JP2003114532A - Negative image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative image forming material capable of direct recording from digital data of a computer or the like by recording using a solid laser and a semiconductor laser which emit IR and capable of obtaining a planographic printing plate excellent in image forming property and printing resistance. SOLUTION: The negative image forming material is obtained by disposing a silicate film, an intermediate layer comprising an aluminum compound having a functional group capable of reacting with a hydroxyl group on the silicate film under heat and a photosensitive layer comprising (A) an IR absorbent, (B) a radical generator and (C) a radical polymerizable compound in order on an aluminum support.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a so-called direct plate-making negative type image forming material capable of making a plate directly by scanning an infrared laser on the basis of a digital signal from a computer or the like.

[0002]

2. Description of the Related Art Conventionally, as a system for directly making a plate from digital data of a computer, an electrophotographic method, a photopolymerization system in which a laser emitting blue or green light is used for exposure, and a silver salt on a photosensitive resin are used. Layered products, silver salt diffusion transfer processes, etc. have been proposed.

However, in the method using the electrophotographic method, the process of image formation such as charging, exposure and development is complicated, and the apparatus becomes complicated and large-scale. Further, with the photopolymerization system of (1), since a plate material having high sensitivity to blue and green light is used, handling in a bright room becomes difficult. The methods (1) and (2) have drawbacks such that the processing such as development is complicated because a silver salt is 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 rays having a wavelength of 760 nm to 1200 nm have been readily available in 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 cannot be image-recorded with these infrared lasers because the photosensitive wavelength is in the visible light region of 760 nm or less. Therefore, a material that can be recorded by an infrared laser is desired.

As an image recording material capable of recording with such an infrared laser, there is a recording material described in US Pat. No. 4,708,925, which comprises an onium salt, a phenol resin and a spectral sensitizer. This image recording material is a positive type image recording material utilizing the effect of suppressing dissolution in a developing solution which is exhibited by an onium salt and a phenol resin, and is not a negative type image recording material as in the present invention. On the other hand, as a negative image recording material, a recording material composed of an infrared absorber, an acid generator, a resole resin and a novolac resin is US Pat.
0,699. However, such a negative-type image recording material needs a heat treatment of heating at 140 to 200 ° C. for about 50 to 120 seconds after laser exposure for image formation. It required extensive equipment and energy.
For example, JP-A-8-108621 discloses a negative image-forming material using a photopolymerizable composition, in which heating is performed at the same time as image exposure in order to accelerate thermal polymerization of the recording layer. There is a statement to that effect. Simultaneous heating in the exposure process has problems such as heat fluctuations in the nearby air due to heating, defocusing the laser, affecting image forming properties, and shortening the life of the laser element due to heat. , Not preferable.

Further, Japanese Patent Publication No. 7-103171 discloses a heat treatment after imagewise exposure comprising a cyanine dye having a specific structure, an iodonium salt and an addition-polymerizable compound having an ethylenically unsaturated double bond. Although a recording material that is not required is described, this image recording material has a polymerization sensitivity due to oxygen in the air during the polymerization reaction, resulting in a decrease in sensitivity and insufficient strength of the formed image area. There was a problem that the printability was insufficient.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to record by using a solid-state laser and a semiconductor laser that emits infrared rays, so that it is possible to record directly from digital data of a computer or the like, and image forming properties and It is an object of the present invention to provide a negative image-forming material capable of obtaining a lithographic printing plate having excellent printing durability.

[0008]

The present inventor has paid attention to the physical properties of a negative image-forming material, and as a result of earnest studies, formed a specific intermediate layer between a support and a photosensitive layer for image formation. The inventors have found that this can be solved, and have completed the present invention.

The present invention is directed to an infrared laser recordable aluminum support, a silicate film, an intermediate layer containing an aluminum compound having a functional group capable of reacting with a hydroxyl group on the silicate film by heat, (A) infrared light The present invention relates to a negative image-forming material comprising a photosensitive layer containing an absorber, a radical generator (B) and a radically polymerizable compound (C), which are sequentially provided.

The present invention provides a silicate film on an aluminum support, an intermediate layer containing an aluminum compound having a functional group capable of reacting with a hydroxyl group on the silicate film by heat, an infrared absorber (A), and a radical (B). An infrared laser is irradiated to a negative image-forming material that is sequentially provided with a photosensitive layer containing a generator and a radically polymerizable compound (C).
The present invention relates to an image forming method characterized by polymerizing a radical-polymerizable compound to cure a photosensitive layer and reacting a hydroxyl group on a silicate film with a functional group of an aluminum compound in an intermediate layer in a portion irradiated with an infrared laser. .

In the present invention, the heat generated by the exposure causes the hydroxyl groups on the silicate film and the functional groups of the aluminum compound to react with each other and bond with each other, and the aluminum compound on the silicate film is replaced with an aluminum compound having good adhesion to the photosensitive layer. ,
Adhesion between the anodized film or silicate film formed on the aluminum support by a conventional method and the photosensitive layer, that is, printing durability is improved.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The negative image-forming material of the present invention comprises
After performing a known surface treatment such as anodizing treatment on the aluminum substrate to form a silicate film to make it hydrophilic, through an intermediate layer containing an aluminum compound having a functional group capable of reacting with a hydroxyl group on the Si film by heat. And a photosensitive layer is formed.

[Intermediate Layer] The negative image-forming material of the present invention comprises a functional group capable of reacting with a hydroxyl group on a silicate film by heat on a support having a silicate film formed thereon and subjected to a hydrophilic treatment (hereinafter, referred to as a reaction (Also referred to as a functional group) is formed to form an intermediate layer containing an aluminum compound. The formation of this intermediate layer is performed by preparing an intermediate layer coating solution using an aluminum compound as a raw material and coating the same on the support. It is preferable to carry out by the method.

As described above, the anodic oxide film and the silicate film are provided on the aluminum substrate, and the photosensitive layer described below is formed on the support formed by forming the intermediate layer of the present invention. Although an image forming material is obtained, the aluminum compound used for this intermediate layer is OH.
Group, an OR group, an O-COR group, a halogen group, a nitric acid group, a sulfonic acid group, an alcoholate group, and an aluminum compound having a reactive functional group such as an alkyl ethyl acetate group. Aluminum, aluminate, aluminum fluoride, fluoroaluminate,
Aluminum chloride, aluminum bromide, aluminum iodide, aluminum sulfate, alum, aluminum nitrate, aluminum thiocyanide, aluminum sulfide, aluminum nitride, aluminum methylate, aluminum ethylate, aluminum isopropylate, mono se
c-Butoxy aluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, aluminum-tris (ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetonate-bis (ethylacetoacetate) , Aluminum-tris (acetylacetonate)
Etc. Of these, organic aluminum compounds such as ethyl acetoacetate aluminum diisopropylate and aluminum-tris (ethylacetoacetate) are particularly preferable. In the above formula, R is a methyl group,
It represents an alkyl group such as an ethyl group, a propyl group and a butyl group. These may be used alone or in combination of two or more.

Such an intermediate layer can be provided, for example, by the following method. That is, water or methanol, ethanol, a method in which a solution prepared by dissolving the above organoaluminum compound in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied on a substrate provided with a silicate film and dried, and water or methanol , Ethanol, a solution prepared by dissolving the above organoaluminum compound in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof, a substrate provided with a silicate film is immersed to adsorb the organoaluminum compound, and then,
This is a method of providing an intermediate layer by washing with water and drying. In the former method, a solution of the organoaluminum compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used. In the latter method, the concentration of the solution is 0.01-2.
0% by weight, preferably 0.05 to 5% by weight, the immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C,
The immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute.

The film thickness of the intermediate layer is preferably from 5 to 100 mg / m ^2, and more preferably 10 to 50 mg / m ^2.

As described above, on the support provided with the intermediate layer, the photosensitive layer described in detail below, and further, if desired,
The negative image forming material of the present invention can be obtained by forming any other layer such as a surface protective layer and a back coat layer.

The photosensitive layer provided in the image forming material of the present invention contains (A) an infrared absorber, (B) a radical generator and (C) a radical polymerizable compound, and is recordable by an infrared laser. It is what

[Photosensitive Layer] The photosensitive layer of the negative type image forming material will be described below. In such an image-forming material, the infrared absorbent (A) in the exposed portion undergoes photothermal conversion by imagewise exposure with an infrared laser, and the generated heat decomposes the radical generator (B) to generate radicals. As a result, the photosensitive layer containing the radically polymerizable compound (C) is cured to form an image portion, and the intermediate layer and the radically polymerizable compound in the photosensitive layer are firmly bonded. Then, by developing with an alkaline developer described later, the unexposed unexposed photosensitive layer and intermediate layer are removed, the hydrophilic silicate film is exposed, and a non-image area is formed.

Each constituent component of the photosensitive layer will be described in order. [(A) Infrared absorber] An object of the present invention is to record an image with a laser emitting infrared rays. For this purpose, it is essential to use an infrared absorber. The infrared absorber has a function of converting the absorbed infrared rays into heat.
The heat generated at this time decomposes the radical generator to generate radicals. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum in the wavelength range of 760 nm to 1200 nm.

As the dye, commercially available dyes and known dyes described in documents such as "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry, published in 1945) can be used. Specifically, dyes such as azo dyes, metal complex 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 are, for example, JP-A-5
Cyanine dyes described in JP-A No. 8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and JP-A-58-1736.
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent Application No. 94595, JP-A-Sho 5
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940, JP-A-60-63744 and the like, JP-A-58-1
Squarylium dyes described in No. 12792,
Examples thereof include cyanine dyes described in British Patent 434,875.

Further, the near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A Nos. 58-181051, 58-220143, 59-41363 and 59-11363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
The pyrylium compounds disclosed in Nos. 514 and 5-19702 are also preferably used.

Another preferred example of the dye is represented by the formula (I) in US Pat. No. 4,756,993:
The near infrared absorbing dye described as (II) can be mentioned.

Among these dyes, particularly preferable 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 (I) is most preferable.

[0026]

[Chemical 1]

In the general formula (I), X ¹ is a halogen atom,
Alternatively, it represents 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. From the viewpoint of storage stability of the photosensitive layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and further, R ¹ and R ²
It is particularly preferable that and are bonded to each other to form a 5-membered ring or a 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. Examples of preferable substituents 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 represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ^{4, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. As a preferable substituent, an alkoxy group having 12 or less carbon atoms,
Examples thereof include a carboxyl group and a sulfo group. R ⁵ , R ⁶ , R
⁷ and R ⁸ may be the same or different,
It represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, 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 necessary. Preferred Z ¹⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, in view of the storage stability of the photosensitive layer coating solution.
And a sulfonate ion, particularly preferably a perchlorate ion, a hexafluorophosphate ion, and an arylsulfonate ion.

Specific examples of the cyanine dye represented by the general formula (I) which can be preferably used in the present invention ([I
R-1] to [IR-12]) are listed below, but the present invention is not limited thereto.

[0030]

[Chemical 2]

[0031]

[Chemical 3]

[0032]

[Chemical 4]

The pigment used in the present invention includes:
Commercial pigment and color index (CI) handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
The pigments described in 1. can be used.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, 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. The surface treatment method includes a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above surface treatment method is "property and application of metal soap" (Koushobo),
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 0.1 μm to 1 μm.
It is preferably in the range of. Particle size of pigment is 0.01μ
When it is less than m, it is not preferable from the viewpoint of stability of the dispersion in the coating liquid for the image-sensitive layer, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the image-sensitive layer.

As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, etc. 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, see "Latest Pigment Application Technology" (CMC Publishing, 1
986).

These infrared absorbing agents may be added to the same layer as other components, or may be added to another layer provided, but when the negative image forming material is prepared, The optical density at the absorption maximum in the wavelength range of 760 nm to 1200 nm of the photosensitive layer is preferably 0.1 to 3.0. If it is out of this range, the sensitivity tends to be low. Since the optical density is determined by the amount of the infrared absorber added and the thickness of the photosensitive layer, the predetermined optical density can be obtained by controlling the conditions of both. The optical density of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, a transparent or white support, a coating amount after drying to form a photosensitive layer having a thickness appropriately determined in the range necessary for a lithographic printing plate, with a transmission type optical densitometer Examples thereof include a measuring method and a method of forming a photosensitive layer on a reflective support such as aluminum and measuring the reflection density.

[(B) Radical Generating Agent] The radical generating agent used in the present invention is a compound used in combination with (A) an infrared absorbing agent to generate a radical when irradiated with an infrared laser. Examples of the radical generator include an onium salt, a triazine compound having a trihalomethyl group, a peroxide, an azo-based polymerization initiator, an azide compound, and a quinonediazide, and an onium salt is preferable because of its high sensitivity. The onium salt that can be preferably used as the radical generator in the present invention will be described. Preferred onium salts include iodonium salts, diazonium salts and sulfonium salts. In the present invention, these onium salts function not as an acid generator but as an initiator of radical polymerization. The onium salt preferably used in the present invention is an onium salt represented by the following general formulas (III) to (V).

[0040]

[Chemical 5]

In the formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an alkyl group having 12 or less carbon atoms. An aryloxy group is mentioned. Z ^{11 −} represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and preferably a perchlorate ion and a hexafluorophosphate ion. An ion and an aryl sulfonate ion.

In the formula (IV), Ar^{twenty one}Has a substituent
It represents an aryl group having 20 or less carbon atoms which may be present.
Preferred substituents are halogen atom, nitro group, carbon
Alkyl group with 12 or less elementary atoms, 12 or less carbon atoms
The lower alkoxy group, arylo having 12 or less carbon atoms
Xy group, alkylamino group having 12 or less carbon atoms, charcoal
Dialkylamino group having 12 or less elementary atoms, number of carbon atoms
12 or less arylamino groups or 12 carbon atoms
Up to and including 4 diarylamino groups. Z ^{twenty one-}Is Z
^11-Represents a counter ion having the same meaning as.

In the formula (V), R ³¹ , R ³² and R ^{33, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the present invention, specific examples of the onium salt which can be suitably used as the radical generator include:
Paragraph number [003 of JP 2001-133969 A
[0] to [0033] may be mentioned.

Preferred specific examples of the radical generator used in the present invention will be given below, but the present invention is not limited thereto.

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

The maximum absorption wavelength of the radical generator used in the present invention is preferably 400 nm or less, more preferably 360 nm or less. By thus setting the absorption wavelength in the ultraviolet region, the image forming material can be handled under a white light.

These radical generators are contained in an amount of 0.1 to 50% by weight, preferably 0.1% by weight based on the total solid content of the photosensitive layer coating solution.
It can be added to the photosensitive layer coating liquid in an amount of 5 to 30% by weight, particularly preferably 1 to 20% by weight. If the amount added is less than 0.1% by weight, the sensitivity will be low, and if it exceeds 50% by weight, non-image areas will be stained during printing. These radical generators may be used alone, or 2
You may use together more than one kind. Further, these radical generators may be added to the same layer as other components, or may be added to another layer provided separately.

[(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 1
, Preferably two or more compounds. Such a compound group is widely known in the industrial field, and these compounds can be used in the invention without particular limitation. These have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of the monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and their esters and amides. 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 polyhydric amine compound are used. Further, unsaturated carboxylic acid esters having a nucleophilic substituent such as a hydroxyl group, an amino group and a mercapto group, monofunctional or polyfunctional isocyanates with amides, addition reaction products with epoxies, monofunctional or polyfunctional, or A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogens. 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.
Further, as another example, it is also possible to use a compound group in which unsaturated phosphonic acid, styrene or the like is substituted for the above unsaturated carboxylic acid.

Specific examples of radically polymerizable compounds which are esters of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, such as acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester and maleic acid ester. An example is JP-A-2001-
Paragraph Nos. [0037] to [004 of Japanese Patent No. 133969
2], and these can also be applied to the present invention.

Examples of other esters include, for example, Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-473334, aliphatic alcohol esters described in JP-A-57-196231, 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 an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriamine tris acrylamide, xylylene bis acrylamide, and xylylene bis methacrylamide.

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

Further, urethane-based addition-polymerizable compounds produced by addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, Japanese Examined Patent Publication No.
In a molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (VI) to a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-8-41708, Examples thereof include vinyl urethane compounds containing one or more polymerizable vinyl groups.

General formula (VI) CH ₂ = C (R ⁴¹ ) COOCH ₂ CH (R ⁴² ) OH (wherein R ⁴¹ and R ⁴² represent H or CH ₃ ).

Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58-
49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62
The urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, radically polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, may be used. good.

Another example is JP-A-48-641.
No. 83, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in Japanese Patent No. 490 and each publication can be given. Also,
JP-B-46-43946, JP-B1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
The vinylphosphonic acid compounds described in JP-A-2-25493 can also be used. In some cases, the structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesive Association magazine vol. 20, No. 7, pages 300-308 (198
Those introduced as photocurable monomers and oligomers in 4 years) can also be used.

Regarding these radically polymerizable compounds,
The 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 according to the performance design of the final recording material. For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, bifunctional or more is preferable. Further, in order to increase the strength of the image area, that is, the cured film, a compound having a trifunctional or higher functionality is preferable, and further, a compound having different functional numbers and different polymerizable groups (for example, an acrylic ester compound, a methacrylic ester compound Compounds, styrenic compounds, etc.) are used in combination to control both photosensitivity and strength. Large molecular weight compounds and highly hydrophobic compounds have excellent sensitivity and film strength, but
It may not be preferable in terms of development speed and precipitation in a developing solution. In addition, compatibility and dispersibility with other components in the photosensitive layer (for example, a binder polymer, an initiator, a colorant, etc.) are important factors in selecting and using the radical polymerization compound. Use of low purity compounds, 2
The compatibility may be improved by the combined use of one or more compounds. In addition, a specific structure may be selected for the purpose of improving the adhesiveness of the support, the overcoat layer and the like. Regarding the blending ratio of the radical-polymerizable compound in the image recording layer, the larger the amount, the more advantageous in terms of sensitivity. However, if the amount is too large, undesired phase separation may occur or the adhesiveness of the image recording layer may affect the production process. May occur (for example, transfer of recording layer components, manufacturing failure due to adhesion), or precipitation from a developing solution. From these viewpoints, the preferable compounding ratio of the radically polymerizable compound is often 5 to 80% by weight, preferably 20 to 20% by weight based on the total components of the composition.
It is 75% by weight. These may be used alone or in combination of two or more. In addition, the method of using the radically polymerizable compound, the degree of inhibition of polymerization with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, etc., an appropriate structure, formulation, and addition amount can be arbitrarily selected. Depending on the case, a layer constitution / coating method such as undercoating or topcoating can be carried out.

[Binder Polymer] In the present invention, it is preferable to further use a binder polymer. It is preferable to use a linear organic polymer as the binder. Any of these "linear organic polymers" may be used. A linear organic polymer that is soluble or swellable in water or weak alkaline water is preferably selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent for forming a photosensitive layer but also as a developer such as water, weak alkaline water or an organic solvent developer. For example, water development becomes possible by using a water-soluble organic polymer. As such a linear organic polymer, a radical polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No. 58-12577 / 54-2595
7, JP-A-54-92723, and JP-A-59-538.
36, JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial Examples include esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group.

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

Further, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-2004
-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. 1-271741,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 and the like is extremely excellent in strength and is advantageous in terms of printing durability and suitability for low exposure.

In addition to these, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.

The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, further 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, more preferably 1.1 to 10.

These polymers are random polymers,
It may be either a block polymer or a graft polymer, but a random polymer is preferable.

The polymer used in the present invention can be synthesized by a conventionally known method. As the 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, etc. may be mentioned. These solvents may be used alone or in admixture 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 polymers used in the present invention may be used alone or as a mixture. These polymers are 20 to 95% by weight based on the total solid content of the photosensitive layer coating solution,
It is preferably added to the photosensitive layer in a proportion of 30 to 90% by weight. When the addition amount is less than 20% by weight, the strength of the image area is insufficient when an image is formed. The addition amount is 95% by weight.
If it exceeds, the image is not formed. The weight ratio of the compound having a radical-polymerizable ethylenically unsaturated double bond and the linear organic polymer is preferably 1/9 to 7/3.

[Other Components of Photosensitive Layer] In the present invention, various compounds other than these may be added, if necessary. For example, a dye having a large absorption in the visible light region can be used as a colorant for images. In particular,
Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black B
Y, Oil Black BS, Oil Black T-505
(All manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue (CI52015), etc., and JP-A-62-29324.
The dyes described in No. 7 can be mentioned. Further, pigments such as phthalocyanine-based pigments, azo-based pigments, carbon black and titanium oxide can also be preferably used.

It is preferable to add these coloring agents because it is easy to distinguish the image area from the non-image area after the image formation. The addition amount is based on the total solid content of the photosensitive layer coating liquid.
The proportion is 0.01 to 10% by weight.

Further, in the present invention, a small amount of thermal polymerization is prevented in order to prevent unnecessary thermal polymerization of the compound having a radically polymerizable ethylenically unsaturated double bond during preparation or storage of the photosensitive layer coating solution. It is desirable to add agents. Hydroquinone as a suitable thermal polymerization inhibitor,
p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4 -Methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by weight to about 5% by weight based on the weight of the entire composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of higher fatty acid derivative added is about 0.
1 wt% to about 10 wt% is preferred.

In the photosensitive layer coating solution of the present invention, in order to broaden the stability of processing under developing conditions, nonionic materials such as those described in JP-A-62-251740 and JP-A-3-208514 are used. Surfactants, JP 59
Amphoteric surfactants such as those 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 trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether.

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N. , N-betaine type (for example,
Examples of the brand name include Amogen K, manufactured by Daiichi Kogyo Co., Ltd. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive layer coating liquid is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer is added to the coating solution for the photosensitive layer according to 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 order to produce the image-forming material according to the present invention, the above-mentioned components necessary for the photosensitive layer coating solution are usually dissolved in a solvent and coated on a suitable support, and then, if desired, an overcoat which will be described later. The coating liquid for the coat layer may be applied. As the solvent used for the photosensitive layer coating liquid, 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, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
Examples thereof include methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1-5.
It is 0% by weight.

The coating amount (solid content) of the photosensitive layer obtained after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g / m ² for the image forming material. Various methods can be used for 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 photosensitive layer that functions as an image recording deteriorate.

The photosensitive layer coating solution according to the present invention contains a surfactant for improving the coating property, such as JP-A-62-17.
Fluorine-based surfactants such as those described in No. 0950 can be added. The preferable addition amount is 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight, based on the solid content of the material of the entire photosensitive layer.

[Support] The image recording material of the present invention can be used as a lithographic printing plate precursor by coating it on a suitable support to form a tourist layer. Examples of the support to which the image recording material of the present invention can be applied include an aluminum plate which is a dimensionally stable plate.

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

The publicly known techniques regarding aluminum materials that can be used for the support are listed below. (1) Regarding JIS 1050 material, the following technologies are disclosed. JP-A-59-153861, JP-A-6-
1-51395, JP-A-62-146694, JP-A-6-
0-215725, JP-A-60-215726, JP-A-60-215727, JP-A-60-215728, JP-A-61-272357, JP-A-58-11759, JP-A-58-42493, JP-A-58-42493. -212254, JP-A-62-148295, JP-A-4-254545, JP-A-4-165041, JP-B-3-68939, JP-A-3.
-234594, Japanese Patent Publication No. 1-447545, Japanese Patent Laid-Open No. 62-
140894, etc. In addition, Japanese Patent Publication No. 1-3591
No. 0, Japanese Patent Publication No. 55-28874 and the like are also known.

(2) Regarding JIS 1070 material, the following techniques are disclosed. JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-73974, JP-A-8-108659, JP-A-8-
92679, etc.

(3) Regarding Al-Mg type alloys, the following techniques have been disclosed. Japanese Patent Publication No. 62-5080, Japanese Patent Publication No. 63-60823, Japanese Patent Publication No. 3-61753, and Japanese Unexamined Patent Publication No.
0-203496, JP-A-60-203497, JP-B-3-11635, JP-A-61-274993, JP-A-6-63.
2-23794, JP-A-63-47347, JP-A-63.
-47348, JP-A-63-47349, JP-A-64-
61293, JP-A-63-135294, JP-A-63-135294
87288, Japanese Patent Publication 4-73392, Japanese Patent Publication 7-100
844, JP-A-62-149856, JP-B-4-733.
94, JP-A-62-181191, JP-B-5-7653.
0, JP-A-63-30294, JP-B-6-37116 and the like. Further, JP-A-2-215599 and JP-A-61-2
01747 and the like are also known.

(4) Regarding Al-Mn alloys, the following techniques have been disclosed. Japanese Unexamined Patent Publication No. 60-230951,
JP-A-1-306288, JP-A-2-293189 and the like. In addition, Japanese Examined Patent Publication No. 54-42284, Japanese Examined Patent Publication No. 4-192
90, Japanese Patent Publication No. 4-19291, Japanese Patent Publication No. 4-19292,
JP-A-61-35995, JP-A-64-51992, U
S5009722, US5028276, Japanese Patent Laid-Open No. 4-2
26394 and the like are also known.

(5) Regarding Al-Mn-Mg based alloys, the following techniques have been disclosed. JP-A-62-861
43, JP-A-3-222796. In addition, Japanese Examined Japanese Patent Publication Sho 63-6
0824. JP-A-60-63346, JP-A-60-63
347, EP223737, JP-A-1-283350,
US4818300, BR1222777, etc. are known.

(6) The following techniques are known for Al-Zr alloys. JP-B-63-15978 and JP-A-61-51395. Further, JP-A-63-143234,
JP-A-63-143235 is also known.

(7) Regarding the Al-Mg-Si type alloy, BR1421710 and the like are known.

The following contents can be used as the method for producing the aluminum plate for the support. The aluminum alloy melt having the above-mentioned content components and alloy component ratios is subjected to a cleaning treatment according to a conventional method and cast. 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, ceramic foam filters, etc., and alumina flakes Filtering using a filter that uses alumina, alumina balls, etc., or a glass cloth filter. Alternatively, a process that combines degassing and filtering is performed. It is desirable that these cleaning treatments be carried out in order to prevent defects due to foreign substances such as non-metallic inclusions and oxides in the molten metal and defects due to the gas melted into the molten metal.

Regarding the filtering of the molten metal, JP-A-6-57342, JP-A-3-162530, and JP-A-5-34253.
140659, JP-A-4-231425, JP-A-4-4-2
76031, JP-A-5-311261, JP-A-6-13
6466 and the like are known.

Regarding the degassing of the molten metal, JP-A-5-51
659, Japanese Patent Laid-Open No. 5-51660, and Japanese Utility Model Laid-Open No. 5-4914
8, JP-A-7-40017 and the like are known.

As described above, casting is performed using the molten metal that has been subjected to the cleaning treatment. Regarding the casting method, there are a method using a fixed mold represented by a DC casting method and a method using a driving mold represented by a continuous casting method. When the DC casting method is used, the cooling rate is solidified in the range of 1 to 300 ° C / sec. If it is less than 1 ° C./sec, many coarse intermetallic compounds are formed.

As the continuous casting method, a method using a cooling roll, represented by the Hunter method and the 3C method, a Hazley method, a method using a cooling belt represented by the Alsui caster II type, and a cooling block are industrial. Is done in a regular manner. The cooling rate when the continuous casting method is used is 100 to 1000 ° C /
It solidifies in the range of seconds. In general, the cooling rate is higher than that of the DC casting method, so that the solid solubility of the alloy component with respect to the aluminum matrix is high. Regarding the continuous casting method, the inventors of the present invention disclosed in JP-A-3-7
9798, JP-A-5-201166, JP-A-5-156
414, JP-A-6-262203, and JP-A-6-1229.
49, JP-A-6-210406, JP-A-6-26230.
8 etc. are disclosed.

When DC casting is performed, the plate thickness is 300-80.
A 0 mm ingot can be manufactured. The ingot, according to the usual method,
The surface is chamfered and the surface is 1 to 30 mm. Desirably 1 to
10 mm is cut. After that, soaking treatment is performed if necessary. When carrying out soaking treatment, it should be done at 450-620 ° C. for 1 hour so that the intermetallic compound does not become coarse.
The heat treatment is performed for not less than 48 hours and not more than 48 hours. If it is shorter than 1 hour, the effect of soaking treatment becomes insufficient. Then, hot rolling and cold rolling are performed to obtain an aluminum rolled plate. The starting temperature of hot rolling is 350 to 500
It shall be in the range of ° C. Intermediate annealing treatment may be performed before, after, or during the cold rolling. The intermediate annealing condition in this case is 280 ° C. to 6 using a batch type annealing furnace.
2 to 20 hours at 00 ° C. Desirably 350 ~ 500 ℃
By heating for 2 to 10 hours or using a continuous annealing furnace.
360 seconds or less at 00 to 600 ° C., preferably 450 to
Heat treatment at 550 ° C. for 120 seconds or less can be adopted. The crystal structure can be made finer by heating at a temperature rising rate of 10 ° C./sec or more using a continuous annealing furnace.

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

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

A thin oil film may be provided on the surface of the Al plate in order to prevent the occurrence of scratches due to friction between the Al plates. If necessary, the oil film may be volatile or
A non-volatile material is appropriately used. If there is too much oil,
Slip failure occurs in the production line, but if there is no oil, scratches will occur during coil transportation. Therefore, the oil amount is 3 mg / m ² or more and 100 mg / m ² or less, and the 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, Japanese Unexamined Patent Publication No.
-210308 and the like are disclosed.

When continuous casting is performed, for example, when a cooling roll such as a Hunter method is used, a cast plate having a plate thickness of 1 to 10 mm can be directly continuously cast and rolled, and a merit that a hot rolling step can be omitted can be obtained. Further, if a cooling roll such as the Hazley method is used, a cast plate having a plate thickness of 10 to 50 mm can be cast,
Generally, a continuous casting and rolling plate having a plate thickness of 1 to 10 mm is obtained by placing a hot rolling roll immediately after casting and continuously rolling. These continuously cast rolled plates are finished to a plate thickness of 0.1 to 0.5 mm through the steps of cold rolling, intermediate annealing, flatness improvement, slitting, etc. as described in the case of DC casting. To be Regarding the intermediate annealing condition and the cold rolling condition in the case of using the continuous casting method, see JP-A-6-2205.
93, JP-A-6-210308, JP-A-7-5411
1, JP-A-8-92709 and the like are disclosed.

The aluminum plate produced by the above method may be subjected to surface treatment such as surface roughening treatment and coated with a photosensitive layer to prepare a lithographic printing plate. The surface roughening treatment includes mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening, either alone or in combination. In addition, it is also preferable to perform anodizing treatment for ensuring the scratch resistance of the surface and treatment for increasing the hydrophilicity.

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

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 carried out to roughen the surface of the support. Specific means of this graining method include sand blasting, ball grain, wire grain, nylon brush and brush grain with abrasive / water slurry,
There is a mechanical graining method such as honing grain which sprays abrasive / water slurry onto the surface at high pressure, and there is also a chemical graining method where the surface is roughened with an etching agent consisting of alkali or acid or a mixture thereof. . Also, British Patent No. 896,563 and JP-A-5
3-67507, JP-A-54-146234 and JP-B-48-28123, or an electrochemical graining method, or JP-A-53-1232.
No. 04, JP-A-54-63902, a method combining a mechanical graining method and an electrochemical graining method, and a mechanical method described in JP-A-56-55261. It is also known to combine a graining method and a chemical graining method with a saturated aqueous solution of an aluminum salt of a mineral acid. Further, to the support material, a method of adhering a granular material with an adhesive or a method having its effect to roughen the surface, or a continuous band or roll having fine unevenness is pressure-bonded to the support material to form unevenness. A rough surface may be formed by transferring.

A plurality of such surface-roughening methods may be used in combination, and the order, the number of repetitions, etc. can be arbitrarily selected. When a plurality of surface-roughening treatments are combined, chemical treatment with an acid or alkali aqueous solution can be performed during that time so that the subsequent surface-roughening treatment can be performed uniformly. Specific examples of the acid or alkali aqueous solution include acids such as hydrofluoric acid, fluorozirconic acid, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid, and alkaline aqueous solutions such as sodium hydroxide, sodium silicate and sodium carbonate. . These acid or alkali aqueous solutions may be used alone or in combination of two or more. The chemical treatment is carried out using a 0.05 to 40% by weight aqueous solution of these acids or alkalis at 40 ° C to 10
Generally, the treatment is performed at a liquid temperature of 0 ° C. for 5 to 300 seconds.

Since smut is formed on the surface of the support obtained by the above-mentioned roughening treatment, that is, graining treatment, appropriate treatment such as washing with water or alkali etching is carried out to remove the smut. It is generally preferred to do As such a process, for example, Japanese Patent Publication No.
Treatment methods such as the alkali etching method described in JP-A-8-28123 and the sulfuric acid desmutting method described in JP-A-53-12739 are mentioned.

In the case of the aluminum support used in the present invention, after the above-mentioned pretreatment, the support is usually anodized in order to improve abrasion resistance, chemical resistance and water retention. An oxide film is formed on.

As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film. Generally, sulfuric acid,
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 electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because it varies depending on the electrolyte used, but generally the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., the current density is 5 to 60 A / dm ^2. , Voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are suitable. 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. If the anodic oxide film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the lithographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. "Scratch dirt"
Is likely to occur.

The anodized support, after being washed with water, suppresses the dissolution of the anodized film in the developer, suppresses the residual film of the photosensitive layer components, improves the anodized film strength, and improves the hydrophilicity of the anodized film. For the purpose of improving the adhesion with the photosensitive layer, the following treatments can be performed.

[Silicate Film] Here, the hydrophilic treatment performed after the anodizing treatment will be described. The hydrophilic treatment in the present invention is formation of a silicate film, and the silicate film has an Si element amount of 2 to 40 m.
g / m ² , more preferably 4 to 30 mg / m ² . The coating amount can be measured by a fluorescent X-ray analysis method, and the amount of Si element can be measured. The above hydrophilic treatment is performed, for example, in U.S. Pat. Nos. 2,714,066 and 3,181.
No. 461, No. 3,280,734 and No. 3,90
The alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in No. 2,734 can be applied. According to this method, the alkali metal silicate is 1 to 30% by weight, preferably 2 to 15% by weight,
An aluminum substrate on which an anodized film is formed is added to an aqueous solution having a pH of 10 to 13 at 25 ° C., for example, 15 to 80
The substrate is immersed at 0.5 ° C. for 0.5 to 120 seconds, washed with water and dried to obtain a silicate-treated substrate.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. The hydroxides used to raise the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide.
In addition, alkaline earth metal salt or IV
You may mix | blend a B group metal salt. Examples of the alkaline earth metal salt include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. Can be mentioned. Examples of Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. You can The alkaline earth metal salt or Group IVB metal salt may be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight.

An intermediate layer containing an aluminum compound having a functional group capable of reacting with the support thus hydrophilized is formed. Specifically, the reactive functional group is a group capable of binding to a metal, a metal oxide, a hydroxide, an -OH group on the surface of the substrate by the heat at the time of exposure, or a silanol group formed by the chemical conversion treatment of the substrate. Refers to O
H group, OR group, O-COR group, halogen group, nitric acid group,
It represents a sulfonic acid group, an alcoholate group, an alkyl ethyl acetate group or the like.

After the surface of the support is subjected to the above-mentioned treatments, a back coat is provided on the back surface of the support, if necessary. As such a back coat, JP-A-5-45
Organic polymer compounds described in JP-A-885 and JP-A-6-
A coating layer made of a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in 35174 is preferably used. Of these coating layers, Si
(OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ )
Silicon alkoxy compounds such as ₄ , Si (OC ₄ H ₉ ) ₄ are inexpensive and easily available, and a metal oxide coating layer obtained from them is excellent in developing solution resistance, and is particularly preferable.

A preferable characteristic for the support is a center line average roughness of 0.10 to 1.2 μm. 0.10μ
When it is less than m, the adhesion to the photosensitive layer is lowered and the printing durability is remarkably reduced. If it is larger than 1.2 μm, the stain resistance during printing will deteriorate. Further, the color density of the support is 0.15 to 0.65 as the reflection density value,
When it is whiter than 0.15, halation during image exposure is too strong, which hinders image formation. When it is blacker than 0.65, the image is difficult to see in the plate inspection after development, and the plate inspection property is remarkably poor. It becomes a thing.

In the negative image-forming material of the present invention, an overcoat layer can be provided on the support, if desired.

The negative image-forming material of the present invention can be recorded with an infrared laser. Also, thermal recording with an ultraviolet lamp or a thermal head is possible. In the present invention,
Image exposure is preferably performed by a solid-state laser or a semiconductor laser that emits infrared rays having a wavelength of 760 nm to 1200 nm. The laser output is preferably 100 mW or more,
To reduce the exposure time, it is preferable to use a multi-beam laser device. The exposure time per pixel is preferably within 20 μsec. The energy applied to the recording material is preferably 10 to 300 mJ / cm ² .

In the image forming material of the present invention, the energy of the irradiated infrared laser or the like is converted into heat by the infrared absorbent (A), and the radical generator (B) generates radicals by the heat. By the action of the radicals, the radically polymerizable compound (C) and the binder polymer accelerate the polymerization and curing reaction, thereby recording an image,
That is, plate making is performed. Further, in the image-forming material of the present invention, the energy of the irradiated infrared laser or the like is converted into heat by the infrared absorbent (A), and the heat of the hydroxyl group on the silicate film and the aluminum compound contained in the intermediate layer The reactive functional groups react with each other and bond to each other, thereby improving the adhesion of the photosensitive layer, that is, the printing durability of the planographic printing plate.

After being exposed by an infrared laser, the negative image-forming material of the present invention is preferably developed with water or an alkaline aqueous solution.

When an alkaline aqueous solution is used as the developing solution, a conventionally known alkaline aqueous solution can be used as the developing solution and the replenishing solution of the image forming material of the present invention. For example,
Sodium silicate, potassium, sodium triphosphate, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium, Examples thereof include inorganic alkali salts such as sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium borate, potassium borate and lithium borate. 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 alkaline agents may be used alone or in combination of two or more.

Further, in the case of developing using an automatic processor, the same developer as the developer or an aqueous solution (replenisher) having a higher alkalinity than the developer is added to the developer, so that the developer is stored in the developer tank for a long time. It is known that a large amount of planographic printing plate material can be processed without replacing the developing solution. Also in the present invention, this replenishment system is preferably applied.

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

Further, in the developing solution and the replenishing solution, if necessary, an inorganic salt reducing agent such as hydroquinone, resorcin, sodium salt and potassium salt of sulfurous acid or bisulfite, an organic carboxylic acid, an antifoaming agent and hard water are further added. A softening agent can also be added.

A developing solution containing such a surfactant, an organic solvent and a reducing agent is described in, for example, JP-A-51-51.
No. 77401, benzyl alcohol,
A developer composition consisting of an anionic surfactant, an alkaline agent and water, consisting of an aqueous solution containing benzyl alcohol, an anionic surfactant and a water-soluble sulfite described in JP-A-53-44202. Developer composition,
Examples thereof include a developer composition containing an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent, and water, which are described in JP-A-55-155355, and are also suitable for the present invention. Used for.

The lithographic printing plate developed using the above-described developing solution and replenishing solution is post-treated with washing water, a rinse solution containing a surfactant, a desensitizing solution containing gum arabic and a starch derivative. To be done. As the post-treatment when the image forming material of the present invention is used as a printing plate material, various combinations of these treatments can be used.

In recent years, automatic developing machines for printing plates have been widely used in the plate making / printing industry in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate material, each processing liquid tank, and a spray device. Each of the processing liquids pumped up is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate material is dipped and conveyed by a submerged guide roll or the like in a treatment liquid tank filled with the treatment liquid for treatment. In such automatic processing,
It is possible to carry out the processing while supplementing the replenishing solution to each processing solution according to the processing amount, operating time and the like. Also, the electric conductivity can be detected by a sensor and automatically replenished. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

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

When the lithographic printing plate is burned, before the burning, JP-B-61-2518 and 55-280.
62, JP-A-62-31859 and JP-A-61-1596.
It is preferable to treat with a leveling solution as described in JP-A-55.

As a method for this, a sponge or absorbent cotton soaked with the surface-adjusting solution may be applied onto the planographic printing plate, or
A method in which the printing plate is dipped in a vat filled with a surface-adjusting solution to be applied, or an application by an automatic coater is applied. Further, making the coating amount uniform with a squeegee or a squeegee roller after coating gives more preferable results. The amount of the surface conditioning solution applied is generally 0.03 to 0.8 g / m ^2.
(Dry weight) is suitable.

The planographic printing plate coated with the surface-adjusting solution is dried if necessary and then burned with a burning processor (for example,
It is heated to a high temperature with a burning processor: BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and the heating time in this case depend on the kinds of components forming the image, but are within the range of 180 to 300 ° C.
The range of up to 20 minutes is preferred.

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

[0129]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 4 [Support] 99.5% or more of aluminum and Fe
0.30%, Si 0.10%, Ti 0.02%, Cu
A molten JIS A1050 alloy containing 0.013% was subjected to a cleaning treatment and cast. The cleaning process is a degassing process to remove unnecessary gases such as hydrogen in the melt.
Ceramic tube filter treatment was performed. The casting method was a DC casting method. The solidified ingot having a plate thickness of 500 mm was chamfered by 10 mm from the surface, and homogenized at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound. Then, after hot rolling at 400 ° C., intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate 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, a tension leveler was applied to improve the flatness.

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

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%
45 nitric acid and an aqueous solution containing 0.5% aluminum nitrate
While maintaining the temperature at ℃, while flowing the aluminum web in the aqueous solution, the anode side electricity quantity of 240 C / dm with an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell.
Electrolytic graining was performed by giving ² . Then 10%
Etching is performed with a sodium aluminate aqueous solution at 50 ° C for 30 seconds, and neutralization is performed with a 30 %% sulfuric acid aqueous solution at 50 ° C for 30 seconds.
Smut removal processing was performed.

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

[Silicate Film] Thereafter, a silicate treatment was carried out in order to secure hydrophilicity as a non-image portion of the printing plate. The treatment was carried out by keeping a 1.5% aqueous solution of sodium silicate No. 3 at 70 ° C so that the contact time of the aluminum web was 15 seconds,
Further, it was washed with water and dried at 100 ° C. for 60 seconds. Si
Was 10 mg / m ² . Ra (center line surface roughness) of the support prepared as described above was 0.25 μm.

[Intermediate layer] Next, the following intermediate layer forming liquid (hereinafter referred to as "undercoating liquid") was applied to this aluminum support with a wire bar, and the aluminum support was dried at 90 ° C for 3 hours at 90 ° C.
It was dried for 0 seconds. The coating amount after drying was 20 mg / m ² .

[0136]   <Undercoat liquid A>   -AL compound (aluminum compound described in Table 1) 0.3 g   ・ Methanol 100g

[0137]

[Table 1]

[Photosensitive layer] Next, the following solution [P] was prepared, and this solution was applied to the above-mentioned undercoated aluminum plate using a wire bar, and was applied with a warm air dryer 11
Dry for 45 seconds at 5 ° C. and dry negative lithographic printing plate [P-
1] to [P-4] were obtained. Coating amount after drying is 1.3 g / m
^{Was 2} .

[0139]   <Photosensitive layer forming liquid [P]>   ・ Infrared absorber [IR-1] 0.10 g   ・ 0.30 g of the radical generator described in Table 2   ・ Dipentaerythritol hexaacrylate 1.00 g   ・ Of allyl methacrylate and methacrylic acid     Copolymer with a molar ratio of 80:20     (Weight average molecular weight 120,000) 1.00 g   ・ Victoria Pure Blue Naphthalene Sulfonate 0.04g   ・ Fluorosurfactant 0.01g   (Megafuck F-176, manufactured by Dainippon Ink and Chemicals, Inc.)   ・ Methyl ethyl ketone 9.0 g   ・ Methanol 10.0g   ・ 1-Methoxy-2-propanol 8.0 g

[0140]

[Table 2]

Comparative Examples 1 to 4 In the same manner as in Example 1 except that the undercoat layer forming liquid A in Example 1 was replaced with the following undercoat layer forming liquid B, the negative type lithographic printing plate precursors [P-5] to [P-5] to [P-5]. P-8] was prepared and evaluated in the same manner as in Example 1. The coating amount of the undercoat layer after drying was 20.
It was mg / m ² .

[0142]   <Undercoat liquid B>   -0.3 g of the compounds listed in Table 3   ・ Methanol 100g

[0143]

[Table 3]

[Exposure] The obtained negative type planographic printing plates [P-1] to [P-4] and [P-5] to [P-8] were Creo equipped with a water-cooled 40 W infrared semiconductor laser. Company T
Output of 9W with the redsetter 3244VFS,
External drum rotation speed 210 rpm, plate surface energy 100
Exposure was performed under the conditions of mJ / cm ² and resolution of 2400 dpi.

[Development processing] After exposure, development processing was carried out using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. The developing solution used was a diluting solution of DN-3C 1: 2 in water from Fuji Photo Film Co., Ltd. for both the charging solution and the replenishing solution, and the unexposed area was removed to obtain a negative image. This lithographic printing plate was attached to a printing machine SOR-KZ manufactured by Heidel and printed.

[Evaluation of Printing Durability] The Heidel SOR-K
The Z machine was used to evaluate how many sheets can be printed normally when printed. The larger the number of printed sheets, the better the printing durability. The results are shown in Table 4.

[0147]

[Table 4]

From the results shown in Table 4, using a negative lithographic printing plate precursor having an intermediate layer containing the compounds of Examples 1 to 4,
It can be seen that 100,000 or more good prints were obtained in each case and that the printing durability was excellent. On the other hand, in the printing base plates of Comparative Examples 1 and 2, the image area deteriorated after about 10,000 sheets, and good printed matter could not be obtained. Further, in Comparative Examples 3 and 4, a background stain was generated and a good printed matter was not obtained.

[0149]

According to the present invention, by recording using a solid-state laser and a semiconductor laser that emits infrared rays,
It is possible to provide a negative type lithographic printing plate precursor which can be directly plate-formed from digital data of a computer or the like and has excellent stain performance and printing durability.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA04 AA12 AB03 AC08 AD01                       BC13 BC42 CA00 CB13 CB14                       CC11 DA18 DA35 DA36 FA17                 2H096 AA06 BA05 CA03 CA05 EA04                       GA08                 2H114 AA04 AA14 AA23 AA24 AA28                       BA02 BA10 DA04 DA05 DA14                       DA41 EA01 EA03 EA08 GA01                       GA34

Claims (2)

[Claims] 1. A silicate film on an aluminum support, an intermediate layer containing an aluminum compound having a functional group capable of reacting with a hydroxyl group on the silicate film by heat, an infrared absorber (A), and a radical generator (B). And (C) a photosensitive layer containing a radically polymerizable compound, which is sequentially provided, and a negative type image forming material. 2. A silicate film on an aluminum support, an intermediate layer containing an aluminum compound having a functional group capable of reacting with a hydroxyl group on the silicate film by heat, an infrared absorber (A), and a radical generator (B). And (C) a photosensitive layer containing a radically polymerizable compound is sequentially irradiated with an infrared laser on a negative image-forming material, and the radically polymerizable compound is polymerized in the irradiation portion of the infrared laser to cure the photosensitive layer. An image forming method characterized by reacting the hydroxyl groups on the silicate film with the functional groups of the aluminum compound in the intermediate layer.