JP2002303969A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image recording material capable of utilizing conven tional processing apparatus and printers as they are, capable of direct plate making from digital data of a computer or the like and having good recording and printing performances. SOLUTION: The image recording material contains a binder, a material which absorbs light and generates heat and a diazonium salt or a quinonediazide compound as a thermally decomposable material which substantially lowers the solubility of the binder in the undecomposed state.

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 positive type photosensitive lithographic printing plate for so-called direct plate making which can make a plate directly from a digital signal of 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 using a combination of exposure with an Ar laser and post-heating, and a silver salt photosensitive material laminated on a photosensitive resin are used. Known examples include a silver master type, a silicon master type, and a method in which a silicone rubber layer is broken by a discharge breakdown or a laser beam.

However, in the case of using an electrophotographic method, processes such as charging, exposure, and development are complicated, and the apparatus is complicated and large. In the above method, a post-heating step is required, and a high-sensitivity plate material is required, which makes it difficult to handle in a bright room. In the methods (1) and (2), the use of a silver salt complicates the processing and has the disadvantage of increasing the cost. The other method is a method with a relatively high degree of perfection, but has a problem in removing silicone residue remaining on the plate surface. On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared have become easily available in high output and small size. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

A conventional image recording material is disclosed in
No. 27919 discloses that a recording material containing a recording layer containing a polymer compound or a composition which is insoluble or slightly soluble before heating and which can be made more soluble in a solvent under the influence of heat is heated according to the information. And a method of forming an image. JP-A-56-69192 discloses a heat-sensitive recording material having a heat-sensitive layer containing a novolak type phenol resin and carbon black. However, these publications only disclose examples in which an image is recorded without using a laser beam, and use the above-mentioned near-infrared to infrared light as an exposure light source when performing plate making directly from digital data of a computer or the like. When an image was recorded using a laser having a light emitting area, a good printed matter could not always be obtained due to background smearing and a decrease in printing durability. In order to obtain good printed matter, the part irradiated with light during the alkali development treatment after exposure (non-image part)
Is easily dissolved and the area where no light hits (image area)
It is necessary that the remaining image portions have good durability. That is, in the above-described known technique, when laser light is used, the non-image portion is hardly dissolved and the image portion is easily melted because the recordability of the image is not good. Therefore, there is a demand for an image recording material capable of obtaining good printed matter with good image recording properties by laser light.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image recording material having good recording properties and printing durability, which can directly make a plate from digital data of a computer or the like, and can use a conventional processing device or printing device as it is. It is to be.

[0006]

The object of the present invention can be achieved by the following constitutions (1) to (13). (1) A binder, a substance that absorbs light and generates heat, and contains a diazonium salt as a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. Characteristic image recording material. (2) A binder, a substance that absorbs light and generates heat, and contains a quinonediazide compound as a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. Characteristic image recording material.

(3) The image recording material as described in (1) or (2) above, which contains an alkali-soluble resin as a binder. (4) The image recording material according to the above (1) or (2), which contains a phenol resin as a binder. (5) The image recording material according to the above (1) or (2), which contains an acrylic resin as a binder. (6) The above (1) containing a polyurethane resin as a binder
Or the image recording material according to (2).

(7) A binder, a substance which absorbs infrared light or near-infrared light and generates heat, and a solution of the binder when thermally decomposable and not decomposed. (1) The image recording material as described in (1) or (2), further comprising a layer containing a substance that substantially reduces the property. (8) a layer containing a substance that absorbs infrared light or near-infrared light and generates heat, on a support, and the solubility of the binder is substantially decomposed in a state of being thermally decomposable and not decomposed. The image recording material as described in the above item (1) or (2), further comprising a layer containing a substance to be reduced.

(9) The image recording material according to the above (7) or (8), wherein a dye is used as a substance which absorbs infrared light or near infrared light and generates heat. (10) The image recording material according to the above (7) or (8), wherein a pigment is used as a substance that absorbs infrared light or near infrared light and generates heat. (11) The image recording material according to the above (7) or (8), wherein carbon black is used as a substance that absorbs infrared light or near infrared light and generates heat. (12) The image recording material as described in (7) or (8) above, wherein a polyester film is used as the support. (13) The image recording material according to the above (7) or (8), wherein an aluminum plate is used as a support.

[0010] The image recording material of the present invention has a binder, a substance which absorbs light and generates heat on a support, and substantially dissolves the binder in a state of being thermally decomposable and not decomposed. A recording layer (photosensitive layer) made of a positive photosensitive composition containing at least a substance (hereinafter also referred to as an additive of the present invention) that reduces the amount of the photosensitive material is provided. When the additive of the present invention is contained, the image strength of the image area is improved, and the difference from the non-image area can be increased. That is, the additive of the present invention improves the solubility of the non-image portion of the binder resin forming an image and the non-solubility of the image portion.

In the present invention, it is preferable that the binder is an alkali-soluble resin in that an image can be easily formed by alkali development, and if the binder is a phenol resin, it is easily insolubilized by the additive of the present invention. When the binder is an acrylic resin, it is preferable in that a good film property and a durable image can be obtained, and when the binder is a polyurethane resin, a durable image having a strong image strength is obtained. Is preferred. In the present invention, it is preferable to use a dye as a substance that absorbs infrared light or near-infrared light and generates heat and absorbs infrared light or near-infrared light to generate heat. The use of a pigment as a substance is preferred in that heat generation efficiency is high, and the use of carbon black as a substance that absorbs infrared light or near-infrared light and generates heat has high heat generation efficiency and is inexpensive. preferable. In the present invention, in the state of being thermally decomposable and not decomposed, it is preferable to use an onium salt as a substance that substantially lowers the solubility of the binder, since the binder insolubilization efficiency is high, and a diazonium salt is used. When used, the binder insolubilizing efficiency is high, and the safety of the compound is high, which is preferable.In addition, when a quinonediazide compound is used, the binder insolubilizing efficiency is high, and the effect of assisting dissolution of the binder after thermal decomposition is high. Is preferred. In the present invention, the use of a polyester film as the support is inexpensive and is preferable in that the productivity of the image recording material is excellent, and the use of an aluminum plate as the support has high durability and dimensional stability of the image recording material. It is preferable in terms of excellent properties.

The binder is a polymer which is not easy to dissolve in an alkali developer, but preferably has an affinity for printing ink. In addition, a substance that absorbs light and generates heat decomposes a substance that absorbs laser light and generates heat, and the heat decomposes the substance that substantially reduces the solubility of the binder when it is thermally decomposable and does not decompose. What forms an image is preferable. In addition, a substance that substantially decomposes the solubility of the binder when thermally decomposable and does not decompose is thermally decomposed in the exposed portion to help dissolve the binder, and increases the solubility of the binder in the non-exposed portion. It is preferable to increase the lowering durability.

[0013] The above prior art does not clearly describe the addition of a substance which substantially lowers the solubility of the binder before pyrolysis. Particularly, the alkali-soluble phenol resin preferably used in the present invention is not described. It has been difficult to infer from the additives additives that substantially insolubilize binders such as acrylic resins and polyurethane resins. As a result of extensive studies, the present inventors have found that various onium salts, quinonediazide compounds, and the like are bound as substances that are thermally decomposable and substantially reduce the solubility of the binder when not decomposed. The present invention has been found to be excellent in lowering the solubility of the agent and to be suitably used, and has reached the present invention.

Hereinafter, the present invention will be described in detail. Examples of the onium salt include a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, a sulfonium salt, a selenonium salt, and an arsonium salt. Suitable onium salts used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng.,
18, 387 (1974), TS Bal et al, Polymer, 21, 423
(1980), diazonium salts described in JP-A-5-158230, U.S. Patent Nos. 4,069,055 and 4,069,056
Ammonium salt described in the specification of Japanese Patent Application No. 3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc.Con
f. Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JV Crivello et al, Macromorecules, 10 (6),
1307 (1977), Chem. & Eng. News, Nov. 28, p31 (198
8), European Patent No. 104,143, US Patent Nos. 339,049, 410,201, JP-A-2-150848, Iodonium salts described in JP-A-2-29514, JV Crivello et al, Polyme
r J. 17, 73 (1985), JV Crivelloetal. J. Org. Ch
em., 43, 3055 (1978), WR Watt et al, J. Polymer.
Sci., Polymer Chem. Ed., 22, 1789 (1984), JVC
rivello et al, Polymer Bull., 14, 279 (1985), J.
V. Crivello et al, Macromorecules, 14 (5), 1141 (19
81), JV Crivello et al, J. Polymer Sci., Polyme
r Chem. Ed., 17, 2877 (1979), EP 370,693
Nos. 3,902,114, 233,567, 297,443, 2
No. 97,442, U.S. Pat.Nos. 4,933,377, 161,811,
No. 410,201, No. 339,049, No. 4,760,013, No. 4,73
4,444, 2,833,827, German Patent 2,904,626,
The sulfonium salts described in JP-A-3,604,580 and JP-A-3,604,581, JVCrivello et al, Macromorecules, 10 (6), 13
07 (1977), JV Crivello etal, J. Polymer Sci., Po
selmerium salt described in lymer Chem. Ed., 17, 1047 (1979), CS Wen et al, Teh, Proc. Conf. Rad. Cur
ing ASIA, p478 Tokyo, Oct (1988).

In the present invention, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230. Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder by thermal decomposition and the fact that o-quinonediazide itself changes to an alkali-soluble substance. O used in the present invention
Examples of the quinonediazide compound include: "Wright-Sensitive Systems" by Coser (John Wil
ey & Sons. Inc.) pp. 339-352 can be used. Particularly, sulfonic acid esters or sulfonic acid amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds can be used. It is suitable. Also, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403. Of the benzoquinones described in U.S. Patent Nos. 3,046,120 and 3,188,210.
Esters of (1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride with a phenol-formaldehyde resin are also suitably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol-formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride with pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96
No. 575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
No. 2,797,213, No. 3,454,400, No. 3,544,323, No. 3,573,917, No. 3,674,495
No. 3,785,825; British Patent No. 1,227,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
No. 1,330,932, and German Patent No. 854,890, etc. can be mentioned. The amount of the o-quinonediazide compound used in the present invention is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, particularly preferably from 1 to 50% by mass, based on the total solid content of the photosensitive composition.
It is in the range of 0 to 30% by mass. These compounds can be used alone, but may be used as a mixture of several kinds. o
If the amount of the quinonediazide compound is less than 1% by mass, the recording properties of the image are deteriorated, and if it exceeds 50% by mass, the durability of the image area is deteriorated and the sensitivity is lowered.

The counter ions of the onium salts include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Benzoyl-benzenesulfonic acid, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable. The amount of the additive of the present invention other than the o-quinonediazide compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass.
It is. It is preferable that the additive and the binder of the present invention are contained in the same layer.

In the present invention, various pigments or dyes can be used as the substance that absorbs light and generates heat. Examples of pigments include commercially available pigment and color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977), “Latest Pigment Application Technology” (CM
C Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984) can be used.

The pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments,
Quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dye 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. Methods of surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. 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, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferred in terms of stability in a photosensitive layer coating solution, and when it exceeds 10 μm, it is not preferred in terms of uniformity of the photosensitive layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Dispersers include ultrasonic dispersers, sand mills, attritors, pearl mills, super mills,
Examples include 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, 1986).

As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) 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. In the present invention, among these pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment that absorbs infrared light or near infrared light, carbon black is preferably used. Dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246 and JP-A-59-125246.
-84356, JP-A-59-202829, JP-A-60-78787 and the like.
JP-A-58-173696, JP-A-58-18169
0, methine dyes described in JP-A-58-194595, JP-A-58-112793, and JP-A-58-112793.
Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like; And the cyanine dyes described in British Patent No. 434,875.

Further, as a dye, US Pat.
No. 938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 42645 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt described in JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363
Nos. 59-84248, 59-84249, 59-146063, and 59-146061 and pyrylium compounds described in JP-A-59-2161.
No. 46, a cyanine dye disclosed in U.S. Pat. No. 4,283,4.
A pentamethine thiopyrylium salt described in No. 75 and a pyrylium compound disclosed in Japanese Patent Publication Nos. 5-135514 and 5-19702 are particularly preferably used.

Another particularly preferred example of the dye is a near-infrared absorbing dye 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 mass, preferably 0.1 to 10% by mass, particularly preferably 0.5 to 10% by mass in the case of dyes, based on the total solid content of the photosensitive composition. In this case, particularly preferred is 3.1.
It can be added to the photosensitive composition at a ratio of from 10 to 10% by mass. If the amount of the pigment or dye is less than 0.01% by mass, the sensitivity is lowered. If the amount exceeds 50% by mass, the uniformity of the photosensitive layer is lost and the durability of the recording layer is deteriorated.
These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto. If it is a separate layer, it is desirable to add it to a layer adjacent to the layer containing a substance which substantially reduces the solubility of the binder when it is thermally decomposable and does not decompose. Also,
Although the same layer is preferable for the dye or pigment and the binder resin,
Another layer may be used.

The binder used in the present invention is preferably a water-insoluble and alkali-water-soluble resin. Although various resins having this property can be used, preferred resins include the following novolak resins.
For example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m-
/ P- mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m- / p-,
m- / o- or o- / p-mixture) and cresol formaldehyde resins such as mixed formaldehyde resins. Other resol type phenol resins are also preferably used, and phenol / cresol (m
−, P−, o− or m− / p−, m− / o−, o− /
Mixed formaldehyde resins are preferred, and phenol resins described in JP-A-61-217034 are particularly preferred. Phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, phenolic hydroxyl group-containing acrylic resin as disclosed in JP-A-51-34711, described in JP-A-2-866 Various alkali-soluble polymer compounds such as an acrylic resin having a sulfonamide group and a urethane resin can also be used. Acrylic resins having a sulfonamide group are particularly preferred. As the urethane resin, JP-A-63-12
No. 4047, No. 63-261350, No. 63-287
No. 942, No. 63-287943, No. 63-2879
No. 44, No. 63-287946, No. 63-28794
No. 7, 63-287948, 63-287949
And those disclosed in JP-A-1-134354 and JP-A-1-255854 are preferably used.
These alkali-soluble polymer compounds have a mass average molecular weight of 500 to 200,000 and a number average molecular weight of 200 to 200.
Those of 60,000 are preferred. These alkali-soluble polymer compounds may be used alone or in combination of two or more.
It is used in an amount of 9% by mass, preferably 10 to 90% by mass, particularly preferably 20 to 80% by mass. If the amount of the alkali-soluble polymer compound is less than 5% by mass, the durability of the recording layer deteriorates. If the amount exceeds 99% by mass, both sensitivity and durability are not preferred.

Various additives can be further added to the positive photosensitive composition of the present invention, if necessary. For example, it is preferable to use a condensate of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as octylphenol formaldehyde resin, in combination with formaldehyde in order to improve the oil sensitivity of an image. For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride, and tetrachlorophthalic anhydride described in U.S. Patent No. 4,115,128. , Maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride, and the like. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4
4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane and the like. Further, as organic acids, JP-A-60
-88942, JP-A-2-96755, and the like, and include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, and carboxylic acids. Sulfonic acid,
Dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,
4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4
-Cyclohexene-1,2-dicarboxylic acid, erucic acid,
Lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The proportion of the above cyclic acid anhydride, phenols and organic acids in the photosensitive composition is from 0.05 to
It is preferably 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10% by mass.

In the photosensitive composition of the present invention, in order to widen the stability of processing under development conditions, the photosensitive composition described in JP-A-62-251740 or JP-A-3-208514 is used. Nonionic surfactant, JP-A-59-121044
And an amphoteric surfactant described in JP-A-4-13149 can be added. Specific examples of the non-ionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N
-Betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition,
It is preferably 0.05 to 15% by mass, more preferably 0.1 to 15% by mass.
1 to 5% by mass. A printing-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image colorant can be added to the photosensitive composition of the present invention. Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128,
No. 53-36223, No. 54-74728, No. 60-3626, No. 61-14
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 3748, 61-151644 and 63-58440 can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, Japanese Patent Application Laid-Open No.
The dyes described in JP 93247 A are particularly preferred. These dyes, based on the total solid content of the photosensitive composition,
It can be added to the photosensitive composition at a ratio of 0.01 to 10% by mass, preferably 0.1 to 3% by mass. Further, a plasticizer may be added to the photosensitive composition of the present invention, if necessary, in order to impart flexibility and the like to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,
For example, oligomers and polymers of tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid are used.

The image recording material of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution on a suitable support. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, and the like. However, the present invention is not limited to this. These solvents are used alone or as a mixture.
The concentration of the above components (total solids including additives) in the solvent,
Preferably it is 1 to 50% by mass. The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally ranges from 0.5 to 0.5 for photosensitive printing plates.
-5.0 g / m < ² > is preferable. As a method of applying,
Various methods can be used, 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 film deteriorate. In the photosensitive layer according to the invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. A preferable addition amount is 0.01 to 1% by mass of the whole photosensitive composition, more preferably 0.05 to 0.
5% by mass.

The support used in the present invention is a dimensionally stable plate-like material such as paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film on which a metal is laminated or vapor-deposited as described above. As the support of the present invention,
Polyester film or aluminum plate is preferred,
Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon,
There are iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of the foreign element in the alloy is at most 10% by mass. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm ~
About 0.6 mm, preferably 0.15 mm to 0.4 m
m, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary,
If desired, anodizing treatment is performed to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming a porous oxide film can be used, and 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 the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat.No. 2,714,
Nos. 066, 3,181,461, 3,280,734 and 3,90
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in US Pat. No. 2,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. Others
No. 063, U.S. Pat.Nos. 3,276,868, 4,153,461, and
For example, a method of treating with polyvinyl phosphonic acid as disclosed in 4,689,272 is used.

The image recording material of the present invention has a positive photosensitive composition provided on a support. If necessary, an undercoat layer may be provided between the photosensitive composition and a matt layer on the photosensitive composition layer. Layers can be provided. Various organic compounds are used as the undercoat layer component, for example, carboxymethyl cellulose,
Dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, naphthylphosphonic acid,
Organic phosphonic acids such as alkyl phosphonic acid, glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, phenylphosphoric acid which may have a substituent, naphthyl phosphoric acid, organic phosphoric acid such as alkyl phosphoric acid and glycerophosphoric acid, Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, amino acids such as glycine and β-alanine, and hydroxy groups such as triethanolamine hydrochloride Or a mixture of two or more of them.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the above compound by immersing the aluminum plate, and then washed and dried with water or the like to provide an organic undercoat layer. . In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by mass can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass, and the immersion temperature is 20 to 90 ° C, preferably 25 to 90%.
To 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this can be adjusted to pH 1 to 12 with a basic substance such as ammonia, triethylamine, potassium hydroxide or the like, or an acidic substance such as hydrochloric acid or phosphoric acid. Further, a yellow dye can be added for improving the tone reproducibility of the image recording material. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

Further, a mat layer can be provided on the surface of the positive photosensitive composition layer of the present invention in order to prevent abrasion, adhesion failure and the like. Specifically, a method of providing a mat layer as described in JP-A-50-125805, JP-B-57-6658, and JP-A-61-28986 is described in JP-B-62-62337. And a method of thermally fusing such solid powder. The average diameter of the mat layer used in the present invention is preferably 100 μm or less, and more preferably 2 to 8 μm. When the average diameter is large, it is difficult to form a thin line and the number of highlight dots is reduced, which is not preferable in tone reproduction. If the average diameter is 2 μm or less, it is not preferable in terms of scratches and the like. The coating amount of the mat layer is 5-200 mg / m
² is preferred, and more preferably 20 to 150 mg / m ² . A coating amount larger than this range causes abrasion, while a coating amount smaller than this range is not preferable in terms of adhesion failure.
The positive image recording material prepared as described above is usually subjected to image exposure and development processing. Examples of the light source of the actinic ray used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. As radiation, electron beam, X-ray,
There are ion beams, far infrared rays, and the like. G-line, i-line,
Deep-UV light and high-density energy beams (laser beams) are also used. Helium laser beam
Examples include a neon laser, an argon laser, a krypton laser, a helium / cadmium laser, a KrF excimer laser, and the like. 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 and a semiconductor laser are particularly preferable.

As a developer and a replenisher for the image recording material of the present invention, conventionally known aqueous alkaline solutions can be used. For example, sodium silicate, potassium silicate, tertiary
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 alkali agents are used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate. For example, JP-A-54-62004 discloses An alkali metal silicate described in JP-B-57-7427 is effectively used.

In the case of further developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as required for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and bisulfite, and an organic carboxylic acid, an antifoaming agent, and a water softener. Can be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As a post-process when the image recording material of the present invention is used as a printing plate, these processes can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform 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 case where the image recording material of the present invention is used as a photosensitive lithographic printing plate will be described. Image exposure, development, washing with water and / or
Alternatively, if there is an unnecessary image portion (for example, a film edge mark of an original film) on the lithographic printing plate obtained by rinsing and / or gumming, the unnecessary image portion is erased. Such an erasure is described in, for example,
A method of applying an erasing liquid as described in JP-A No. 93 to unnecessary image areas, leaving the same for a predetermined time, and washing with water is preferable.
The method of irradiating an unnecessary image portion with an actinic ray guided by an optical fiber as described in Japanese Patent Application Laid-Open Publication No. H11-207, and then developing the image portion can also be used.

The lithographic printing plate obtained as described above can be subjected to a printing process after coating with a desensitizing gum if desired. However, when a lithographic printing plate having a higher printing durability is desired to be obtained, Is subjected to a burning process. When burning a lithographic printing plate, before burning,
No. 2518, No. 55-28062, JP-A-62-31859, No. 61-15
It is preferable to carry out treatment with a surface-regulating liquid as described in each publication of 9655. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, Application by an automatic coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to
0.8 g / m ² (dry mass) is appropriate. The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned (for example, Fuji Photo Film Co., Ltd.).
Burning processor sold by: BP-1
300). The heating temperature and time in this case depend on the type of the component forming the image, but are preferably in the range of 180 to 300 ° C. and 1 to 20 minutes. The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming, if necessary. In such a case, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0041]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 (Carbon black dispersion) Carbon black 1 part by mass Copolymer of benzyl methacrylate and methacrylic acid 1.6 parts by mass (molar ratio 72:28, average molecular weight 70,000) Cyclohexanone 1.6 parts by mass methoxypropyl acetate 3 .8 parts by mass

The composition according to the above mass ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, and then its surface was grained using a nylon brush and a 400 mesh pumistone-water suspension, followed by thorough washing with water. This plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching, washed with water, and further immersed in 2% HNO ₃ for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, the plate was provided with a 3 g / m ² DC anodic oxide film at a current density of 15 A / dm ² using 7% H ₂ SO ₄ as an electrolytic solution, and then washed and dried. Next, the following undercoat liquid was applied to this aluminum plate, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 mg / m ² .

(Undercoat solution) β-alanine 0.1 g Phenylsulfonic acid 0.05 g Methanol 40 g Pure water 60 g Further, the following photosensitive solution was applied to this aluminum plate,
Drying at 2 ° C. for 2 minutes gave a positive photosensitive lithographic printing plate. The mass after drying was 2.0 g / m ² .

(Photosensitive solution) Esterified product of naphthoquinone-1,2-diazido-5-sulfonyl chloride and 0.90 g pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) What you have). Cresol formaldehyde-novolak resin 2.00 g (meta: para ratio = 6: 4, mass average molecular weight 1800, containing 0.5% of unreacted cresol 0.5%) p-octylphenol-formaldehyde novolak 0.02 g naphthoquinone-1,2-diazide-4 -Sulfonyl chloride 0.01 g Tetrahydrophthalic anhydride 0.05 g 4- (p-N, N-bis (ethoxycarbonylmethyl) -0.02 g aminophenyl) -2,6-bis (trichloromethyl) -s-triazine 4 -(P-N- (p-hydroxybenzoyl) amino-0.02 g phenyl) -2,6-bis (trichloromethyl) -s-triazine Victoria pure blue BOH with 1-naphthalene-0.03 g sulfonic acid Dyes described above Carbon black dispersion 1. 02 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., 0.06 g fluorine-based surfactant) Methyl ethyl ketone 20 g Methyl alcohol 7 g

After exposing the obtained positive photosensitive lithographic printing plate with a YAG laser adjusted to a plate surface output of 2 W, a developing solution manufactured by Fuji Photo Film Co., Ltd., DP-4 (1: 8), a rinsing solution FR- 3 (1: 7) through an automatic processor. Next, Gum GU-7 manufactured by Fuji Photo Film Co., Ltd.
After processing the printing plate with (1: 1) and leaving it for one day, Heidel KO
Printing was performed with an RD machine. As a result of increasing the image strength of the image area and the developing property of the non-image area, a good printed matter without background smear was obtained.

Comparative Example 1 In Example 1, naphthoquinone-1,2-diazide-
A positive-type photosensitive planographic printing plate was prepared in the same manner except that an esterified product of 5-sulfonyl chloride and pyrogallol-acetone resin and naphthoquinone-1,2-diazide-4-sulfonyl chloride were omitted. When the same exposure and development processes were performed as in Example 1, only a weak image having a small density difference between the image area and the non-image area was obtained. When printing was performed in the same manner as in Example 1 using this, only a printed material having a background stain was obtained.

Example 2 An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of 400 mesh pumistone, and washed thoroughly with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This was converted to 160 coulomb / s in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of VA = 12.7V.
Electrolytic surface-roughening treatment was performed with a dm ² anode charge. When the surface roughness was measured, it was 0.6 μ (Ra display). After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a thickness of 2.7 g / at a current density of 2 A / dm ² in a 20% H ₂ SO ₄ aqueous solution.
Anodized so as to obtain m ² .

Next, the following photosensitive solution was prepared, and this photosensitive solution was applied on an anodized aluminum plate.
After drying for a minute, a photosensitive lithographic printing plate was prepared. The coating amount at this time was 2.5 g / m ² in dry mass.

(Photosensitive solution) Esterified product of naphthoquinone-1,2-diazido-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (see Example 1 in US Pat. No. 3,635,709) What you have). Polyurethane synthesized from 4,4'-diphenylmethane diisocyanate and 2,2-0.30 g bis (hydroxymethyl) propionic acid (described in Synthesis Example 1 of JP-A-63-124047). Cresol formaldehyde-novolak resin 0.80 g 2- (p-methoxyphenyl) -4,6-bis (trichloro 0.02 g methyl) -s-triazine oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01 g Carbon black dispersion 0.62 g Megafax F-177 (manufactured by Dainippon Ink and Chemicals, Inc., 0.06 g fluorine-based surfactant) Ethylene dichloride 10 g Methyl cellosolve 10 g

The obtained positive-type photosensitive lithographic printing plate was exposed to a YAG laser adjusted to a plate surface output of 2 W, and diluted with an 8-fold diluted aqueous solution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. Immersion development was performed for 60 seconds. Using the obtained lithographic printing plate, printing was performed on high quality paper with a commercially available ink using a KOR type printing machine manufactured by Heidelberg. As a result of the increase in the durability of the image area, the final number of printed sheets was 65,000, and the printing durability was excellent.

Comparative Example 2 In Example 2, naphthoquinone-1,2-diazide-
A positive photosensitive lithographic printing plate was prepared in the same manner except that the esterified product of 5-sulfonyl chloride and pyrogallol-acetone resin was removed. When the same exposure and development processing as in Example 2 was performed, only a weak image having a small density difference between the image area and the non-image area was obtained. Example 2 using this
When the same printing as described above was performed, only a small amount of printed matter with background stains was obtained.

Example 3 The following photosensitive solution was applied on the anodized aluminum plate used in Example 2 and dried at 100 ° C. for 2 minutes to prepare a photosensitive lithographic printing plate. The coating amount at this time was 2.5 g / m ² in dry mass.

(Photosensitive Solution) Esterified product of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) What you have). 1.10 g of N- (p-aminosulfonylphenyl) methacrylamide and a copolymer of methyl methacrylate (as described in Synthesis Example 1 in EP 330,239 (A ₂ )). 2- (p-methoxyphenyl) -4,6-bis (trichloro 0.02 g methyl) -s-triazine oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01 g The carbon black dispersion 0.62 g Mega FAK F-177 (manufactured by Dainippon Ink and Chemicals, Inc., 0.06 g fluorine-based surfactant) Methyl ethyl ketone 10 g Methyl cellosolve 10 g

The obtained positive photosensitive lithographic printing plate was exposed with a YAG laser adjusted to a plate surface output of 2 W, and diluted with an 8-fold diluted aqueous solution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. Immersion development was performed for 60 seconds. Using the obtained lithographic printing plate, printing was performed on high quality paper using a commercially available ink and UV ink using a KOR type printing machine manufactured by Heidelberg. When the final number of prints was examined, the durability of the image area was improved. As a result, the number of prints when using the normal ink was 60,000.
The printing durability was excellent, with 30,000 sheets printed using UV ink.

Example 4 A JIS A1050 aluminum plate having a thickness of 0.24 mm was subjected to brush graining with a rotating nylon brush while supplying a suspension of pumistone and water having an average particle size of about 21 μm to the aluminum surface. After that, it was washed well with water.
After etching by immersing in a 10% aqueous sodium hydroxide solution at 50 ° C. for 10 seconds, the substrate was washed with running water, then neutralized and washed with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% HNO ₃ aqueous solution at a voltage of 12.7 V and a current of 160 coulombs / dm ^{2 at} the anode using an alternating waveform current of a sine wave. When the surface roughness was measured,
(Ra display). Subsequently, the substrate was immersed in a 30% aqueous solution of H ₂ SO ₄ and desmutted at 55 ° C. for 2 minutes.
The substrate was prepared by anodic oxidation in a 0% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ^{2 so} that the thickness of the oxide film was 2.7 g / m ² . An undercoat liquid having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² .

(Undercoating solution) Aminoethylphosphonic acid 0.1 g β-alanine 0.1 g Phenylphosphonic acid 0.15 g Methanol 40 g Pure water 60 g
Drying was performed at 2 ° C. for 2 minutes to obtain a positive photosensitive lithographic printing plate.
The weight after drying was 1.5 g / m ² .

(Photosensitive solution) Cresol formaldehyde-novolak resin 2.00 g (meta: para ratio = 6: 4, mass average molecular weight 1100, containing unreacted cresol 0.5%) 2,5-dibutoxy-4-morpholino-benzene 0.29 g diazonium hexafluorophosphate tetrahydrophthalic anhydride 0.05 g 4- (p-N, N-bis (ethoxycarbonylmethyl) -0.02 g aminophenyl) -2,6-bis (trichloromethyl) -s-triazine Phosphorous acid 0.01 g Oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01 g Carbon black dispersion 0.62 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., 0.02 g fluorine) Surfactant) Methyl ethyl ketone 15 g 1-methoxy-2-p Propanol 10 g

Based on the method described in Example 1 of JP-B-61-28986, on the photosensitive layer coated in this manner, (methyl methacrylate / ethyl acrylate /
A mat layer was provided by electrostatic spraying of a copolymer aqueous solution of sodium acrylate (68/20/12). The obtained positive photosensitive lithographic printing plate is exposed to a YAG laser adjusted to a plate surface output of 2 W, and immersed in an 8-fold diluted aqueous solution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. for 60 seconds. Developed. Next, the plate surface was wiped with a burning surface conditioning liquid BC-3 manufactured by Fuji Photo Film Co., Ltd.
Heat treatment was performed at 0 ° C. for 7 minutes. After the plate cooled, the plate surface was treated with a solution obtained by diluting gum GU-7 manufactured by Fuji Photo Film Co., Ltd. with water twice. When the lithographic printing plate was allowed to stand for one day and then printed by a printing machine Heidelberg KOR-D, the durability of the image portion was increased, and as a result, a good printed matter having a high print density was obtained.

Example 5 A positive photosensitive lithographic printing plate was obtained in the same manner as in Example 3, except that the following dye was used in place of the carbon black dispersion used in Example 3. (Dye) 2,6-di-t-butyl-4- {5- (2,6-di-0.01422 g t-butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl} thiopyrylium Tetrafluoroborate (compound described in US Pat. No. 4,283,475)

A semiconductor laser (wavelength: 825 nm, beam diameter: 1 / e ² = 1.11) was used for the obtained positive photosensitive lithographic printing plate.
9 μ), and a printing plate output of 110 m at a linear velocity of 8 m / sec.
Adjusted to W and exposed. Next, when the same developing treatment as in Example 3 was performed, a thin line having a line width of 10 μm was formed. Next, the beam diameter was adjusted to 6 μ (1 / e ² ), and
After exposing a dot image of 200 lpi at a writing resolution of 000 dpi, the same processing was performed to form a dot image.
Using the obtained lithographic printing plate, KOR manufactured by Heidelberg
When printing was performed on high quality paper using a commercially available ink and UV ink with a pattern printing machine, the durability of the image area was improved. As a result, the same excellent printing durability as in Example 3 was obtained.

Example 6 An aluminum plate having a thickness of 0.24 mm was grained with a nylon brush and a 400 mesh pumicestone-water suspension, and washed thoroughly with water to prepare a substrate [I]. Substrate [I] was placed in 10% sodium hydroxide at 70 ° C for 2 hours.
After immersion for 0 seconds and etching, after washing with running water, 20%
Neutralized washing with HNO ₃ , washing with water, and 4% in 0.7% nitric acid aqueous solution using a sinusoidal alternating waveform current at 12.7 V
An electrolytic surface roughening treatment was performed at an amount of electricity of 00 coulomb / dm ² , and the substrate was washed with water to prepare a substrate [II]. This substrate [II] was dissolved in a 10% aqueous sodium hydroxide solution so that the amount of dissolution on the surface was 0.1%.
It processed so that it might be 9 g / m < ² >. After washing with water, neutralize and wash in a 20% nitric acid solution to perform desmutting, then 18%
Anodization was performed in a sulfuric acid aqueous solution such that the amount of the oxide film became 3 g / m ² . Next, the following photosensitive solution was prepared, coated on the anodized aluminum plate, and dried at 100 ° C. for 2 minutes to prepare a photosensitive lithographic printing plate. The coating amount at this time was 2.3 g / m ² in dry mass.

(Photosensitive solution) Esterified product of 2,3,4-trihydroxybenzophenone and 0.45 g naphthoquinone-1,2-diazido-5-sulfonyl chloride (esterification ratio: 90 mol%) N- (p-amino) 1.70 g of sulfonylphenyl) methacrylamide and a copolymer of methyl methacrylate (as described in Example 1 of EP 330,239 (A ₂ )). Naphthalene-2-sulfonic acid 0.007 g Cresol (60% meta form, 40% ortho form) -0.70 g Formaldehyde resin (mass average molecular weight; 4,000) 2- (p-methoxyphenyl) -4,6-bis (Tri-0.02 g chloromethyl) -s-triazine naphthoquinone-1,2-diazide-sulfonyl chloride 0.01 g Victoria Pure Blue BOH 0.015 g (dye manufactured by Hodogaya Chemical Co., Ltd.) 02g Megafax F-177 0.004g (Fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) Dimethylformamide 4g 1-Methoxy-2-propanol 9g Methyl ethyl ketone 7g

The obtained positive photosensitive lithographic printing plate was exposed with a YAG laser adjusted to a plate surface output of 2 W, and diluted at 25 ° C. with an 8-fold diluted aqueous solution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Immersion development was performed for 60 seconds. When the erasing speed of the obtained lithographic printing plate was measured using PR-1 (erasing liquid manufactured by Fuji Photo Film Co., Ltd.), it was as efficient as 10 seconds. Also, as a result of improved durability of the image area, the printing durability was 45,000 sheets when using UV ink,
When the oil-based ink was used, it was excellent at 90,000 sheets. In addition, this lithographic printing plate has excellent UV ink cleaning liquid resistance, and as a result, the difference in developability between the image area and the non-image area has been increased,
It was also excellent in processability with a fatigue developer having reduced activity.

[0064]

According to the present invention, it is possible to provide an image recording material having good recording properties and printing durability, which can directly make a plate from digital data of a computer or the like, and can use a conventional processing apparatus or printing apparatus as it is.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuichi Shiraishi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. Inside (72) Inventor Yuichi Shiraishi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. F term (reference) 2H025 AA12 AB03 AC08 AD03 BA01 BA04 CB00 CC11 CC20 DA31 2H096 AA06 BA09 EA04 EA23

Claims (4)

[Claims] 1. A binder, a substance that absorbs light and generates heat, and a diazonium salt as a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. An image recording material comprising: 2. A binder, a substance that absorbs light and generates heat, and a quinonediazide compound as a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. An image recording material comprising: 3. A binder, a substance which absorbs infrared light or near-infrared light and generates heat, and a binder which is thermally decomposable and does not decompose on a support. The image recording material according to claim 1, further comprising a layer containing a substance that substantially reduces the density. 4. A layer containing a substance that absorbs light and generates heat, and a substance that is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. 3. The image recording material according to claim 1, wherein a layer containing the image recording material is provided.