ratio of the radical polymerizable compound having an ethylenically unsaturated double bond and the linear organic polymer is preferably in the range of 1/9 to 7/3.

[Other Components] In the present invention, various compounds other than these may be further added, if necessary.
For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BO
S, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue,
Crystal violet (CI42555), methyl violet (CI42535), ethyl violet,
Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI520
15) and the dyes described in JP-A-62-293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can be suitably used.

It is preferable to add these colorants since the image area and the non-image area can be easily distinguished after image formation. The addition amount is based on the total solid content of the image recording material.
The ratio is 0.01 to 10% by weight.

In the present invention, if necessary,
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added so as to be unevenly distributed on the surface of the photosensitive layer during drying after coating. The amount of the higher fatty acid derivative added is about 0.1% by weight of the total composition.
~ 10% by weight is preferred.

The image recording material of the present invention contains a nonionic interface as described in JP-A-62-251740 and JP-A-3-208514 in order to increase the stability of processing under development conditions. Activator, JP-A-59
An amphoteric surfactant as described in JP-A-121044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, and polyoxyethylene nonyl phenyl ether.

Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N , N-betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer is added to the image recording material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like are used.

In the image recording material of the present invention, each of the above-mentioned components is usually dissolved in a solvent and coated on a suitable support. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, water and the like. However, the present invention is not limited to this. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight.

The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally about 0.5 to 5.0 g / m ² for lithographic printing plates. . Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

In the image recording material of the present invention, a surfactant for improving coating properties, for example, JP-A-62-1
No. 70950 can be added. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the image recording material.

[Support] The image recording material of the present invention can be used as a lithographic printing plate precursor by forming a sightseeing layer by coating it on a suitable support. The support to which the image recording material of the present invention can be applied is a dimensionally stable plate-like material,
For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited. Preferred supports include a polyester film or an aluminum plate.

When the image recording material of the present invention is used as a lithographic printing plate, it is preferable to use a lightweight aluminum plate having excellent surface treatment properties, workability and corrosion resistance as a support. Aluminum materials used for this purpose include JIS 1050 material, JIS 1100 material, JIS
1070 material, Al-Mg based alloy, Al-Mn based alloy,
Al-Mn-Mg based alloy, Al-Zr based alloy. Al-M
A g-Si alloy or the like is used.

Known techniques relating to aluminum materials that can be used for the support are listed below. (1) The following technology is disclosed for JIS 1050 material. JP-A No. 59-153861, JP-A No. 61-38661
-51395, JP-A-62-1146694, JP-A-60-160
215725, JP-A-60-215726, JP-A-6-215726
JP-A-215727, JP-A-60-215728, JP-A-61-272357, JP-A-58-11759, JP-A-58-42493, JP-A-58-221254, JP-A-62-148295, JP-A-Hei. 254545, Japanese Patent Application Laid-Open No. 4-165041, Japanese Patent Publication No. 3-68939, Japanese Patent Application Laid-Open
234594, Japanese Patent Publication No. 47475 / JP-A-62-1
No. 40894, and the like. In addition, Japanese Patent Publication 1-35910,
Japanese Patent Publication No. 55-28874 is also known.

(2) The following techniques are disclosed for JIS 1070 materials. JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-49034
-73974, JP-A-8-108559, JP-A-8-9
No. 2679.

(3) With respect to Al-Mg based alloys, the following techniques are disclosed. JP-B-62-5080, JP-B-63-60823, JP-B-3-61753, JP-A-60-60
-203496, JP-A-60-203497, Tokuhei 3
-11635, JP-A-61-274993, JP-A-61-27499
-23794, JP-A-63-47347, JP-A-63-473-
47348, JP-A-63-47349, JP-A-64-6
1293, JP-A-63-135294, JP-A-63-8
7288, Tokuhei 4-73392, Tokuhei 7-1008
44, JP-A-62-149856, JP-B-4-7339
4, JP-A-62-181191, Japanese Patent Publication 5-7653
0, JP-A-63-30294 and JP-B-6-37116. Further, JP-A-2-215599, JP-A-61-2
01747 and the like are also known.

(4) With respect to Al-Mn alloys, the following techniques are disclosed. JP-A-60-230951, JP-A-1-306288, JP-A-2-293189, and the like. In addition, Japanese Patent Publication 54-42284, Japanese Patent Publication 4-192
90, Japanese Patent Publication 4-19291, Japanese Patent Publication 4-19292,
JP-A-61-35995, JP-A-64-51992, U
S5009722, US5028276, JP-A-4-24-2
26394 and the like are also known.

(5) Regarding the Al—Mn—Mg alloy,
The following technology is disclosed. JP-A-62-2614
3, JP-A-3-222796. Also, JP-B 63-60
824. JP-A-60-63346, JP-A-60-633
47, EP 223737, JP-A-1-283350, U
S4818300 and BR1222777 are known.

(6) The following techniques are known for Al-Zr alloys. JP-B-63-15978; JP-A-6-15978
1-51395. Further, JP-A-63-143234 and JP-A-63-143235 are also known.

(7) Regarding the Al—Mg—Si alloy,
BR14221710 and the like are known.

The following contents can be used as a method for producing an aluminum plate for a support. The aluminum alloy melt having the above-mentioned content components and alloy component ratios is subjected to a cleaning treatment and cast according to a conventional method. For the cleaning process,
In order to remove unnecessary gases such as hydrogen in the molten metal, flux treatment, degassing treatment using Ar gas, Cl gas, etc., so-called rigid media filters such as ceramic tube filters and ceramic foam filters, and alumina flakes , Filter using alumina ball, etc. as filter medium, or filtering using glass cloth filter. Alternatively, a process combining degassing and filtering is performed. These cleaning treatments are desirably performed in order to prevent defects due to foreign substances such as nonmetallic inclusions and oxides in the molten metal and defects due to gas dissolved in the molten metal.

Regarding the filtering of the molten metal, Japanese Patent Application Laid-Open Nos. Hei 6-57342, Hei 3-162530, Hei 5
140659, JP-A-4-231425, JP-A-4-2
76031, JP-A-5-311261, JP-A-6-13
6466 and the like are known.

Regarding the degassing of molten metal, see Japanese Unexamined Patent Publication No. 5-51
659, JP-A-5-51660, JP-A-5-4914
8, JP-A-7-40017 and the like are known.

As described above, casting is performed using the molten metal subjected to the cleaning treatment. Regarding the casting method, there are a method using a fixed mold typified by a DC casting method and a method using a driving mold typified by a continuous casting method. When the DC casting method is used, the solidification is performed at a cooling rate of 1 to 300 ° C./sec. When the temperature is less than 1 ° C./sec, a large number of coarse intermetallic compounds are formed.

The continuous casting method includes a method using a cooling roll, represented by the Hunter method and the 3C method, a Hadley method, a method using a cooling belt represented by the Al Swiss Caster II type, and a method using a cooling block. It is being done. The cooling rate when using the continuous casting method is 100 to 1000 ° C. /
Coagulated in seconds. Generally, since the cooling rate is higher than that of the DC casting method, the alloy has a feature that the solid solubility of the alloy component in the aluminum matrix can be increased. Regarding the continuous casting method, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 3-7 / 1990.
9798, JP-A-5-201166, JP-A-5-156
414, JP-A-6-262203, JP-A-6-1229
49, JP-A-6-210406, JP-A-6-26230
8 etc. are disclosed.

When DC casting is performed, the thickness is 300 to 80.
A 0 mm ingot can be manufactured. The ingot, according to the usual method,
Facing is performed and the surface layer is 1 to 30 mm. Preferably, 1 to
10 mm is cut. Thereafter, if necessary, a soaking process is performed. In the case of performing the soaking treatment, 1 to 450 ° C. to 620 ° C. is used to prevent the intermetallic compound from becoming coarse.
The heat treatment is performed for at least 48 hours. When the time is shorter than 1 hour, the effect of the soaking treatment becomes insufficient. Next, hot rolling and cold rolling are performed to obtain a rolled aluminum plate. The starting temperature of hot rolling is 350 to 500
It is in the range of ° C. Intermediate annealing treatment may be performed before, after, or during the cold rolling. The intermediate annealing conditions in this case are set to 280 ° C. to 6 ° C. using a batch annealing furnace.
2 hours to 20 hours at 00C. Desirably, 350 to 500 ° C
Heating for 2 to 10 hours or using a continuous annealing furnace for 4 hours.
360 seconds or less at 00 to 600 ° C., desirably 450 to
Heat treatment at 550 ° C. for 120 seconds or less can be employed. Heating at a rate of 10 ° C./sec or higher using a continuous annealing furnace can also make the crystal structure fine.

According to the above steps, a predetermined thickness of 0.1 to 0.1
The flatness of the Al plate finished to 0.5 mm may be improved by a straightening device such as a roller leveler or a tension leveler in order to improve the flatness. The flatness may be improved after the plate is cut into a sheet, but it is desirable to improve the flatness in a continuous coil state in order to improve productivity. Further, in order to process the board width to a predetermined width, a slitter line is usually passed. The end face of the plate cut by the slitter has one or both of a shear surface and a fracture surface when cut by a slitter blade.

The accuracy of the thickness of the plate is preferably within ± 10 μm, preferably within ± 6 μm over the entire length of the coil.
The thickness difference in the width direction is within 6 μm, preferably 3 μm.
Within is good. Also, the accuracy of the board width is within ± 1.0mm,
Preferably, it is within ± 0.5 mm. The surface roughness of the Al plate is easily affected by the surface roughness of the rolling roll,
Finally, the center line surface roughness (Ra) is Ra = 0.1 to
It is preferable to finish to about 1.0 μm. If Ra is too large, the original roughness of Al, that is, the rough rolling streaks transferred by the rolling rolls can be seen from above the photosensitive layer when the surface is roughened for a lithographic printing plate and the photosensitive layer is applied. Is not preferable in appearance. Roughness of Ra = 0.1 μm or less is industrially undesirable because the surface of the rolling roll needs to be finished to an excessively low roughness.

Further, a thin oil film may be formed on the surface of the Al plate in order to prevent scratches due to friction between the Al plates. Oil slicks may be volatile,
A non-volatile one is appropriately used. If there is too much oil,
A slip failure occurs in the production line, but if there is no oil amount, a defect occurs during transportation of the coil. Therefore, the oil amount is 3 mg / m ² or more and 100 mg / m ² or less, and a desirable upper limit is 50 mg / m ^2. m ² or less, more preferably 10
mg / m ² or less is good. Regarding cold rolling,
-210308 and the like are disclosed.

In the case of performing continuous casting, for example, using a cooling roll such as a Hunter method, a cast plate having a thickness of 1 to 10 mm can be directly continuously cast and rolled, and there is an advantage that the step of hot rolling can be omitted. In addition, when a cooling roll such as the Hasley method is used, a cast plate having a plate thickness of 10 to 50 mm can be cast,
In general, a hot-rolled roll is arranged immediately after casting and continuously rolled to obtain a continuously cast rolled plate having a thickness of 1 to 10 mm. These continuous cast rolled sheets are finished to a thickness of 0.1 to 0.5 mm through the steps of cold rolling, intermediate annealing, improvement of flatness, slits, etc., as described in the case of DC casting. Can be Regarding the intermediate annealing condition and the cold rolling condition when the continuous casting method is used, refer to JP-A-6-2205.
93, JP-A-6-210308, JP-A-7-5541
1, JP-A-8-92709 and the like are disclosed.

The aluminum plate manufactured by the above method can be subjected to a surface treatment such as a surface roughening treatment, and a photosensitive layer can be applied to obtain a lithographic printing plate. In the surface roughening treatment, mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening are performed alone or in combination. Further, it is also preferable to perform an anodic oxidation treatment for securing the surface with difficulty in scratching or a treatment for increasing the hydrophilicity.

The surface treatment of an aluminum plate used as a support will be described below. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface may be performed. In the case of alkali, treatment such as neutralization and removal of smut may be performed with an acidic solution.

Next, in order to improve the adhesion between the support and the photosensitive layer and to impart water retention to the non-image area, a so-called graining treatment is performed to roughen the surface of the support. Specific means of the graining method include sand blast, ball grain, wire grain, brush grain using a nylon brush and an abrasive / water slurry,
There is a mechanical graining method using a honing grain or the like in which an abrasive / water slurry is sprayed onto the surface at a high pressure, and a chemical graining method in which the surface is roughened with an etching agent composed of an alkali, an acid, or a mixture thereof. . In addition, British Patent No. 896,563,
JP-A-3-67507, JP-A-54-146234 and JP-B-48-28123 describe the method of electrochemical graining, or JP-A-53-1232.
No. 04, JP-A-54-63902 and a combination of the mechanical graining method and the electrochemical graining method described in JP-A-56-55261. A method is also known in which a graining method is combined with a chemical graining method using a saturated aqueous solution of an aluminum salt of a mineral acid. Also, a method of bonding the granular material to the support material with an adhesive or a method having the effect thereof to roughen the surface, or a continuous band or roll having fine unevenness is pressed against the support material to remove the unevenness. A rough surface may be formed by transferring.

A plurality of such surface roughening methods may be performed in combination, and the order, the number of repetitions, and the like can be arbitrarily selected. When a plurality of surface roughening treatments are combined, a chemical treatment with an acid or alkali aqueous solution can be performed during that time to make the subsequent surface roughening treatment uniform. Specific examples of the above-mentioned acid or alkali aqueous solution include, for example, acids such as hydrofluoric acid, fluorinated zirconic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid, and alkali aqueous solutions such as sodium hydroxide, sodium silicate, and sodium carbonate. . These acid or alkali aqueous solutions can be used alone or in combination of two or more. For the chemical treatment, a 0.05 to 40% by weight aqueous solution of these acids or alkalis is used.
In general, the treatment is performed at a liquid temperature of 0 ° C. for 5 to 300 seconds.

Since a smut is formed on the surface of the support obtained by the above-mentioned surface roughening treatment, ie, graining treatment, a treatment such as washing with water or alkali etching is appropriately performed to remove the smut. Is generally preferred. Examples of such processing include, for example,
Examples thereof include a treatment method such as an alkali etching method described in JP-A-8-28123 and a desmutting sulfate method described in JP-A-53-12739.

In the case of the aluminum support used in the present invention, after the pretreatment as described above, the support is usually anodized to improve abrasion resistance, chemical resistance and water retention. To form an oxide film.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film.
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. Anodizing treatment conditions vary depending on the electrolyte used, and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. It is appropriate that the voltage is in the range of 1 to 100 V and the electrolysis time is in the range of 10 seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. "Scratch dirt"
Tends to occur.

[0095] Although such anodizing treatment is performed on a surface used for printing of the support of the lithographic printing plate, the back around the electric lines of force, on the back surface of 0.01 to 3 g / m ² anode Generally, an oxide film is formed. Further, an anodic oxidation treatment in an alkaline aqueous solution (for example, a caustic soda aqueous solution of several%) or a molten salt, or an anodic oxidation treatment for forming a non-porous anodic oxide film using, for example, an ammonium borate aqueous solution can be performed. .

Before performing the anodic oxidation treatment, refer to
Alternatively, a hydrated oxide film described in JP-A-8991 or JP-A-4-97896 may be formed.
No. 56497 and JP-A-63-67295, a treatment in a metal silicate solution, a hydrated oxide film forming treatment, and a chemical conversion film forming treatment described in JP-A-56-144195. You can do it too.

The aluminum support of the present invention can be treated with an organic acid or a salt thereof after anodic oxidation treatment, or used as an undercoat layer for coating a photosensitive layer. Examples of the organic acid or a salt thereof include an organic carboxylic acid, an organic phosphonic acid, an organic sulfonic acid or a salt thereof, and preferably an organic carboxylic acid or a salt thereof. Examples of the organic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid and stearic acid; unsaturated aliphatic monocarboxylic acids such as oleic acid and linoleic acid; oxalic acid and succinic acid Aliphatic dicarboxylic acids such as adipic acid and maleic acid; oxycarboxylic acids such as lactic acid, gluconic acid, malic acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid, mandelic acid, salicylic acid and phthalic acid; IIb, IIIb, IVa, VIb and VIII
Group metal salts and ammonium salts. Preferred among the organic carboxylate salts are formic acid, acetic acid, butyric acid,
The above-mentioned metal salts and ammonium salts of propionic acid, lauric acid, oleic acid, succinic acid and benzoic acid.
These compounds may be used alone or in combination of two or more.

These compounds are used in water and alcohol in 0.0
It is preferably dissolved in a concentration of from 0.01 to 10% by weight, particularly from 0.01 to 1.0% by weight. The processing conditions include a temperature range of 25 to 95 ° C, preferably 50 to 95 ° C.
H is 1 to 13, preferably 2 to 10, 10 seconds to 20 minutes,
Preferably, the support is immersed for 10 seconds to 3 minutes, or the treatment liquid is applied to the support.

Further, after the anodic oxidation treatment, the following treatment with a compound solution or these compounds can be used as an undercoat layer for coating the photosensitive layer. Suitable compounds include, for example, optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, organic phosphonic acids such as methylenediphosphonic acid and ethylenediphosphonic acid, substituted Phenyl phosphate, naphthyl phosphate, which may have a group,
Organic phosphoric acids such as alkyl phosphoric acid and glycerophosphoric acid, organic phosphinic acids such as optionally substituted phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, glycine, β
-Amino acids such as alanine, valine, serine, threonine, aspartic acid, glutamic acid, arginine, lysine, tryptophan, parahydroxyphenylglycine, dihydroxyethylglycine, and anthranilic acid; aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid; 1-amino acid Methylphosphonic acid, 1-dimethylaminoethylphosphonic acid, 2-aminoethylphosphonic acid, 2-aminopropylphosphonic acid, 4-aminophenylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl Aminophosphonic acids such as methane-1,1-diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid, and ethylenediaminetetramethylenephosphonic acid; Compounds, and the like.

Further, salts of hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid (such as methanesulfonic acid) or oxalic acid with alkali metals, ammonia, lower alkanolamines (such as triethanolamine), lower alkylamines (such as triethylamine), etc. It can be suitably used.

Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine and its mineral salts, poly (meth) acrylic acid and its metal salts, polystyrenesulfonic acid and its metal salts, alkyl (meth) acrylate and 2-acrylamide Water-soluble polymers such as 2-methyl-1-propanesulfonic acid and metal salts thereof, polymers of trialkylammonium methylstyrene styrene and copolymers thereof with (meth) acrylic acid, and polyvinylphosphonic acid can also be suitably used. it can.

Further, soluble starch, carboxymethylcellulose, dextrin, hydroxyethylcellulose, gum arabic, guar gum, sodium alginate, gelatin, glucose, sorbitol and the like can also be suitably used. These compounds may be used alone or in combination of two or more.

In the case of treatment, these compounds are preferably dissolved in water and / or methyl alcohol at a concentration of 0.001 to 10% by weight, particularly 0.01 to 1.0% by weight. The support is immersed in a temperature range of 25 to 95 ° C, preferably 50 to 95 ° C, and the pH is 1 to 13, preferably 2 to 10, 10 seconds to 20 minutes, and preferably 10 seconds to 3 minutes.

When used as an undercoat layer for coating the photosensitive layer, water and / or methyl alcohol may be added in the same manner as above.
10 to 10% by weight, particularly 0.01 to 1.0% by weight, and dissolved as necessary. Basic substances such as ammonia, triethylamine and potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid The pH is adjusted by the substance,
It can also be used in the range of ~ 12. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is 2 to
200 mg / m ² is suitable, preferably 5 to 100 mg / m ^2.
mg / m ² . If the above-mentioned coating amount is less than 2 mg / m ² , a sufficient effect for the original purpose such as prevention of stain cannot be obtained. On the other hand, if it exceeds 200 mg / m ² , the strength of an image formed by curing is reduced.

An intermediate layer for improving the adhesion between the support and the photosensitive layer may be provided. To improve adhesion,
Generally, the intermediate layer is made of a diazo resin or a phosphoric acid compound adsorbed on aluminum, for example. The thickness of the intermediate layer is arbitrary, and must be such a thickness that a uniform bond-forming reaction with the upper photosensitive layer can be performed when exposed. Normal,
The dry solid has a good coating ratio of about 1 to 100 mg / m ² ,
5-40 mg / m ² are particularly good. The usage ratio of the diazo resin in the intermediate layer is 30 to 100%, preferably 60 to 100%.

Before the above-described treatment and the application of the undercoat layer, the support subjected to the anodic oxidation treatment is washed with water, and thereafter, the dissolution of the anodic oxide film in the developing solution, the suppression of the remaining film of the photosensitive layer components, The following treatments can be performed for the purpose of improving the strength of the anodic oxide film, improving the hydrophilicity of the anodic oxide film, and improving the adhesion to the photosensitive layer.

One of them is a silicate treatment in which the anodic oxide film is brought into contact with an aqueous solution of an alkali metal silicate to carry out the treatment. In this case, the concentration of the alkali metal silicate is 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and the pH at 25 ° C is 10 to 13.5 in an aqueous solution at 5 to 80 ° C. The contact is preferably performed at 10 to 70 ° C, more preferably 15 to 50 ° C for 0.5 to 120 seconds.
The contacting method may be any method such as dipping or spraying. When the pH of the aqueous alkali metal silicate solution is lower than 10, the solution gels,
If it is higher than 13.5, the anodic oxide film will be dissolved.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used for adjusting the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The treatment liquid may contain an alkaline earth metal salt or a Group IVb metal salt. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Salts. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, and the like. Alkaline earth metal or No.
Group IVb metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.1.
01 to 10% by weight, more preferably 0.05 to 10% by weight.
5.0% by weight.

In addition, various sealing treatments can be mentioned, and steam sealing, boiling water (hot water) sealing, metal salt sealing (generally known as a method for sealing an anodic oxide film) are also available. Chromate / dichromate seal, nickel acetate seal, etc.), oil impregnated seal, synthetic resin seal, low temperature seal (by red blood salt or alkaline earth salt, etc.) can be used. , Performance as a support for a printing plate (adhesion to the photosensitive layer and hydrophilicity),
From the viewpoints of high-speed processing, low cost, and low pollution, steam sealing is relatively preferred. As the method, for example,
No. 176690 discloses a method for continuously or discontinuously applying pressurized or normal pressure steam to a anodic oxide film at a relative humidity of 70% or more and a steam temperature of 95 ° C. or more for about 2 to 180 seconds. And the like. As another sealing treatment method, a method of immersing or spraying the support in hot water or an aqueous alkali solution at about 80 to 100 ° C.,
Alternatively or subsequently, it can be dipped or sprayed with a nitrous acid solution. Examples of nitrites include Ia, IIa, IIb, IIIb, IVb, IVa, VIa of the periodic table.
a, VIIa, and VIII metal nitrites or ammonium salts, ie, ammonium nitrite, such as LiO ₂ , NaNO ₂ , KNO ₂ , M
g (NO ₂ ) ₂ , Ca (NO ₂ ) ₂ , Zn (NO ₃ ) ₂ , Al
(NO ₂ ) ₃ , Zr (NO ₂ ) ₄ , Sn (NO ₂ ) ₃ , Cr
(NO ₂ ) ₃ , Co (NO ₂ ) ₂ , Mn (NO ₂ ) ₂ , Ni
(NO ₂ ) _{2 and the} like are preferable, and alkali metal nitrite is particularly preferable. Two or more nitrites can be used in combination.

The processing conditions cannot be uniquely determined because they vary depending on the state of the support and the type of alkali metal.
For example, when sodium nitrite is used, the concentration is generally 0.001 to 10% by weight, more preferably 0.01 to 10% by weight.
1-2% by weight, bath temperature generally from room temperature to about 100 ° C
Before and after, more preferably at 60 to 90 ° C., and the treatment time may be generally selected from the respective ranges of 15 to 300 seconds, more preferably 10 to 180 seconds. Nitrous acid aqueous solution
H is preferably adjusted to 8.0 to 11.0, and particularly preferably adjusted to 8.5 to 9.5. To adjust the pH of the nitrous acid aqueous solution to the above range,
For example, it can be suitably prepared using an alkaline buffer or the like. Examples of the alkaline buffer include, but are not limited to, a mixed aqueous solution of sodium hydrogen carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydrogen carbonate, and a mixed aqueous solution of sodium chloride and sodium hydroxide. Mixed aqueous solution,
A mixed aqueous solution of hydrochloric acid and sodium carbonate, a mixed aqueous solution of sodium tetraborate and sodium hydroxide, and the like can be suitably used. Further, as the alkaline buffer, an alkali metal salt other than sodium, for example, a potassium salt can be used.

After performing the silicate treatment or the sealing treatment as described above, in order to improve the adhesion to the photosensitive layer, an acidic aqueous solution treatment and a hydrophilic undercoat disclosed in JP-A-5-278362 are applied. And Japanese Patent Application Laid-Open
An organic layer disclosed in Japanese Patent No. 282637 or JP-A-7-314937 may be provided.

After the above-described treatment or undercoating is applied to the surface of the support, a back coat is provided on the back surface of the support as necessary. As such a back coat, a coating layer comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 is used. It is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC
_{2 H 5) 4, Si (} OC 3 H 7) 4, Si (OC 4 H 9) is easily available and inexpensive alkoxy compounds of silicon such as _4, the coating layer of the obtained therefrom metal oxide in developing solution Excellent and particularly preferred.

The preferred characteristics of the lithographic printing plate support are 0.10 to 1.2 μm in center line average roughness. If it is less than 0.10 μm, the adhesion to the photosensitive layer is reduced,
Significant reduction in printing durability occurs. If it is larger than 1.2 μm, the stain on printing will be deteriorated. Further, the color density of the support is 0.15 to 0.5 as a reflection density value.
65, and when it is whiter than 0.15, the halation at the time of image exposure is too strong and hinders image formation.
When it is darker than 0.65, the image is difficult to see in the plate inspection work after development, and the plate inspection property is extremely poor.

As described above, a planographic printing plate using the image recording material of the present invention can be prepared. This lithographic printing plate can be recorded with an infrared laser. Also,
Thermal recording with an ultraviolet lamp or a thermal head is also possible. In the present invention, the wavelength from 760 nm to 120
It is preferable that the image is exposed by a solid-state laser and a semiconductor laser that emit 0-nm infrared light. The output of the laser is preferably 100 mW or more, and in order to shorten the exposure time,
Preferably, a multi-beam laser device is used.
Further, the exposure time per pixel is preferably within 20 μsec. The energy applied to the recording material is 10
It is preferably ~300mJ / cm ^2.

After exposure with an infrared laser, the image recording material of the present invention is preferably developed with water or an aqueous alkaline solution.

When an alkaline aqueous solution is used as a developer, a conventionally known alkaline aqueous solution can be used as a developer and a replenisher for the image recording material of the present invention. For example,
Sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, Inorganic alkali salts such as sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Also, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. Organic alkaline agents are also used. These alkali agents are used alone or in combination of two or more.

Further, when developing using an automatic developing machine, the same solution as the developing solution or an aqueous solution having a higher alkali strength than the developing solution (replenishing solution) is added to the developing solution to allow the developing tank to be maintained for a long time. It is known that a large amount of lithographic printing plate material can be processed without replacing the developer. This replenishment system is also preferably applied in the present invention.

Various surfactants, organic solvents and the like can be added to the developing solution and the replenishing solution, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof. Further, non-reducing sugars such as arabit, sorbit, and mannitol can also be added.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, and hard water. Softeners can also be added.

Examples of such a developer containing a surfactant, an organic solvent, a reducing agent and the like include, for example, those described in
Benzyl alcohol described in No. 77401,
A developer composition comprising an anionic surfactant, an alkali agent and water, comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite as described in JP-A-53-44202; Developer composition,
Examples thereof include a developer composition containing an organic solvent, an alkali agent, and water having a solubility in water of 10% by weight or less at room temperature described in JP-A-55-155355. Used for

The printing plate developed using the above-described developing solution and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. You. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such automatic processing,
Processing can be performed while replenishing each processing solution with a replenisher according to the processing amount, operating time, and the like. In addition, the electric conductivity can be detected by a sensor and replenished automatically. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitizing gum as required, but when the lithographic printing plate is desired to have a higher printing durability, Is subjected to a burning process.

When burning a lithographic printing plate, prior to burning, JP-B Nos. 61-2518 and 55-280.
No. 62, JP-A-62-131859 and JP-A-61-1596.
It is preferable to treat with a surface-regulating liquid as described in each of the publications No. 55.

[0125] As a method for this, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied onto a lithographic printing plate,
A method in which a printing plate is immersed in a vat filled with a surface conditioning liquid to apply the printing plate, an application using an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ^2.
(Dry weight) is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried, if necessary, and then burned by a burning processor (for example,
It is heated to a high temperature by a burning processor (BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 180 ° C. to 300 ° C.
A range of up to 20 minutes is preferred.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary. However, a surface conditioning solution containing a water-soluble polymer compound or the like can be used. When is used, so-called desensitizing treatment such as gumming can be omitted.

The lithographic printing plate obtained by such a process is set on an offset printing machine or the like, and used for printing a large number of sheets.

[0129]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. (Examples 1 and 2) [Preparation of support] 99.5% or more of aluminum and F
e 0.30%, Si 0.10%, Ti 0.02%, C
u A molten metal of JIS A1050 alloy containing 0.013% was subjected to cleaning treatment and cast. In the cleaning treatment, a degassing treatment was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter treatment was performed. The casting was performed by DC casting. The solidified ingot having a thickness of 500 mm was chamfered from the surface by 10 mm, and homogenized at 550 ° C. for 10 hours to prevent the intermetallic compound from becoming coarse. Next, after hot rolling at 400 ° C. and intermediate annealing in a continuous annealing furnace at 500 ° C. for 60 seconds, cold rolling was performed to obtain a rolled aluminum sheet having a sheet pressure of 0.30 mm. The center line average surface roughness Ra after cold rolling was controlled to 0.2 μm by controlling the roughness of the rolling roll. Then, it was subjected to a tension leveler to improve the flatness.

Next, a surface treatment for forming a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, a degreasing treatment was performed with a 10% aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and a 30% sulfuric acid aqueous solution was neutralized at 50 ° C. for 30 seconds and a smut removal treatment was performed.

Next, in order to improve the adhesion between the support and the photosensitive layer and to impart water retention to the non-image area, a so-called graining treatment for roughening the surface of the support was performed. 1%
Aqueous solution containing 0.5% nitric acid and 0.5% aluminum nitrate
° C while flowing an aluminum web in an aqueous solution, the anode-side electricity quantity 240 C / dm ² with an alternating waveform having a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect feeding cell.
Electrolytic graining was performed by giving ² . Then 10%
Perform an etching treatment with a sodium aluminate aqueous solution at 50 ° C for 30 seconds, and neutralize with a 30% aqueous sulfuric acid solution at 50 ° C for 30 seconds.
Smut removal processing was performed.

To further improve abrasion resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodic oxide film of 2.5 g / m ^{2 is} obtained by performing an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power supply cell while carrying an aluminum web through the electrolyte using a 20% aqueous solution of sulfuric acid at 35 ° C. as an electrolyte. It was created.

Thereafter, a silicate treatment was performed to ensure hydrophilicity as a non-image portion of the printing plate. For the treatment, a 1.5% aqueous solution of sodium silicate No. 3 was maintained at 70 ° C., passed through the aluminum web so that the contact time was 15 seconds, and further washed with water. S
The attached amount of i was 10 mg / m ² . Ra (center line surface roughness) of the support thus prepared was 0.25 μm.

[Undercoat] Next, the following undercoat solution was applied to the aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air drier. The coating amount after drying was 10 mg / m ² .

<Undercoat liquid> 0.1 g of a copolymer of ethyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15 0.1 g 2-aminoethylphosphonic acid 0.1 g 50 g of methanol 50 g of ion exchange water

[Photosensitive layer] Next, the following solution [P] was prepared, and this solution was applied to the above-mentioned primed aluminum plate using a wire bar, and then heated in a hot-air drying apparatus.
After drying at 5 ° C for 45 seconds, a negative type lithographic printing plate [P-
1] and [P-2]. The coating amount after drying is 1.3 g /
m2. Table 1 shows the N-nitrosamine compounds used at this time.

<Solution [P]> ・ Infrared absorber [IR-1] 0.10 g ・ N-nitrosamine-based compound (compound shown in Table 1) 0.30 g ・ Dipentaerythritol hexaacrylate 1.00 g ・ Allyl methacrylate Copolymer with methacrylic acid in a molar ratio of 80:20 (weight average molecular weight 120,000) 1.00 g ・ Victoria pure blue naphthalene sulfonate 0.04 g ・ Behenic acid amide 0.05 g ・ Fluorine surfactant 0.0 01 g (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.) 9.0 g of methyl ethyl ketone 10.0 g of methanol 8.0 g of 1-methoxy-2-propanol

[0138]

[Table 1]

[Exposure] The obtained negative type lithographic printing plate materials [P-1] and [P-2] were used as a Trendsetter manufactured by Creo Corporation equipped with a water-cooled 40 W infrared semiconductor laser.
At 3244VFS, output 9W, outer drum rotation speed 21
Exposure was performed under the conditions of 0 rpm, plate surface energy 100 mJ / cm ² , and resolution 2400 dpi.

[Development processing] After exposure, development processing was carried out using an automatic developing machine Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As a developing solution, a 1: 2 aqueous solution of DN-3C manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing bath was 30 ° C. Also, the finisher
A 1: 1 aqueous dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

[Evaluation of Image Formability] After performing the above operations, it was visually evaluated whether or not an image was formed. [P-1] using an N-nitrosamine-based compound was evaluated.
Clear images were obtained with any of [P-2] using the N-nitrosamine compound and a known radical polymerization initiator in combination.

(Comparative Example 1) A lithographic printing plate was prepared in the same manner as in Examples 1 and 2, except that the N-nitrosamine compound was omitted from the solution [P] used in Examples 1 and 2. Material [Q-1] was obtained. The obtained lithographic printing plate material [Q-1] was exposed and developed in the same manner as in Examples 1 and 2, and whether or not an image was formed was visually checked. No image remained and no image was formed.

Comparative Example 2 In the solution [P] used in Examples 1 and 2, the radical polymerization initiator was replaced with an N-nitrosamine-based compound.
Except for using the benzoyl peroxide described in No.
Coating and drying were performed in the same manner as in Examples 1 and 2 to obtain a lithographic printing plate material [Q-2]. The obtained planographic printing plate material [Q-2]
Was exposed and developed in the same manner as in Examples 1 and 2, and it was visually confirmed whether or not an image was formed. However, nothing was left on the support, and no image was formed.
As described above, when only the conventionally known radical polymerization initiator was used, the image was not formed when the developing treatment was performed without performing the heat treatment.

(Examples 3 to 6) The following solution [R] was prepared on the undercoated aluminum support prepared in Examples 1 and 2, and was applied using a wire bar, and was heated with a hot-air dryer. After drying at 115 ° C. for 45 seconds, a negative type lithographic printing plate material [R
-1] to [R-4] were obtained. 1.3 g of coating after drying
/ M ² . Table 2 shows the N-nitrosamine compounds used at this time.

<Solution [R]> ・ Infrared absorber [IR-6] 0.10 g ・ N-nitrosamine-based compound (compound shown in Table 2) 0.30 g ・ Polyfunctional monomer having the following structure 1.00 g ・ 4 1,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, tetraethylene glycol and 2,2-bis (hydroxymethyl) propionic acid in a molar ratio of 30: 20: 30: 20 (weight average molecular weight: 60,000) 1.00 g・ Naphthalene sulfonate of Victoria Pure Blue 0.04 g ・ Stearic acid 0.05 g ・ Fluorine surfactant 0.01 g (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.) ・ Methyl ethyl ketone 5.0 g ・Methanol 10.0 g ・ 1-Methoxy-2-propanol 8.0 g ・ Methyl lactate 2.0 g ・ γ-butyrolactone 2.0 g

[0146]

Embedded image

[0147]

[Table 2]

[Exposure] The obtained negative type lithographic printing plate materials [R-1] to [R-4] were subjected to Luxel manufactured by Fuji Photo Film Co., Ltd. equipped with a multi-channel laser head.
25 output per beam at T-9000CTP
0 mW, external drum rotation speed 800 rpm, resolution 240
Exposure was performed under the condition of 0 dpi.

After the exposure, development processing was performed in the same manner as in Examples 1 and 2, and whether or not an image was formed was visually evaluated. [R-1]-using N-nitrosamine type compound
In all of [R-4], clear images were obtained.

Comparative Example 3 A lithographic printing plate was coated and dried in the same manner as in Examples 3 to 6, except that the N-nitrosamine compound was omitted from the solution [R] used in Examples 3 to 6. Material [S-1] was obtained. The obtained lithographic printing plate material [S-1] was exposed and developed in the same manner as in Examples 3 to 6, and it was visually confirmed whether or not an image was formed. No image remained and no image was formed.

(Comparative Example 4) In the solution [R] used in Examples 3 to 6, instead of the N-nitrosamine-based compound as the radical polymerization initiator, JP-A-8-108621 was used.
Except for using the benzoyl peroxide described in No.
Coating and drying were performed in the same manner as in Examples 3 to 6 to obtain a lithographic printing plate material [S-2]. The obtained planographic printing plate [S-2]
Was exposed and developed in the same manner as in Examples 3 to 6, and whether or not an image was formed was visually checked. However, nothing was left on the support, and no image was formed.
As described above, when only the conventionally known radical polymerization initiator was used, the image was not formed when the developing treatment was performed without performing the heat treatment.

[0152]

According to the present invention, it is possible to directly record digital data from a computer or the like by recording using a solid-state laser and a semiconductor laser that emit infrared light.
It is possible to provide a negative image recording material capable of forming a clear image without performing a heat treatment at the time of image formation.

 ────────────────────────────────────────────────── ─── Continued on front page F term (reference) 2H025 AA01 AB03 AB09 AB13 AC08 AD01 BC13 BC31 CA22 CB00 CC11 CC20 FA10 FA17 2H114 AA04 AA23 BA01 BA10 DA03 DA21 DA32 DA34 DA41 DA43 DA52 DA53 DA58 DA60 EA01 EA02

Claims (1)

[Claims] 1. An infrared ray recording comprising (A) an infrared absorber, (B) an N-nitrosamine-based compound, (C) a radical polymerizable compound, and (D) a binder polymer. Possible negative type image recording material.