JPH095993A - Negative type image recording material - Google Patents

Abstract

PURPOSE: To provide an image recording material capable of recording in the region from near IR to IR (heat rays) and capable of direct photomechanical process from digital data from a computer, etc. CONSTITUTION: This image recording material contains a substance which absorbs light and generates heat, a high molecular compd. having hydroxyl groups and an o-naphthoquinonediazido compd. represented by the general formula where A is a divalent optionally substd aliphatic residue or a divalent optionally substd. arom. residue.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as an offset printing master, and more particularly to a lithographic printing plate for so-called direct plate making which can be made directly from digital signals of a computer or the like.

[0002]

2. Description of the Related Art The development of lasers in recent years has been remarkable, and particularly solid-state lasers having an emission region from near infrared to infrared.
High-power and small-sized semiconductor lasers have become easily available. These lasers are very useful as exposure light sources when making plates directly from digital data from a computer or the like.

Conventionally, as a lithographic printing plate which can be directly drawn from digital data of a computer, a printing plate used in an electrophotographic system, a photopolymerization type printing plate in which exposure by an argon laser or a YAG laser and, if necessary, post-heating are combined,
There are known a material in which a silver salt sensitive material is laminated on a photosensitive resin, a silver salt diffusion transfer type, a printing plate in which a silicone rubber layer is destroyed by electric discharge or laser light, and the like.

In the case of using the electrophotographic method, charging, exposure and development processing are complicated, and the apparatus is complicated and large.
The photopolymerizable printing plate is inherently limited in sensitivity, and it is difficult to use a small laser, and it is difficult to handle it in a bright room. Laminated silver salt photographic materials and silver salt diffusion transfer type have disadvantages in that processing is complicated and cost is increased. Further, the type in which the silicone rubber layer is destroyed by laser has a problem in removing the silicone slag remaining on the plate surface.

As a technique capable of forming an image using these light sources, Japanese Patent Application Laid-Open No. 52-113219 discloses a compound (for example, a diazonium compound) which decomposes with light and heat and absorbs light to convert it into heat. A positive type recording material composed of substance particles capable of forming and a binder is disclosed. JP-A-58-148792 discloses a positive photosensitive and heat-sensitive recording material containing thermoplastic resin particles, a light-to-heat conversion material and a photocrosslinkable material (for example, a diazonium compound) as main components. I have.

However, a recording material that can use the above laser as a light source has low sensitivity, and further, in the case of direct plate making,
Since the digital data of a computer or the like is directly written on the plate material by scanning the laser beam, the positive type material requires a considerable writing time. Therefore, there has been a demand for the development of a highly sensitive material (preferably a negative type) capable of recording by a solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared, which can shorten the writing time. As described above, the conventional lithographic printing plate capable of directly drawing from digital data of a computer is not sufficiently satisfactory.

[0007]

An object of the present invention is to provide an image recording material capable of recording without depending on the emission wavelength of the exposure light source, and particularly recording from near infrared to infrared (heat rays). It is to provide a possible image recording material. Further, an object of the present invention is to use a solid-state laser / semiconductor laser (thermal mode) having a light emitting region from near infrared to infrared to directly record digital data of a computer and the like, and a conventional processing device. Another object of the present invention is to provide a lithographic printing plate for heat mode writing type direct plate making which can be used as it is or as a printing device.

[0008]

The inventors of the present invention have searched for various negative-working photosensitive materials in order to achieve the above-mentioned object. However, a binder having a hydroxyl group and an O having a specific structure are used.
-A photosensitive composition solution consisting of a naphthoquinone diazito compound is mixed with a substance that absorbs radiation (for example, a carbon black dispersion solution), and a coating obtained by coating and drying the support is irradiated with YAG laser light, Effectively heat crosslinks,
The present invention has been achieved by finding the fact that it becomes insoluble in a solvent or an aqueous alkaline solution. The present invention includes (1) a substance that absorbs light and generates heat, a polymer compound having a hydroxyl group, and an O-naphthoquinonediazide compound represented by the following general formula (I), which is a negative type It is an image recording material.

[0009]

Embedded image In the formula, A is a divalent substituted or unsubstituted aliphatic residue, 2
A valent substituted or unsubstituted aromatic residue is shown. Preferred embodiments of the present invention include the following (2) to (8). (2) A layer containing a substance that absorbs infrared light or near infrared light and generates heat, a polymer compound having a hydroxyl group, and an O-naphthoquinonediazide compound represented by the general formula (I) on a support A negative image recording material which is a lithographic printing plate for heat mode writing and direct plate making, characterized by comprising: (3) The image recording material according to (2) above, which uses a dye as a substance that absorbs infrared light or near infrared light and generates heat. (4) The image recording material according to (2) above, which uses a pigment as a substance that absorbs infrared light or near infrared light and generates heat. (5) The image recording material according to the above (2), wherein carbon black is used as a substance that absorbs infrared light or near infrared light and generates heat. (6) The image recording material according to the above (2), which uses a polyester film as a support. (7) The above (2) using an aluminum plate as the support.
Image recording material. (8) On a support, a substance that absorbs infrared light or near-infrared light to generate heat, a polymer compound having a hydroxyl group, and an O-naphthoquinonediazide compound represented by the general formula (I) are included. A negative-type image recording method, which comprises exposing a negative-type image recording material provided with a layer using a laser emitting near-infrared light or infrared light, and then developing with alkaline water.

According to the present invention, the compound having a hydroxyl group and the thermally decomposed compound of O-naphthoquinonediazide represented by the general formula (I) are thermally crosslinked by the thermal energy generated by converting light energy by exposure to thermal energy. , To create a negative image. Therefore, it is preferable that the radiation is infrared light or near-infrared light, because good recording in the thermal mode can be achieved. In the present invention, a substance that absorbs infrared light or near-infrared light is preferably a dye from the viewpoint of developability after exposure, and a pigment is preferable because the sensitivity is good. Carbon black is preferred because it has a wide absorption wavelength range and high sensitivity.

In the present invention, the use of polyester as the support is preferable in that it is lightweight and can form a light-transmitting image, and the use of an aluminum plate is excellent in dimensional stability and durability. In order to perform recording using the image recording material of the present invention, it is preferable to apply a method of exposing with a laser emitting infrared light or near infrared light, and then developing with alkaline water.

When the image recording material of the present invention is a lithographic printing plate, it is preferably a heat mode writing type lithographic printing plate for direct plate making. The heat mode writing is to record on the image recording material by using an appropriate heat ray source, controlling the heat ray source based on digital data. The heat ray source at this time is a thermal head used in a facsimile machine or a thermal copying machine, or a laser emitting infrared light or near infrared light. For direct plate making, infrared light or near infrared light is used. Lasers that emit light are preferred. The preferred light used in the present invention is near infrared,
It is an infrared ray, and this infrared ray is generally also called a heat ray, and when recording is carried out by an infrared ray, the recording material of the present invention can also be called a heat-sensitive recording material.

Hereinafter, the present invention will be described in detail. Examples of the substance that absorbs light (radiation rays) and emits heat used in the present invention include various pigments or dyes. As the pigment, commercially available pigments and color indexes (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), “Latest Pigment Application Technology” (CMC Publishing,
1986), "Printing ink technology" (CMC Publishing, 1
The pigments described in pp. 984) can be used.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigments, green pigments, fluorescent pigments, and other polymer-bound dyes are included. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments,
Inorganic pigments, carbon black and the like can be used.

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 (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Conceivable. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 198).
6th edition).

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. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like 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. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dye, commercially available dyes and literatures (for example, "Dye Handbook" edited by the Society of Organic Synthetic Chemistry, Showa 4)
A publicly known one described in the fifth edition can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes.

Among these pigments or dyes, those absorbing infrared light or near infrared light are particularly preferable.
Carbon black is preferably used as a pigment that absorbs infrared light or near infrared light. Examples of dyes that absorb infrared light or near infrared light include, for example, JP-A-58-12.
No. 5246, No. 59-84356, No. 59-2028
Cyanine dyes described in JP-A-58-173696 and JP-A-58-18.
Methine dyes described in JP-A-58-112793 and JP-A-58-194595;
No.224793, No.59-48187, No.59-73
No. 996, No. 60-52940, No. 60-63744.
Naphthoquinone dyes described in JP-A-58-
Examples thereof include squarylium dyes described in 112792, cyanine dyes described in British Patent 434,875, and the like.

Further, the near infrared absorber described in US Pat. No. 5,156,938 is also preferably used. Further, U.S. Pat.
881,924, substituted arylbenzo (thio) pyrylium salts, JP-A-57-142645 (US Pat. No. 4,327,169), trimethine thiapyrylium salts, JP-A-58-181051. , Ibid. 58-220
No. 143, No. 59-41363, No. 59-84248.
No. 59-84249, No. 59-146063,
Pyrylium compounds described in JP-A-59-146061, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication No. No. 13514, No. 5-
The pyrylium compound disclosed in 19702 is particularly preferably used.

Another particularly preferred example is the near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total solid content of the image recording material.
More preferably, it can be added to the image recording material in a proportion of 0.5 to 15% by weight. If the addition amount is less than 0.01% by weight, an image cannot be obtained, and if the addition amount is more than 50% by weight, stains occur on the non-image portion during printing.

Next, the O-naphthoquinonediazide compound represented by the general formula (I) used in the present invention will be explained. In the formula, A is a divalent substituted or unsubstituted aliphatic residue, or a divalent substituted or unsubstituted aromatic group. In the general formula (I), the divalent aliphatic residue of A is linear, branched and / or cyclic, has a saturated bond and / or an unsaturated bond, and preferably has 2 carbon atoms. ~ 20. For example, ethylene group, triethylene group, propylene group, ethylethylene group, 1,1-
Dimethylethylene group, 1-ethyl-1-methylethylene group, 1,2-dimethylethylene group, tetramethylethylene group, dodecylethylene group, octadecylethylene group,
2-methyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-3-methyl Trimethylene group, 1,2
-Cyclobutylene group, 1,2-cyclohexylene group,
1,2,2-trimethyl-1,3-cyclopentylene group, 2,3-norbornylene group, vinylene group, methylvinylene group, 1,1-dimethylvinylene group, methyleneethylene group, nonenylethylene group, dodecynyl Ethylene group,
Octadodecenylethylene group, 1-cyclohexene-
1,2-ylene group, 4-cyclohexene-1,2-ylene group, 5-methyl-4-cyclohexene-1,2, -ylene group, 4,5,6-trimethyl-4-cyclohexane-1,2- Irene group, 5-norbornene-2,3ylene group, bicyclo [2,2,2] oct-5-ene-2,3
-Ylene group and the like.

The divalent substituted aliphatic residue of A is a divalent aliphatic residue as described above substituted with an aryl group such as a phenyl group, and an ether bond is formed in the structure by an oxygen atom. And those substituted with a halogen group such as a chloro group. For example, 1-methyl-1-phenylethylene group, 1-benzyl-1-methylethylene group, 1-phenylethylene group, 1,1-diphenylethylene group, 1-phenyltrimethylene group, 2
-Phenyltrimethylene group, 1-ethyl-1-phenyltrimethylene group, phenylvinylene group, 3,6-oxo-1,2,3,6-tetrahydrophthalyl group, 1,4,
5,6,7,7-hexachloro-5-norbornene-
2,3-ylene group and the like. The divalent aromatic residue of A includes an arylene group and a heteroaromatic residue, and is preferably a monocyclic or bicyclic ring, for example, an O-phenylene group, a 1,2-naphthylene group, , 8
-Naphthylene group, 2,3-pyridylyl group, 2,3-pyrazinediyl group, 2,3-benzo [b] thiophendiyl group and the like.

The divalent substituted aromatic residue of A is a divalent aromatic residue as described above substituted with a lower alkyl group such as a methyl group, or a halogen such as a chloro group or a bromo group. Those substituted with a group, or those substituted with a nitro group, an acetamino group and the like are included, for example, 3-methyl-1,2-phenylene group, 4-methyl-1,2-phenylene group, 3-chloro-1 , 2-phenylene group, 4-
Chloro-1,2-phenylene group, 3-bromo-1,2-
Phenylene group, 3,6-dichloro-1,2-phenylene group, 3,6-dibromo-1,2-phenylene group, 3,
4,5,6-tetrachloro-1,2-phenylene group,
3,4,5,6-tetrabromo-1,2-phenylene group, 3-nitro-1,2-phenylene group, 3-acetoamino-1,2-phenylene group, 4-chloro-1,8-naphthylene group, 4-bromo-1,8-naphthylene group, 4,
5-dibromo-1,8-naphthylene group, 4-bromo-5
-Chloro-1,8-naphthylene group, 4-nitro-1,8
-Naphthylene group, 5-methyl-2,3-benzo [b] thiophenediyl group, 5-chloro-2,3-benzo [b]
A thiophenediyl group, a 1-ethyl-2,3-indolediyl group and the like.

The O-naphthoquinonediazide compounds represented by the above general formula (I) used in the present invention are described in G. F.
Jaubert, Berichte der Deu
tschen Chemischen Gesells
chaft, 28, 360-364 (1895). E. FIG. Ames et al., Journal of
the Chemical Society. 351
8-3521 (1955), M. A. St
olberg et al., Journal of the C
chemical Society. 79, 2615-2
617 (1957), L. By Bauer et al.,
Journal of OrganicChemist
ry, 24, 1293-1296 (1959), or L. M. Werbel et al., Journa
l of Medical Chemistry, 1
Compounds represented by the following general formula (II) synthesized according to the method described in 0,32 to 36 (1967) and 1,2-
It can be synthesized by subjecting naphthoquinone-2-diazide-4-sulfonic acid chloride to a dehydrochlorination condensation reaction in the presence of a dehydrochlorination agent.

[0025]

Embedded image (Here, A is synonymous with the case of general formula (I))

This reaction proceeds in either an aqueous solvent or an organic solvent as long as it is in the presence of a dehydrochlorination agent. When used in a water solvent, lithium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like are suitable as the dehydrochlorinating agent. When the reaction is carried out in an organic solvent, the organic solvent does not have an OH group, for example, diethyl ether, diisopropyl ether, acetone, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, ethyl acetate, benzene, toluene, acetonitrile, etc. Is preferable, and as the dehydrochlorination agent, pyridine, diethylamine, triethylamine,
N, N-dimethylaniline and the like are preferable. In the reaction, it is preferable to use 1-1.5 equivalents of 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride and 1-1.5 equivalents of a dehydrochlorinating agent to 1 equivalent of the compound of the general formula (II). The reaction temperature is preferably -10 ° C to 40 ° C. Next, the O-naphthoquinonediazide compound used in the present invention will be exemplified, but the present invention is not limited thereto.

[0027]

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[0028]

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[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

[Chemical 12]

The addition amount of the compound represented by the above general formula (I) is usually 0.00 based on the total solid content of the image recording material.
It is in the range of 1 to 40% by weight, preferably 0.1 to 20% by weight, and more preferably 0.2 to 10% by weight.
The polymer compound having a hydroxyl group used in the present invention can be arbitrarily selected and used as long as it is capable of thermally reacting with an N-hydroxyimide compound in the presence of an acid to form a chemical bond. The above-mentioned polymer compound can be generally synthesized by a known method for obtaining a linear polymer. For example, it can be obtained by copolymerizing a vinyl monomer having a hydroxyl group with another vinyl monomer copolymerizable therewith.

As the vinyl monomer having a hydroxyl group used in the present invention, butanediol monoacrylate, EHC-modified butyl acrylate, 3-chloro-2-
Hydroxypropyl methacrylate, glycerol methacrylate, glycerol acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, phenoxyhydroxypropyl acrylate, EO-modified phthalic acid acrylate, EO, PO-modified phthalate Examples thereof include acid methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, p-2-hydroxyethyl styrene, m-hydroxy styrene, etc., but are not limited thereto.

Examples of other monomers copolymerizable with the above monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, isocrotonic acid, p-
Vinylbenzoic acid, p-vinylbenzenesulfonic acid, p-
Vinyl cinnamic acid, maleic acid monomethyl ether, maleic acid monoethyl ether, acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl methacrylate,
Vinyl benzoate, vinyl chloride, vinylidene chloride, styrene, vinyl acetate, N- (4-sulfamoylphenyl) methacrylamide, N-phenylphosphonylmethacrylamide, butadiene, chloroprene, isoprene,
Examples thereof include 2-mercaptoethyl acrylate, but the invention is not limited thereto.

The vinyl monomer containing a hydroxyl group and the other copolymerizable monomer can be copolymerized in any combination and in an arbitrary number of monomers, but the vinyl monomer containing a hydroxyl group can be copolymerized with another monomer. The appropriate proportion of the monomer is 0.5 to 90: 99.5 to 10 by weight, and the preferable range is 1 to 70:99.
-30, more preferably 3-40: 97-6
0. A linear polymer having a hydroxyl group can be obtained by cocondensation of a dicarboxylic acid compound having a hydroxyl group and a diol compound. For example, dicarboxylic acids such as 2-hydroxyterephthalic acid, 3-ethylhydroxyterephthalic acid, 2-hydroxy-propyldicarboxylic acid and ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3-butylene glycol, bisphenol A. Examples thereof include co-condensates of diol compounds such as hydrogenated bisphenol A and hydrogenated bisphenol F, but are not limited thereto.

If necessary, the above linear polymer can be co-condensed with other diols and dicarboxylic acids to obtain a multidimensional linear polymer. The weight ratio of the dicarboxylic acid having a hydroxyl group to the other monomer is 0.5 to 90:99.
A range of 5 to 10 is suitable, and a preferable range is 1
-70: 99-30, more preferably 3-4
It is 0: 97-60. Examples of the linear polymer having a hydroxyl group used in the present invention include various epoxy resins and phenoxy resins which are soluble in a solvent. The linear polymer having a hydroxyl group used in the present invention may be a resin containing a phenolic hydroxyl group.

Specifically, novolak resins such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol formaldehyde resin, and resole. Type of phenolic resins,
Examples thereof include phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and acrylic resin having a phenolic hydroxyl group, but are not limited thereto. The molecular weight of these linear polymers is 1,000 to 1,000,000, preferably 1,500 to 200,000, more preferably 2,000 to
It is 100,000. The linear polymer of the present invention can be used alone, but may be used as a mixture of several kinds. The amount of the linear polymer added to the image recording material is generally 1 to 95% by weight, preferably 20 to 95% by weight based on the total solid content of the image recording material.
90% by weight, more preferably 30 to 80% by weight.

The image recording material of the present invention is coated on a support using a solvent which dissolves or disperses the above-mentioned components. As the solvent used here, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- There are methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. , These solvents are used alone or as a mixture.

A mixed solvent obtained by adding a small amount of water, a solvent such as toluene, which does not dissolve the diazo resin or the polymer compound, to these solvents or the mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is 1 to 50% by weight.
A liquid dissolved or dispersed in these solvents is applied and dried to form a film, but when a negative image recording material is produced, it is desirable to dry at 50 ° C to 100 ° C.
On the other hand, when making a positive type image recording material, 100 to 15
It is preferable to dry at 0 ° C.

Alkyl ethers (eg ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg fluorine-containing surfactants), plasticizers for imparting film flexibility and abrasion resistance. (For example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added.
The amount of these additives added varies depending on the purpose of use, but generally 0.5 to 3 based on the total solid content of the image recording material.
0% by weight.

As a printout agent for obtaining a visible image immediately after absorption of radiation, a combination of a compound which releases an acid by heat from exposure and an organic dye capable of forming a salt can be mentioned as a representative. Specifically, JP-A-50-362
09- and JP-A-53-8128, combinations of O-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-362.
No. 23, JP-A-54-74728, and combinations of trihalomethyl compounds and salt-forming organic dyes. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used.
Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue B
OS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above,
Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

These printout agents and dyes are used in an amount of 0 to 30% by weight in the image recording material. When a visible image having a sufficient density can be obtained by the substance that absorbs radiation according to the present invention, it is not necessary to add such a dye.
Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate (heat-sensitive lithographic printing plate), generally, the solid content is preferably 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate. If necessary, a mat or a mat layer may be provided on the photosensitive film.

The support to which the image recording material of the present invention is applied is, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), such as aluminum (including aluminum alloy), zinc, Plates of metal such as copper, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate,
Films of plastics such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like, papers or plastic films laminated or vapor-deposited with the above metals are included. Among these supports, it is preferable to use a polyester film or an aluminum plate, and an aluminum plate is particularly preferable because it is extremely dimensionally stable. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is desirable to carry out a suitable hydrophilic treatment. Examples of such hydrophilization treatment include mechanical methods such as wire brush graining, brush graining in which a slurry of abrasive particles is poured to roughen the surface with a nylon brush, and ball graining, and HF and AlCl _3. After graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these roughening methods, acid or Etching with alkali, followed by anodic oxidation with a DC or AC power supply in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof to provide a strong passivation film on the aluminum surface preferable. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, U.S. Pat.
No. 066 and U.S. Pat. No. 3,181,461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat. No. 2,946,638, potassium zirconate fluoride treatment, U.S. Pat. 3,201,24
Phosphomolybdate treatment described in the specification of No. 7,
Alkyl titanate treatment described in British Patent 1,108,559, polyacrylic acid treatment described in German Patent 1,091,433, described in German Patent 1,134,093 and British Patent 1,230,447 Polyvinylphosphonic acid treatment, the phosphonic acid treatment described in JP-B-44-6409, U.S. Pat.
The phytic acid treatment described in Japanese Patent No. 951 and the hydrophilic organic polymer compounds described in JP-A-58-16893 and JP-A-58-18291 and a divalent metal ion Undercoat treatment with complex, JP-A-59-101
The water-soluble polymer having a sulfonic acid group described in Japanese Patent No. 651, which is hydrophilized by undercoating, is particularly preferable. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like.
Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. Also, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser / argon laser / krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser, a semiconductor laser and the like are particularly preferable.

As the developing solution and replenishing solution for the image recording material of the present invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, third
Sodium phosphate, same potassium, same ammonium, second
Sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium And the like. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. These alkaline agents may be used alone or in combination of two or more.

Various surfactants and organic solvents 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 development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. In addition, if necessary for the developer and replenisher,
It is also possible to add a reducing agent such as sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid or bisulfite, and further an organic carboxylic acid, an antifoaming agent or a water softener.

Among these developers, particularly preferable ones are, for example, JP-A-54-62004 and JP-A-57-57.
Those described in Japanese Patent No.
No. 77401, benzyl alcohol,
A developer composition comprising an anionic surfactant, an alkali agent and water, and a developer comprising an aqueous solution containing benzyl alcohol, an anionic surfactant and a water-soluble sulfite described in JP-A-53-44202. Examples of the liquid composition include a developer composition described in JP-A-55-155355, which contains an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent, and water.

When the image recording material of the present invention is used as a printing plate, it is developed with the above-mentioned developing solution and replenishing solution, and then rinse water, a rinse solution containing a surfactant, gum arabic and a starch derivative are contained. It is preferably post-treated with a desensitizing solution. These processes can be used in various combinations for post-processing.

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, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The photosensitive lithographic printing plate using the image recording material of the present invention is subjected to imagewise exposure, development, washing with water and / or rinsing and / or gumming. For example, if there is a film edge mark of the original image film), the unnecessary image portion is erased. Such erasing is performed by applying an erasing liquid as described in Japanese Patent Publication No. 2-13293 to an unnecessary image portion,
There is a method in which it is left as it is for a predetermined time and then washed with water. The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitizing gum if desired.

[0056]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 [Production of Substrate] A substrate was produced by the method disclosed in JP-A-56-28893. That is, the thickness is 0.24 mm
The aluminum plate of 1 was washed with water after the surface of the aluminum plate was grained using a nylon brush and a 400-mesh aqueous suspension of pumice. Then, the substrate was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% nitric acid, and washed with water. Next, this plate was subjected to 160 coulomb / 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition that the voltage at the anode was 12.7 V and the ratio of the electricity at the cathode to the electricity at the cathode was 0.8. The electrolytic surface-roughening treatment was carried out with an amount of electricity at the anode of dm ² .
The surface roughness at this time was measured and found to be 0.6 μ (Ra indication). Subsequent immersion in 30% sulfuric acid, 5
After desmutting at 5 ° C. for 2 minutes, it was anodized in 20% sulfuric acid for 2 minutes at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² . Then 70 ℃ sodium silicate
It was immersed in a 2.5% aqueous solution for 1 minute, washed with water and dried.

[Preparation of Carbon Black Dispersion] A composition having the following weight ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. Carbon black 1 part by weight Copolymer of benzyl methacrylate and methacrylic acid 1.6 parts by weight (molar ratio 72:28, weight average molecular weight 70,000) Cyclohexanone 1.6 parts by weight Methoxypropyl acetate 3.8 parts by weight

[Preparation of negative photosensitive lithographic printing plate] The aluminum plate obtained above was coated with the following photosensitive solution, and 8
It was dried at 0 ° C. for 2 minutes to obtain a negative photosensitive lithographic printing plate. The weight after drying was 2.0 g / m ² . Photosensitive solution Carbon black dispersion 10 g Compound I-14 0.5 g Benzyl methacrylate / methacrylic acid / 10 g 2-hydroxyethyl methacrylate = 60/20/20 molar ratio copolymer, weight average molecular weight 38,000 FC-430 ( Fluorosurfactant manufactured by US 3M) 0.1 g Methyl ethyl ketone 50 g The obtained negative photosensitive lithographic printing plate was exposed with a YAG laser adjusted to a plate surface output of 2 W, and then developed by Fuji Photo Film Co., Ltd., DN- 3C (1: 1), gum solution FN-
When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was printed on a Heidel SOR-KZ machine, good printed matter was about 3
I got 10,000 copies.

Comparative Example 1 In the photosensitive liquid composition of Example 1, an oil-soluble dye (Victoria Pure Blue BOH) was used in place of the carbon black dispersion.
A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that 3 g was used. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 1, all the photosensitive film was dissolved in the developing solution, and no image was obtained.

Examples 2 to 4 Samples were prepared in the same manner as in Example 1 except that the compound of Table 1 was used in place of 0.5 g of the compound (I-14) in the composition of the photosensitive solution of Example 1. Similarly, write with YAG laser,
After development, a negative image was obtained. When this printing plate was used and printed under the same conditions as in Example 1, the number of sheets shown in Table 1 and good printed matter were obtained.

[0062]

[Table 1] Table 1 ────────────────────────────── Example O-naphthoquinonediazide compound Number of printed sheets 2 I-16 Approx. 35,000 I-18 approx. 254,000 I-19 approx. 30,000

Example 5 A negative photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that the linear polymer was changed to the following resin.

[0064]

Embedded image

The negative photosensitive lithographic printing plate thus obtained was exposed with a YAG laser adjusted to a plate surface output of 2 W, and then developed by Fuji Photo Film Co., Ltd., DN-3C (1: 1), gum solution FN-. When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was printed with a Heidel SOR-KZ machine, about 50,000 good prints were obtained. Example 6 A negative photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that the following dye was used instead of the carbon black dispersion used in Example 1.

Dye 2,6-di-t-butyl-4- {5- (2,6-di-t-0.02g butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl} Thiopyrylium tetrafluoroborate (compound described in US Pat. No. 4,283,475) The obtained negative-type photosensitive lithographic printing plate was processed with a semiconductor laser (wavelength 825 nm, spot diameter: 1 / e ² = 11.9 μ). ) Was used to adjust the plate surface output to 110 mW at a linear velocity of 8 m / sec, and exposure was performed. Next, when the same developing treatment as in Example 1 was performed, a fine line having a line width of 10 μ could be formed.

Next, the beam diameter is adjusted to 6 μ (1 / e ² ), and similarly, at a writing resolution of 4000 dpi, 20
After exposing the dot image of 0 lpi, the same processing was performed to form a dot image. When the obtained lithographic printing plate was used to print on high-quality paper with a commercially available ink using a SOR-KZ type printer manufactured by Heidelberg, excellent printability was obtained as in Example 1. Comparative Example 2 A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 6 except that 0.2 g of an oil-soluble dye (Victoria Pure Blue BOH) was used in place of the dye in the photosensitive liquid composition of Example 6. did. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 6, all the photosensitive film was dissolved in the developing solution, and no image was obtained.

[0068]

INDUSTRIAL APPLICABILITY The image recording material of the present invention can be recorded without depending on the emission wavelength of the exposure light source, and particularly from near infrared to infrared (heat rays). Further, the image recording material of the present invention is recorded by using a solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared,
It is possible to directly make a printing plate from digital data of a computer or the like, and further, it is possible to obtain a heat mode writing type direct printing plate for which a conventional processing device or printing device can be used as it is.

Claims (1)

[Claims] 1. A negative image recording containing a substance that absorbs light and generates heat, a polymer compound having a hydroxyl group, and an O-naphthoquinonediazide compound represented by the following general formula (I). material. Embedded image In the formula, A is a divalent substituted or unsubstituted aliphatic residue, 2
A valent substituted or unsubstituted aromatic residue is shown.