JPH08211614A - Planographic printing plate - Google Patents

Abstract

PURPOSE: To provide a planographic printing plate having high sensitivity, stable photographic characteristics with time and little contamination with ink during printing by incorporating a specified water-soluble polymer containing specified functional groups into a layer containing physical developing nuclei. CONSTITUTION: This planographic printing plate consists of a base body and a silver halide emulsion layer and a layer containing physical developing nuclei formed on the base body and uses a silver complex salt diffusion transfer method. The layer containing physical developing nuclei contains a water-soluble polymer containing at least one functional group expressed by formulae I, II and III. In formula I, R3 is a hydrogen atom, alkyl group, phenyl group, amino group or amidino group, R4 is a hydrogen atom or amino group. In formula II, X is a carbon or phosphorus atom, Y is an oxygen, sulfur or nitrogen atom, Z is a sulfur or nitrogen atom or NH group, R5 is an alkyl group or alkoxy group. In formula III, W is a nitrogen-contg. heterocyclic ring and n is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material for producing a lithographic printing plate using a silver salt diffusion transfer method, which has high sensitivity, little printing stain, and excellent storage stability. It relates to an improved lithographic printing plate.

[0002]

2. Description of the Related Art A lithographic printing plate utilizing a silver salt diffusion transfer method is generally composed of an oleophilic image-forming portion that accepts oily ink and an oil-repellent non-image-forming portion that does not accept ink. The image area is composed of a hydrophilic area that receives water. In a normal lithographic printing plate, therefore, both water and ink are supplied to the plate surface, and the image area is colored ink.
The non-image area is formed by selectively receiving water and transferring the ink on the image area onto a substrate such as paper. Therefore, in order to obtain a good printed matter, the difference in lipophilicity and hydrophilicity between the surface of the image area and the background non-image area is sufficiently large, and the image area is sufficient when water and ink are applied. It is necessary to accept a certain amount of ink and not accept any ink in the non-image area.

A printing plate has been already put into practical use in which the formed surface metal silver image is made lipophilic by applying the silver salt diffusion transfer system and is used as an ink receiving property. The present invention is disclosed in JP-B-48-30562 and JP-A-53-
Starting from a lithographic printing plate material having a physical development nucleus layer comprising a heavy metal or a sulfide thereof described in JP-A No. 21602, 54-103104, etc. on a silver halide emulsion layer, and printing the lithographic printing plate material. It relates to novel materials with improved properties and photographic properties. As described above, the ideal as a lithographic printing plate is that ink is satisfactorily accepted in the image area, whereas ink is not accepted in the non-image area at all, and print stain does not occur. Therefore, various desensitizing methods have been studied depending on the respective plate materials and printing methods.

In general, it is well known in the art that the occurrence of print stains in lithographic printing is not a single cause but a combination of various factors. For example, it may be due to the inherent properties of the plate material, or may be due to printing ink, fountain solution, printing paper, or even the condition of the printing press.
Or, it may be the influence of environmental conditions such as temperature and humidity during printing. When printing, it is important to properly maintain those conditions and environment. However, from a practical point of view, there is a demand for a material that can be printed under as wide a condition as possible.

Further, in recent years, in response to an increase in the amount of information, there has been a strong demand for speeding up information processing, so that it is desired to shorten the plate making processing time, that is, to increase the sensitivity of the photosensitive printing material. .

[0006]

In the description of JP-A-53-21602 proposed by the present applicant, the effect of the binder contained in the layer containing physical development nuclei on printing is described in detail. A synthetic polymer compound applied thereto is disclosed. However, these plate-making printing materials have deterioration in photographic characteristics (softening) over time in terms of photographic characteristics, printability, etc., and accompanying reduction in printing durability and printing stains, etc. It wasn't possible. The present invention has improved these and provides a lithographic printing plate having high sensitivity, stable photographic characteristics over time, and less ink stains during printing.

[0007]

The problems relating to the present invention can be solved by using the following method. That is, in a lithographic printing plate utilizing a silver complex salt diffusion transfer method comprising a silver halide emulsion layer and a layer containing physical development nuclei on a support, the general formula (A) in the layer containing the physical development nuclei, A target printing plate was obtained by containing a water-soluble polymer containing at least one functional group represented by (B) and (C).

[0008]

[Chemical 4]

In the general formula (A), R ₃ represents a hydrogen atom, an alkyl group, a phenyl group, an amino group or an amidino group, and R 3
₄ represents a hydrogen atom or an amino group.

[0010]

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In the general formula (B), X represents a carbon atom or a phosphorus atom, and Y represents an oxygen atom, a sulfur atom or a nitrogen atom. Z represents a sulfur atom, a nitrogen atom or an NH group. R ₅ represents an alkyl group, an alkoxy group, an aryl group, a pyrrolidino group, a piperidino group, a mercapto group or a thiosemicarbazide group. R ₅ when X is a phosphorus atom
Is an alkoxy group, and two X are substituted. Further, Y and R ₅ may form a ring via a carbon atom, a nitrogen atom or the like. When Z is a nitrogen atom or an NH group, the atomic group of X (= Y) R ₅ represents a dithiocarbamic acid group or an N-substituted thiourea residue.

[0012]

[Chemical 6]

In the general formula (c), W represents a nitrogen-containing heterocycle and n represents 1 or 2.

Preferred examples of the water-soluble polymer having a functional group represented by the above general formula (A), (B) or (C) are the following general formulas (A-1) and (B-1), respectively.
And a water-soluble polymer containing a repeating unit represented by (C-1).

[0015]

[Chemical 7]

In the general formula (A-1), R ₁ represents a hydrogen atom or a methyl group, and Q represents an alkylene group, a phenylene group, a COO group, an NHCOO group, an NHCOOC ₂ H ₅ group, C
It represents a divalent linking group such as an ONH group. R ₂ is a divalent linking group and represents an alkylene group, an alkyleneoxy group or the like,
R ₂ may not be included in some cases. R ₃ represents a hydrogen atom, an alkyl group, a phenyl group, an amino group or an amidino group. R ₄
Represents a hydrogen atom or an amino group.

[0017]

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In the general formula (B-1), R ₁ represents a hydrogen atom or a methyl group, Q represents an alkylene group, a phenylene group, a COO group, an NHCOO group, an NHCOOC ₂ H ₅ group, C
It represents a divalent linking group such as an ONH group. R ₂ represents an alkylene group, an alkyleneoxy group or an arylene group, R ₂
May not be included. X represents a carbon atom or a phosphorus atom, and Y represents an oxygen atom, a sulfur atom or a nitrogen atom. Z represents a sulfur atom, a nitrogen atom or an NH group. R ₅ represents an alkyl group, an alkoxy group, an aryl group, a pyrrolidino group, a piperidino group, a mercapto group or a thiosemicarbazide group. When X is a phosphorus atom, R ₅ is an alkoxy group and two X's are substituted. Further Y and R ₅
May form a ring via a carbon atom, a nitrogen atom or the like.
Further, when Z is a nitrogen atom or an NH group, X (= Y)
The atomic group of R ₅ represents a dithiocarbamic acid group or an N-substituted thiourea residue.

[0019]

[Chemical 9]

In formula (C-1), R ₁ represents a hydrogen atom or a methyl group, and Q represents an alkylene group, a phenylene group, a benzyl group, a COO group, an NHCOO group, an NHCOO.
It represents a divalent linking group such as a C ₂ H ₅ group, a CONH group, or a functional group represented by the following general formula (C-2). A is a nitrogen-containing heterocyclic substituent having a mercapto group, and represents an atomic group necessary for forming an oxadiazole ring, a thiadiazole ring, a selenadiazole ring, a triazole ring, a triazine ring, etc. May be combined with each other.

[0021]

[Chemical 10]

In the general formula (C-2), R ₆ represents a hydrogen atom or a methoxy group.

Specific preferred examples of the repeating unit represented by formula (A-1) include repeating units obtained by polymerizing the monomers shown below.

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

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[0028]

[Chemical 15]

[0029]

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[0030]

[Chemical 17]

[0031]

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[0032]

[Chemical 19]

[0033]

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[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

Specific preferred examples of the repeating unit represented by the general formula (B-1) include the following (b-1) to (b-1).
The repeating unit obtained by polymerizing the monomer as shown in 2) is mentioned.

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

[0043]

[Chemical 29]

[0044]

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[0045]

[Chemical 31]

[0046]

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[0047]

[Chemical 33]

[0048]

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Preferred specific examples of the repeating unit represented by the general formula (C-1) include the following (C-1) to (C-1).
The repeating unit obtained by polymerizing the monomer as shown in 1) is mentioned.

[0050]

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[0051]

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[0052]

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[0053]

[Chemical 38]

[0054]

[Chemical Formula 39]

[0055]

[Chemical 40]

[0056]

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[0057]

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[0058]

[Chemical 43]

[0059]

[Chemical 44]

[0060]

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Further, if the water-soluble polymer contained in the layer containing physical development nuclei has the functional groups represented by the general formulas (A), (B) and (C), it is an object of the present invention. The effect of
-1), (B-1) and (C-1) may be a homopolymer consisting of repeating units, or a repeating unit represented by the following general formula (D) may be combined with such a repeating unit. By using the above-mentioned copolymer, it is possible to improve the coatability, improve the adhesion to the silver halide emulsion layer, and provide a printing plate with excellent printing durability.

[0062]

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In the general formula (D), R ₇ and R ₈ represent a hydrogen atom or a methyl group, and R ₉ represents a hydrogen atom or an alkyl group, an alkoxymethyl group or a hydroxymethyl group.

The ratio of the repeating unit represented by the general formula (A-1) to the repeating unit represented by the general formula (D) in the copolymer is 0.1 for the repeating unit of the general formula (A-1). The effect of the present invention is most prominent when the amount is from 100% by weight to 100% by weight, and the effect may not be observed when the repeating unit of the general formula (A-1) is 0.1% by weight or less. . On the other hand, the general formula (B-1) or (C
-1) The ratio of the repeating unit represented by formula (D) to the repeating unit represented by formula (D) in the copolymer is 0.1% by weight of the repeating unit represented by formula (B-1) or (C-1). % Or more and 50% by weight or less, the effect of the present invention is most prominent, and the effect of the general formula (B-1) or (C
If the repeating unit of -1) is less than 0.1% by weight, the effect may not be observed, and if it exceeds 50% by weight, the solubility of the formed copolymer in water is insufficient. In some cases, it may be unfavorable because it may hinder application.

Preferred monomers for providing the repeating unit represented by the general formula (D) include acrylamide, methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide and the like. By introducing into the water-soluble polymer as a copolymerization component,
By appropriately adjusting the viscosity of the polymer, the coating property of the coating liquid containing the polymer can be improved as described above, and a printing plate having excellent printing durability can be obtained.

In the present invention, the object can be sufficiently achieved by using the homopolymer or the copolymer composed of two components as described above. However, depending on the individual brand to be applied, the water-soluble It may be preferable to improve the properties of the polymer. For example, for the purpose of increasing the hydrophobicity of the layer containing physical development nuclei to some extent and improving the ink acceptability at the time of printing, the (meth) acrylic acid alkyl ester (carbon Various hydrophobic monomers such as saturated alkyl esters of the number 1 to 20), (meth) acrylic acid benzyl ester, styrene and derivatives thereof may be introduced as a copolymerization component into the water-soluble polymer. Alternatively, for various purposes, monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or salts thereof, sodium vinyl sulfonate, p-
Monomers having sulfonic acid groups such as sodium styrene sulfonate and sodium (meth) allyl sulfonate, and hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate Monomers with methoxyethyl (meth) acrylate, methoxypolyethylene glycol mono (meth)
Monomers having a methoxy group and an ethyleneoxy group such as acrylate, or vinylimidazole, 4-vinylpyridine, 2-vinylpyridine, N,
N-dimethylaminoethyl (meth) acrylate, N,
N-diethylaminoethyl (meth) acrylate, N,
Monomers having a basic nitrogen atom such as N-dimethylaminopropylacrylamide, allylamine and diallylamine, and vinyl ester derivatives such as vinyl acetate, vinyl propionate and vinyl benzoate, N-vinylpyrrolidone, acrylonitrile, methyl vinyl ether, Various monomers such as butyl vinyl ether can also be introduced as a copolymerization component. Furthermore, if it is a small amount, it is possible to introduce a monomer such as divinylbenzene, ethylene glycol di (meth) acrylate, or methylenebisacrylamide as a bifunctional monomer.

However, when the above-mentioned monomers are introduced as a copolymerization component into the water-soluble polymer, the proportion of these components in the copolymer composition is 50% by weight.
It is preferably not more than, and the solubility of the water-soluble polymer obtained by adding more than that is lowered, or the degree of ink stain at the time of printing is deteriorated in the printing plate prepared in such a case, which is not preferable. Effects may appear.

The molecular weight of the polymer given in the present invention is preferably in the range of 5,000 or more and 1,000,000 or less as the weight average molecular weight, and a polymer having a molecular weight higher than this has a high solution viscosity and may be difficult to apply. Not preferable. Further, a printing plate formed by using a polymer having a low molecular weight in the above range is not preferable because the printing durability may decrease.

As the method of adding the polymer in the present invention, the polymer can be added before or after the coating of the physical development nuclei, but the physical development nuclei are used because of the stability of quality and the ease of production. The method of applying with is most advantageous. The usual range in which the polymer can be used is the type of colloidal substance as physical development nuclei,
Although there is some dependence on the amount and properties, the applied amount per square meter generally influences the printing characteristics of the printing plate formed. On average, it is used in an amount of 2 g / m ² or less is applied preferably such that the amount of 0.01 to 1 g / m ^2.

As the method for producing the polymer disclosed in the present invention, the usual radical polymerization method can be applied as it is. Besides water, various alcohols miscible with water are preferably used as the polymerization solvent for the purpose of appropriately controlling the degree of polymerization. At the time of polymerization, a compound having a mercapto group and a polymerizable double bond through a heterocycle, for example, (C-
It is preferable to polymerize the monomer as shown in 1), but in order to prevent the chain transfer reaction due to such a mercapto group, a base such as sodium hydroxide, potassium hydroxide or sodium hydrogen carbonate is added. Then, it is preferable to carry out the polymerization in a state in which the mercapto group is converted into a salt form. Alternatively, it is also possible to synthesize various esterified monomers in advance for the purpose of protecting the mercapto group, and deprotect after polymerization to synthesize the desired polymer, or, apart from such a method. Alternatively, a precursor polymer may be synthesized in advance and a low molecular weight compound having a functional group represented by the general formula (C) may be bound to the precursor polymer. It is usually necessary to remove the low molecular weight compound which has not been performed, and there may occur a problem that it is difficult to quantitatively bond the calculated amount of the functional group to the precursor polymer.

The polymers of the present invention are various common water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylamide, polyacrylic acid, dextran, pullulan and various modified starches. It can also be used as a mixture or in combination with a hydrophilic polymer.

In the silver salt diffusion transfer method, the exposed silver halide material is usually an alkaline one-bath developing and fixing composition liquid which is basically composed of a developing agent, its preservative and a solvent of silver halide. Is processed in. According to the general concept of the silver complex salt diffusion transfer process, the silver halide grains that have become developable by exposure are (in the case of a direct positive type silver halide light-sensitive material, the reverse) the reducing agent in the composition liquid. Although it is immediately reduced by the (developing agent component) to metallic silver (chemical development), the unexposed silver halide grains do not undergo direct reduction by the reducing agent and are halogenated in the composition liquid. It is once complexed and dissolved by a silver solvent such as thiocyanate and amines, diffused, and reduced mainly on the surface of the physical development nucleus as a reduction catalyst (physical development). The water-soluble polymer according to the present invention sufficiently exerts its effect by being present in the vicinity of such physical development nuclei, but due to its structural characteristics, it interacts with silver ions and, in some cases, forms a complex. Sometimes. In this case, the silver complex salt diffused by the silver halide solvent is captured by the water-soluble polymer according to the present invention to more effectively supply silver ions for physical development to the physical development nuclei and to be formed. It is envisioned that the physically developed silver will grow sufficiently in the matrix of the water soluble polymer to provide a strong adhesion of the silver image. When forming a lithographic printing plate by this method, the adhesiveness of the silver image to the substrate is extremely important for enhancing the printing durability, and its sufficient growth is an important factor that influences ink transfer. The water-soluble polymer obtained according to the present invention gives such a very favorable effect to physically developed silver, and in the non-silver image area where physically developed silver is not originally present, the presence of it on the surface of the silver salt light-sensitive material makes it compatible with water on the surface. It also has the effect of increasing the ink repellent property. Therefore, in the printing plate, the ink repulsion property in the non-silver image area is increased, so that a very favorable effect of hardly causing printing stains is also exhibited.

The water-soluble polymer represented by the general formula (C) is characterized by having a nitrogen-containing heterocyclic substituent having a mercapto group, and examples of the above-mentioned patents include JP-A-53-2.
Japanese Patent No. 1602 describes an example in which a polymer having a mercapto group is used for the same purpose. In this example, since the mercapto group is bonded to the polymer without passing through a heterocycle, reactions such as oxidation by oxygen in the air or formation of disulfide bonds occur in the aqueous polymer solution and in the coating film. There have been some inconveniences such as the characteristics of the silver halide photosensitive material changing with time, or the printing characteristics such as printing durability and ink transfer markedly changing during storage. On the other hand, by binding the mercapto group to the nitrogen-containing heterocycle as in the present invention, a thiol-thione tautomerism occurs between the nitrogen atom in the heterocycle and the mercapto group, resulting in a solution or solid film. In many cases, the mercapto group is often present in a substantially thione form in such a state, and such effects dramatically improve the temporal stability of the polymer to which the mercapto group is bound, and improve the photographic characteristics or printing characteristics of the light-sensitive material. The feature is that no adverse effect due to storage time of is also observed. Furthermore, since the mercapto group is bound to the heterocycle, the acidity of the mercapto group increases, and it can be easily converted to a mercaptide such as a sodium salt by a base such as sodium hydroxide or sodium hydrogen carbonate. As described above, it has a feature that a desired polymer can be stably synthesized without causing a chain transfer reaction during the polymerization. On the contrary, when mercapto group-introduced polymer is synthesized without passing through a heterocycle, formation of such mercaptide is carried out under normal polymerization conditions.
It is difficult in the H range and has various problems in synthesis.

Regarding the developing agent, in the development processing of a general photographic light-sensitive silver halide material, the developing agent may be contained in the photosensitive material or in the developing solution, or in both. It is also well known that the development processing of the present invention is carried out according to such a method, so that the development speed can be adjusted.

Examples of the developing agent used here include the following. Hydroquinone, catechol, pyrobenzene, and other hydroxybenzene-based developing agents and their derivatives, such as methylhydroquinone, dimethylhydroquinone, chlorohydroquinone, 4-methylcatechol, 4-ethylcatechol, 4-t-butylcatechol, gallic acid, and methyl gallate. Esters, gallic acid ethyl ester, etc., and para-aminophenol and its derivatives, such as N-methylparaaminophenol, 2,4-diaminophenol sulfate, or 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-. 3-pyrazolidone and the like. These developing agents are added after being dissolved in an aqueous solution thereof or a water-miscible organic solvent such as methanol, ethanol, propanol, acetone or ethylene glycol. It is preferably applied together with a liquid containing heavy metals or their sulfide colloids.

[0076] The required amount of developing agent to be added, for example, 1.0 g / m ² from 0.02 g / m ² hydroquinone,
Further, with 1-phenyl-3-pyrazolidone, 0.00
An amount of 1 g / m ² to 0.1 g / m ² is sufficient. The effect known by this is that not only the printing stain is remarkably improved, but also the photographic material and the printing characteristics have high contrast, the image sharpness is high, and the resolution is good, and thus a photosensitive material with little change in characteristics over time is obtained. .

The present invention is a lithographic printing plate to which the silver complex salt diffusion transfer method is applied, in which a specific polymer is contained in the image receiving layer, and therefore, other constitution or support, a silver halide emulsion layer, It is not limited by the silver complex salt transfer treatment method and the like. Next, examples of the polymer having a functional group according to the present invention are shown, but the present invention is not limited thereto. In addition, all the numbers in the formulas represent the weight% of each repeating unit in the copolymer composition.

[0078]

[Chemical 47]

[0079]

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[0080]

[Chemical 49]

[0081]

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[0082]

[Chemical 51]

[0083]

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[0084]

Embedded image

[0085]

[Chemical 54]

[0086]

[Chemical 55]

[0087]

[Chemical 56]

[0088]

[Chemical 57]

[0089]

Embedded image

[0090]

Embedded image

[0091]

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[0092]

[Chemical formula 61]

[0093]

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[0094]

[Chemical formula 63]

[0095]

[Chemical 64]

[0096]

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[0097]

[Chemical formula 66]

[0098]

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[0099]

[Chemical 68]

[0100]

[Chemical 69]

[0101]

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[0102]

【Example】

(I) Synthesis of Polymer Synthesis Example (Exemplified Polymer, P-1) 5 equipped with a stirring group, thermometer, reflux tube and nitrogen introducing tube
45 g of acrylamide and a-1 (thiourea and chloromethylstyrene (m,
(p-form mixture) was heated to reflux in ethanol for synthesis. Similarly, the compound a-2 was synthesized from guanylthiourea and chloromethylstyrene, and the others were synthesized in the same manner. 5 g of the monomer shown in FIG.
g and 100 g of ethanol were added and dissolved. 50 ° C
Place the flask on a water bath heated to 2, and stir under a nitrogen stream while using 2,2'-azobis (2-
Amidinopropane) dihydrochloride (V-50,
Polymerization was initiated by adding 0.5 g of Wako Pure Chemical Industries, Ltd. The mixture was heated and stirred at 50 ° C. for 1 hour, and then the temperature inside the flask was raised to 75 ° C., and the mixture was heated and stirred for 3 hours. As a result of GPC analysis, the polymer thus obtained was a polymer having a weight average molecular weight of about 100,000.

(I) Synthesis of Polymer Synthesis Example (Exemplified Polymer, P-9) 5 equipped with a stirring group, thermometer, reflux tube and nitrogen introducing tube
45 g of acrylamide and b-1 (thioacetic acid and chloromethylstyrene (m,
(p-form mixture) was heated to reflux in a water / ethanol mixed solvent (1: 2) in the presence of equimolar sodium hydroxide to synthesize. Similarly, the compound b-2 was synthesized from sodium xanthate and chloromethylstyrene, and the other compounds were synthesized in the same manner. 5 g of the monomer represented by 1) was introduced, and 200 g of distilled water and 100 g of ethanol were added and dissolved. The flask was placed on a water bath heated to 50 ° C., and 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, as a polymerization initiator was added while stirring under a nitrogen stream.
Polymerization was initiated by adding 0.5 g of Wako Pure Chemical Industries, Ltd. The mixture was heated and stirred at 50 ° C. for 1 hour, and then the temperature inside the flask was raised to 75 ° C., and the mixture was heated and stirred for 3 hours. As a result of GPC analysis, the polymer thus obtained was a polymer having a weight average molecular weight of about 100,000.

(I) Synthesis of Polymer Synthetic Example (Exemplified Polymer, P-17) 5 equipped with a stirring group, thermometer, reflux tube and nitrogen introducing tube
45 g of acrylamide and c-1 (bismuthiol and chloromethylstyrene (m, p body mixture)) were heated to reflux in a water / ethanol mixed solvent (1: 2) in the presence of equimolar sodium hydroxide in a 00 ml four-necked flask. Similarly, the compound of c-2 was synthesized from thiocyanuric acid monosodium salt and chloromethylstyrene, and the other compounds were also synthesized in the same manner.
g was introduced, 0.77 g of sodium hydroxide was added, and 200 g of distilled water and 100 g of ethanol were added and dissolved. The flask was placed on a water bath heated to 50 ° C., and 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, as a polymerization initiator was added while stirring under a nitrogen stream.
Polymerization was initiated by adding 0.5 g of Wako Pure Chemical Industries, Ltd. The mixture was heated and stirred at 50 ° C. for 1 hour, and then the temperature inside the flask was raised to 75 ° C., and the mixture was heated and stirred for 3 hours. As a result of GPC analysis, the polymer thus obtained was a polymer having a weight average molecular weight of about 100,000.

By the completely same method, P-1 to P-2
The polymer shown in 4 was synthesized. In addition, the polymers represented by R-1 and R-2 were similarly synthesized as comparative polymers.

[0106]

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[0107]

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Example 1 (II) Preparation of lithographic printing plate 135 g / m ² polyethylene-coated paper was subjected to corona discharge machining, coated with a gelatin solution containing silica particles and carbon black, and further ortho-sensitized thereon. High contrast silver halide emulsion was coated. The emulsion layer contained silver halide amount are basically composed of 1.5 g / m ² gelatin 1.5 g / m ^2, the formalin and dimethylolurea as a hardening agent as silver nitrate. The photosensitive silver halide photographic material was heated at 40 ° C. for 3 days, and then a coating solution containing a physical development nucleus having the following formulation and the polymer of the present invention was prepared and applied.

(1) Preparation of palladium sulfide sol Liquid A Palladium chloride 5 g Hydrochloric acid 40 ml Distilled water 1000 ml Liquid B Sodium sulfide 8.6 g Distilled water 1000 ml Mix liquid A and liquid B with stirring, and after 30 minutes, ion It was passed through a column packed with an exchange resin (IR-120E, IRA-400) to obtain a palladium sulfide sol.

(2) Preparation of Physical Development Nucleation Coating Solution Containing Polymer of the Present Invention Palladium Sulfide Sol 100 ml Hydroquinone 100 g Polymer of the Present Invention (as Solid Content) 5 g 10% Saponin (Surfactant) 2 ml Was 2000 ml. A lithographic printing plate was prepared by applying the main coating solution onto the silver halide light-sensitive material obtained above.

(III) Processing Method After exposing the light-sensitive material image-wise, it is immersed in a transfer developing solution (C) having the following formulation for 30 seconds at 30 ° C. to perform transfer development, and then the following formulation (D) is used. 30 in stop solution
It was soaked for 25 seconds (25 ° C.), squeezed to remove excess liquid, and the material was dried under atmospheric conditions.

Formulation C (transfer developer) Water 1500 ml Sodium hydroxide 20 g Sodium sulfite 100 g Hydroquinone 12 g 1-Phenyl-3-pyrazolidone 1 g Sodium thiosulfate 10 g Potassium thiocyanate 5 g Potassium bromide 5 g Add water to make a total volume of 2 l. .

Formulation D (stop solution) Water 2 l Citric acid 10 g Sodium citrate 35 g

(IV) Printing Method The printing plate thus obtained was mounted on an Ryobi 3200CD offset printing machine, the plate surface was wiped with the liquid of formula (E), and then printing was performed. Printing temperature is 22 ℃ and humidity is 6
It was 0%.

Formulation E Water 400 ml Citric acid 1 g Sodium citrate 3.5 g 2-Mercapto-5-heptyl-1,3,5-oxadiazole 0.5 g Ethylene glycol 50 ml

Commercially available fountain solution was used as the wetting liquid, and F gloss black B and F gloss indigo blue manufactured by Dainippon Ink Co., Ltd. were used as the printing inks. F-gloss indigo blue is one of the inks that easily causes stains on the offset printing plate.

(V) Evaluation of Photographic Properties For the plate-making materials obtained as described above, the polymers shown in Chemical formulas 27 and 28, which are comparative polymers outside the present invention, were similarly used in place of the polymer of the present invention. The printing plate exposed with an optical wedge together with the plate-making material obtained by the above, and subjected to development processing was subjected to measurement of reflection density using an ordinary optical densitometer, and sensitivity (S) and tone (gamma γ)
I asked. The sensitivity (S) was shown as a relative value with the value of Fresh comparative polymerization 27 being 100. Further, in order to investigate deterioration when stored under heating, the fresh plate material was heated at 50 ° C. for 4 days. After that, the same treatment as above is performed, and the sensitivity (S ′) and tone (γ ′) after the heating treatment
I asked. The results are shown in Table 1.

[0118]

[Table 1]

From the results shown in Table 1, all the polymers having the functional group shown in the present invention are comparative polymers R-1 and R-2.
It is preferable because it has a higher sensitivity and a harder tone than that of. Further, it was found that even when it was stored under heating, almost no change in photographic characteristics was observed and good characteristics were retained.

(VI) Evaluation of printing characteristics Next, the plate material obtained as described above was printed by the above-mentioned offset printing machine according to a predetermined process. The printing characteristics were evaluated by visually observing the degree of print stains on the printed matter, and evaluated according to the following 5 levels. 5: No dirt at all 4: Almost no dirt (middle between 5 and 3) 3: Partially dirt exists 2: Between 3 and 1 Intermediate 1 ... Slight stains occur on the entire surface. The results are shown in Table 2. Further, as the evaluation of printing durability, 5000 copies were printed under the same printing conditions and evaluated.
It was found that any plate material including the comparative polymer could be printed without any problems.

[0121]

[Table 2]

From the results shown in Table 2, the degree of occurrence of print stain is
It was revealed that it was dramatically improved as compared with the comparative polymers R-1 and R-2, and that it exhibited stable printing characteristics even after storage under heating.

Example 2 Example 1 was repeated for the polymers [P-9] to [P-16]. The results are shown in Tables 3 and 4.

[0124]

[Table 3]

From the results shown in Table 3, the polymers having the functional group shown in the present invention are comparative polymers R-1 and R-2.
It is preferable because it has a higher sensitivity and a harder tone than that of. Further, it was found that even when it was stored under heating, almost no change in photographic characteristics was observed and good characteristics were retained.

Next, Table 4 shows the results of evaluation of printing characteristics according to Example 1. Further, as the evaluation of printing durability, 5000 copies were printed under the same printing conditions and evaluated.
It was found that any plate material including the comparative polymer could be printed without any problems.

[0127]

[Table 4]

From the results of Table 4, the degree of occurrence of print stains is
It was revealed that it was dramatically improved as compared with the comparative polymers R-1 and R-2, and that it exhibited stable printing characteristics even after storage under heating.

Example 3 Example 1 was repeated for the polymers [P-17] to [P-24]. The results are shown in Tables 5 and 6.

[0130]

[Table 5]

From the results shown in Table 5, the polymers having a functional group shown in the present invention are comparative polymers R-1 and R-2.
It is preferable because it has a higher sensitivity and a harder tone than that of. Further, it was found that even when it was stored under heating, almost no change in photographic characteristics was observed and good characteristics were retained.

Next, Table 6 shows the results of evaluation of printing characteristics according to Example 1. Further, the printing durability was evaluated by printing 5000 copies under the same printing conditions, and it was found that any plate material including the comparative polymer could be printed without any problem.

[0133]

[Table 6]

[0134]

INDUSTRIAL APPLICABILITY As shown in the above examples, the lithographic printing plate to which the silver complex salt diffusion transfer system is applied has at least one functional group represented by the general formulas (A), (B) and (C). By containing the water-soluble polymer in the layer containing physical development nuclei, a lithographic printing material having high sensitivity, excellent heat storage stability, and dramatically improved printing characteristics can be provided.

Claims (3)

[Claims] 1. A lithographic printing plate utilizing a silver complex salt diffusion transfer method comprising a silver halide emulsion layer and a layer containing physical development nuclei on a support, wherein the chemical compound 1 is contained in the layer containing the physical development nuclei. A lithographic printing plate comprising a water-soluble polymer containing the functional group shown. Embedded image In the chemical formula 1, R ₃ represents a hydrogen atom, an alkyl group, a phenyl group, an amino group or an amidino group, and R ₄ represents a hydrogen atom or an amino group. 2. A lithographic printing plate utilizing a silver complex salt diffusion transfer method comprising a silver halide emulsion layer and a layer containing physical development nuclei on a support, wherein A lithographic printing plate comprising a water-soluble polymer containing the following repeating unit. Embedded image In Chemical formula 2, X represents a carbon atom or a phosphorus atom, and Y represents an oxygen atom, a sulfur atom or a nitrogen atom. Z represents a sulfur atom, a nitrogen atom or an NH group. R ₅ represents an alkyl group, an alkoxy group, an aryl group, a pyrrolidino group, a piperidino group, a mercapto group or a thiosemicarbazide group. When X is a phosphorus atom, R ₅ is an alkoxy group and two X's are substituted. Furthermore, Y and R ₅ may form a ring via a carbon atom, a nitrogen atom or the like. When Z is a nitrogen atom or an NH group, the atomic group of X (= Y) R ₅ represents a dithiocarbamic acid group or an N-substituted thiourea residue. 3. A lithographic printing plate utilizing a silver complex salt diffusion transfer method comprising a silver halide emulsion layer and a layer containing physical development nuclei on a support, wherein the chemical formula 3 is contained in the layer containing physical development nuclei. A lithographic printing plate comprising a water-soluble polymer containing the functional group shown. Embedded image In Chemical formula 3, W represents a nitrogen-containing heterocycle, and n represents 1 or 2.