JP3395931B2 - Method for producing lithographic printing plate by silver salt diffusion transfer method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a method of making improved lithographic printing plates by the silver salt diffusion transfer process.

[0002]

BACKGROUND OF THE INVENTION The principle of the silver complex diffusion transfer reversal method, hereinafter referred to as the DTR-method, is described, for example, in US Pat. No. 2,352,014.
Issue and the book "Photographic Silver Halide Diffusion Pro" by Andre Rott and Edith Weyde.
cesses), The Focal Press-London and New Yor
k), (1972).

In the DTR-method, the undeveloped silver halide of a photographic silver halide emulsion layer material that has been information-wise exposed is converted into a soluble silver complex compound using a so-called silver halide solvent, which is the image receiving material. It is diffused in the element and reduced therein with the developer, generally in the presence of physical development nuclei, and inverted with respect to the black silver image obtained on the exposed part of the photographic material. To form a silver image (DTR-image) having a different image density value.

The DTR-image bearing material can be used as a planographic printing plate in which the DTR-silver image portion produces a water repellent ink receptive portion on a water receptive ink repellent background.

The DTR-image can be formed in the image-receiving layer of a sheet or web material which is a separate element for photographic silver halide emulsion materials (so-called 2-sheet DTR elements),
Alternatively it can be formed in a so-called single support element image receiving layer, also referred to as a mono-sheet element containing at least one photographic silver halide emulsion layer which is in water permeable relationship with the image receiving layer. The latter mono-sheet method is preferred for the production of offset printing plates by the DTR method.

There are two types of mono-sheet DTR offset printing plates. For example, U.S. Pat. No. 4,722,53
No. 5, and British Patent No. 1,241,661, a support having a silver halide emulsion layer and a layer containing physical development nuclei which act as image receiving layers in the order described. The body is provided. After information-wise exposure and development, the imaging element is used as a printing plate without removing the emulsion layer.

According to a second type of mono-sheet DTR offset printing plate, a hydrophilic support, most of which has a layer containing physical development nuclei and a silver halide emulsion layer in the order listed, is anodized aluminum. The body is provided. After information-wise exposure and development, the imaged element is processed to remove the emulsion layer, leaving a support bearing the silver image, which is used as a printing plate. Such a type of lithographic printing plate is disclosed, for example, in US Pat. No. 3,511,656.

With regard to other printing plates, a second type of mono-
The offset printing plates belonging to the sheet DTR offset printing plates have good printing properties: high contrast, high printing resistance, good ink acceptance in the printed area, non-
It is required to have a low number of copies that have to be discarded due to ink non-receptivity in the printed part (no contamination) and ink acceptance in the non-printed part (so-called toning) at the start of the printing process.

1,2,4-Triazolium-3-thiolates are suitable silver halide solvents for use in the method of making the first type of lithographic printing plate by the silver salt diffusion transfer process, for example as disclosed in European Patent Publication No. 535,678
No., 554,585 and JP Pi04 / 324
478. 1,2,4-triazolium-
3-Thiolates are suitable as halogenated solvents for use in a method of making a second type of lithographic printing plate according to the silver salt diffusion transfer method, EP-A-554,5.
No. 85.

European Patent Application Publication No. 9320231
0.4, a low viscosity in the emulsion layer of an imaging element suitable for use in a method of making a second type mono-sheet DTR offset printing plate to improve the printing properties of said printing plate. The use of gelatin is disclosed. 1,2,4-Triazolium-3-thiolates are listed as suitable silver halide solvents. However, when these compounds are used as silver halide solvents in the process of making lithographic printing plates from the above imaging elements, the results are unsatisfactory.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to have good printing properties such as high contrast, good ink acceptance in the printed areas, ink non-receptivity in the non-printed areas,
An object of the present invention is to provide a method for manufacturing an offset printing plate by the DTR-method, which has good reproduction characteristics and high printing durability.

Other objects of the present invention will be apparent from the following description.

According to the invention, (i) an image-receiving layer containing physical development nuclei and (ii) a silver halide emulsion and a 10% by weight aqueous solution in the order described at 36 ° C. on the hydrophilic surface of the support. And image-wise exposing an imaging element comprising a photosensitive layer in water-permeable relationship with said image receiving layer containing gelatin having a viscosity of less than 20 mPa.s at a shear rate of 1000 s ^-1 at pH 6. An imaging element in the presence of (i) one or more developing agents, (ii) 1,2,4-triazolium-3-thiolate and (iii) one or more additional silver halide solvents. An aqueous alkaline solution to form a silver image in the image-receiving layer and the imaging element is treated to remove one or more layers on top of the image-receiving layer, thereby forming in the image-receiving layer. The exposed silver image A method of manufacturing an offset printing plate by a silver salt diffusion transfer method comprising a C ₁ -C ₈ alkyl group, wherein the 1,2,4-triazolium-3-thiolate contains at least 3 fluorine atoms, C
₄ -C ₁₀ hydrocarbon group, and comprising at least three fluorine atoms and / or C ₄ -C ₁₀ hydrocarbon radical C ₁ -
There is provided a production method characterized by being substituted with at least one substituent selected from the group consisting of a 4-amino group substituted with a C ₈ alkyl group.

According to the present invention there is also provided an imaging element and an alkaline processing liquid for use in the method as defined above.

[0015]

DETAILED DESCRIPTION OF THE INVENTION From an imaging element comprising low viscosity gelatin in a silver halide emulsion layer, according to the DTR-method, 1,2,4-triazolium-defined above.
Lithographic printing plates made in the presence of 3-thiolate and one or more other silver halide solvents have increased print resistance, good ink acceptance at the beginning of the printing process, good reproducibility and high It was found to have print contrast.

The 1,2,4-triazolium-3-thiolates suitable for use in the method of making a first type lithographic printing plate are used to make a second type lithographic printing plate from the above imaging elements. The problem of non-conformance has not been disclosed so far, and thus no solution to this problem is suggested.

The C ₁ -C ₈ alkyl group comprising at least 3 fluorine atoms, provided that it is not a CF ₃ -group,
Further, it may be substituted with a fluorine atom or another substituent. Suitably said C ₁ -C ₈ group is at least one CF
₃ - group and / or at least two -CF ₂ - comprising group.

The C ₄ -C ₁₀ hydrocarbon group may be an unsubstituted or substituted C ₄ -C ₁₀ alkyl group, each containing one or more, for example, --O--, --S--, --CH = CH
_{-, - C = C- C 5} -C 10 cycloalkyl groups or substituted also be unsubstituted which such contain divalent linking group such as, C ₇ -C ₁₀ which is unsubstituted or substituted aralkyl groups, unsubstituted or substituted C ₆ -C ₁₀ aryl groups, and C ₄ -C ₁₀ heterocyclic group which is unsubstituted or substituted, and the like.

The synthesis of the above defined 1,2,4-triazolium-3-thiolates suitable for use in the present invention is known, and for example the Journal of Heterocyc.
licChemistry, 2,105 (1965), Journal of O
rganic Chemistry, 32, 2245 (1967), Jour
nal of The Chemical Society, 3799 (1969)
And Journal of The American Chemical Society, 8
0, 1895 (1958).

1,2,4-triazolium-according to the invention
The 3-thiolates are preferably at least one CF ₃
- group and / or at least two -CF ₂ - comprising group C ₁ -C ₅ alkyl group, C ₄ -C ₈ hydrocarbon group or at least one of CF _3, - group and / or at least two -CF ₂ - is substituted with at least one substituent selected from the group, or C ₄ -C ₈ comprising a hydrocarbon radical C ₁ -C ₅ group consisting of substituted 4-amino group with an alkyl group, and It has a total number of carbon atoms less than 18.

Further preferred 1,2,4-triazolium-3-thiolates for use according to the invention correspond to one of the two following formulas I or II:

[0022]

[Chemical 1]

[Wherein R ¹ represents a C ₁ -C ₅ alkyl group comprising at least one CF ₃ -group and / or at least two -CF ₂ -groups, R ² is unsubstituted or substituted. Alkyl group, alkenyl group, alkynyl group,
Represents a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group, A ¹ represents an unsubstituted or substituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or -N
R ³ represents R ⁴ , and R ³ and R ⁴ each independently represent hydrogen or an unsubstituted or substituted alkyl group or aryl group, or R ³ and R ⁴ are bonded to each other to form 5- or 6- A member ring can be formed, and where the total number of carbon atoms is less than 14],

[0024]

[Chemical 2]

[Wherein R^FiveAnd R⁶Each is independent
A substituted or substituted alkyl group, alkenyl group, or
Quinyl group, cycloalkyl group, aralkyl group, aryl
Represents a group or a heterocyclic group, A²Is not replaced or replaced
Alkyl group, alkenyl group, alkynyl group, cyclo
Low alkyl group, aralkyl group, aryl group, heterocyclic group
Or -NR⁷R⁸Represents R⁷And R⁸Each independently
Hydrogen or an unsubstituted or substituted alkyl group or
Represents an aryl group, wherein the substituent R^Five, R⁶, R ⁷Also
Is R⁸At least one of C is an unsubstituted or substituted C_Four
-C₈A hydrocarbon radical and where the total number of carbon atoms is
Less than 14].

More preferably, the 1,2,4-triazolium-3-thiolates are C ^{1 in} which R ¹ is at least one.
Represents a C ₁ -C ₅ alkyl group comprising an F ₃ — group and / or at least two —CF ₂ — groups and R ² and A ¹ are each independently unsubstituted or substituted C ₁ -C ₄
Formula I representing an alkyl, alkenyl or alkynyl group, or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶
And C ₁ in which A ² is independently unsubstituted or substituted
-C ₄ alkyl group, an alkenyl group or alkynyl group, C ₄ to the third substituent is unsubstituted or substituted -
It represents a C ₈ alkyl group, a C ₄ -C ₈ alkenyl group, a C ₄ -C ₈ alkynyl group, a C ₅ -C ₈ cycloalkyl group and corresponds to any of the formula II in which the total number of carbon atoms is less than 14.

Particularly preferably, the 1,2,4-triazolium-3-thiolates are C ₁ -C ₅ alkyl in which R ¹ contains at least 3 fluorine atoms and are optionally substituted. A group I and R ² and A ¹ each independently represents an unsubstituted or substituted methyl or ethyl group, or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶ and A ² each independently and represent an unsubstituted or substituted methyl or ethyl group and the third substituent is unsubstituted or substituted C ₄ -C ₈ alkyl group, C ₄ -
C ₈ alkenyl group, C ₄ -C ₈ alkynyl or C ₅ -C
Corresponds to formula II, which represents an ₈ cycloalkyl group.

Most preferably, the 1,2,4-triazolium-3-thiolate is such that R ¹ represents a CF ₃ CH ₂ --group and R ² and A ¹ are each independently unsubstituted or substituted. Formula I representing a methyl or ethyl group, or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶ and A ² each independently represents an unsubstituted or substituted methyl or ethyl group and a third substituent Corresponds to formula II in which C represents an unsubstituted or substituted C ₄ -C ₈ alkyl group or a C ₄ -C ₈ alkenyl group.

Specific examples of 1,2,4-triazolium-3-thiolates suitable for use in accordance with the present invention are shown in Table 1.

Table 1

[0031]

[Chemical 3]

[0032] Compound No. _{R 'R "A 1 CF 3} CHFCF 2 CH 2 - CH 3 - CH 3 - 2 H (CF 2) 4 CH 2 - CH 3 - CH 3 - 3 CF 3 CH 2 - CH 3 - CH 3 - 4 _{CF 3 CH 2 - CH 3 -} CH 2 = CHCH 2 - 5 CH 3 - nC 5 H 11 - CH 3 - 6 CH 3 - C 2 H 5 CH = CHCH 2 - (CH 3) 2 N- 7 CH 3 - _{CH 3 - CH 2 = CH (} CH 2) 2 - 8 CH 3 - CH 3 - nC 6 H 13 - 9 C 6 H 5 - CH 3 - CH 3 - 10 CH 3 - CH 3 - nC 6 H 13 NH- According to the invention, 1,2,4-triazolium-3-thiolate is preferably present in an alkaline liquid in an amount of 0.1 mmol / mol.
in an amount of between 1 and 25 mmol / l, more preferably between 0.5 and 10 mmol / l and most preferably between 2 and 8 mmol / l, or the image In the forming element preferably between 0.1 and 10 mmol / m ² , more preferably between 0.1 and 5 mmol / m ² and most preferably between 0.5 and 1.5 mmol / m ^2. It is added in an amount between m ² .

According to a preferred embodiment of the present invention at least a portion, and most preferably all of the 1,2,4-triazolium-3-thiolate is used by developing the image-wise exposed imaging element. Existing in the alkaline processing liquid. However, 1,2,4-triazolium-
The 3-thiolate may be incorporated in one or more layers comprised on the support of the imaging element. This is the 1,2,4-triazolium-3-
It also gives the advantage of thiolate supplementation. Suitably 1,
The 2,4-triazolium-3-thiolate is added in layers of the imaging element that do not contain silver halide, such as in the backing layer, in the image-receiving layer, in the subbing layer.

According to the present invention, a silver image is formed in the light-sensitive layer and unreduced silver halide or a complex thereof formed is image-wise diffused from the light-sensitive layer to the image-receiving layer to form a silver image therein. Development and diffusion transfer of the information-wise exposed imaging element for imprinting are carried out in the presence of one or more developers and one or more additional silver halide solvents. One or more developers and / or one or more silver halide solvents can be added in the aqueous alkaline solution and / or in the imaging element.

Preferably, the alkaline processing liquid used to develop the imaging element contains another silver halide solvent. Preferably, another silver halide solvent is used in an amount of between 0.05% and 5% by weight, and more preferably between 0.5% and 2% by weight. Another silver halide solvent suitable for use in connection with the present invention is, for example:
Sulfites, amines, 2-mercaptobenzoic acid, cyclic imide compounds such as uracil and 5,5-dialkylhydantoins, alkyl sulfones and oxasolidones.

Preferred silver halide solvents for use in connection with the present invention are alkanolamines. Examples of alkanolamines that may be used in connection with the present invention is represented by the following _{formula: C l H 2l -X N-} C m H 2m -X 'C n H 2n -OH [ wherein, X and X' independently represent hydrogen, hydroxyl Represents a group or an amino group, l and m represent 0 or an integer of 1 or more, and n represents an integer of 1 or more]. Alkanolamines preferably used are, for example, diethanolamine, N-
Methylethanolamine, triethanolamine, N-
Ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N
-Dimethylethanolamine, 3-aminopropanol, N, N-ethyl-2,2'-iminodiethanol and the like or mixtures thereof. A particularly preferred alkanolamine for use with the present invention is N- (2-aminoethyl) ethanolamine.

According to the invention, the alkanolamines are preferably present in the alkaline processing liquid in a concentration of between 0.1 and 5% by weight. However, some or all of the alkanolamine may be present in one or more layers of the imaging element.

Still other preferred silver halide solvents for use in connection with the present invention are thioethers. Suitably thioethers used are the following general _{^{formula: Z- (R 9 -S) t}} -R 10 -S-R 11 -Y [ wherein, Z and Y are each independently hydrogen, an alkyl group,
Amino group, ammonium group, hydroxyl, sulfo group,
Represents carboxyl, aminocarbonyl or aminosulfonyl, R ⁹ , R ¹⁰ and R ¹¹ each independently represents alkylene, which may be substituted and optionally contains an oxygen bridge, and t is 0-10
Represents an integer of]. Examples of thioether compounds corresponding to the above formula are disclosed, for example, in US Pat. No. 4,960,683 and European Patent Application Publication 554,585.

Combinations of different alternative silver halide solvents can also be used, and at least one additional silver halide solvent can be added in a suitable layer of the imaging element as well as at least one other. It is also possible to add another silver halide solvent to the developing solution.

The alkaline aqueous solution according to the invention further comprises a sulfite, for example sodium sulfite, up to 4 per liter.
0 g to 180 g, preferably 60 to 1 per liter
It may be contained in combination with another silver halide solvent in an amount in the range of 60 g.

The alkaline processing liquid may contain one or more developers used in accordance with the present invention. In this case, the alkaline processing liquid is called a developer. On the other hand, some or all of the one or more developers can be present in one or more layers of the imaging element. When all of the developer is contained in the imaging element, the alkaline processing liquid is called the activator or activating liquid.

Silver halide developers suitable for use in accordance with the present invention are preferably of the p-dihydroxybenzene type, for example hydroquinone, methylhydroquinone or chlorohydroquinone, which are preferably combined with a secondary developer. The sub-developer is a 1-phenyl-3-pyrazolidinone type developer and / or p-monomethylaminophenol. Particularly useful secondary developers are of the phenidone type, such as 1-phenyl-3-pyrazolidinone, 1
-Phenyl-4-monomethyl-3-pyrazolidinone and 1-phenyl-4,4-dimethyl-3-pyrazolidinone. However, other developers can be used. The preferred amount of hydroquinone type developer is in the range of 0.05 to 0.25 mol per liter, and the preferred amount of one or more secondary developers is 1.8 × 10 ^-3 per liter. The range is up to 2.0 × 10 ^-2 mol.

The quantitative ranges specified for developers, silver halide solvents, and sulfites are such that the application of alkaline aqueous solutions from the layers in which these compounds form part of or contain them. Even if it is sometimes dissolved, it applies to the amount of these compounds present as solutes in the alkaline aqueous solution during DTR-treatment.

In order to prevent the emulsion layer from sticking to the transfer roller when the emulsion swells with the alkaline aqueous solution, the alkaline aqueous solution suitable for use according to the invention preferably contains aluminum ions in an amount of at least 0.3 g / l.
More preferably it comprises at least 0.6 g / l.

The alkaline processing liquid preferably has a pH of between 9 and 14, and more preferably of between 10 and 13, which means the type of silver halide emulsion material to be developed, the intended development time and the processing. Depends on temperature.

The processing conditions such as temperature and time are as follows:
A wide range can be varied, so long as the mechanical strength of the material to be treated is not adversely affected and decomposition does not occur.

The pH of the alkaline processing liquid can be set by an organic or inorganic alkaline substance or a combination thereof. Suitable inorganic alkaline substances are, for example, sodium and potassium hydroxides, alkali metal salts of phosphoric acid and / or silicic acid, such as trisodium phosphate, sodium or potassium orthosilicates, metasilicates, hydrodisilicates, and sodium carbonate. And so on. Suitable organic alkaline substances are, for example, alkanolamines. In the latter case, the alkanolamine produces or helps to produce its pH and acts as a silver halide complexing agent.

The alkaline aqueous solution may further contain a hydrophobizing agent for improving the hydrophobicity of the silver image obtained in the image receiving layer. Generally, these compounds contain a mercapto group or thiolate group and one or more hydrophobic substituents. A particularly suitable hydrophobizing agent is DE-A1,
228,927 and mercapto-1,3,4-thiadiazoles, 2-mercapto-5-heptyl-oxa-3, as described in U.S. Pat. No. 4,563,410.
4-diazoles and long-chain (at least 5 carbon atoms) alkyl-substituted mercaptotetrazoles. The hydrophobizing agents can be used alone or in combination with one another.

These hydrophobizing compounds can be added to the alkaline aqueous solution in an amount of preferably 0.1 to 3 g per liter and preferably mixed with 1-phenyl-5-mercaptotetrazole, the latter compound being It can be used in an amount of, for example, 50 mg to 1.2 g per liter of solution, which can contain a small amount of ethanol to improve the solubility of the compound.

The alkaline aqueous solution contains other components such as antioxidants, compounds that release bromide ions, calcium-
Hardeners may be included, including capture compounds, anti-sludge agents, and latent hardeners.

Regardless of whether the solution is added to one or more developing agents and / or one or more halogenated solvents, it is of course possible to regenerate the alkaline aqueous solution according to known methods.

It is also possible, although not necessary, to stop the development with so-called stabilizing solutions, which in practice are preferably acidic stop baths having a pH in the range 5-6.

A buffer stop bath comprising a mixture of sodium dihydrogen orthophosphate and disodium hydrogen orthophosphate and having a pH in the range is preferred.

Development and diffusion transfer are carried out in different ways, for example by rubbing with a roller, by wiping with an absorbent means, for example cotton or a sponge stopper, or by dipping the material to be treated in a liquid composition. It can be started by Preferably, they are carried out in an automatic operating device. They are generally carried out at temperatures in the range 18 ° C to 30 ° C.

After the silver image is formed on the hydrophilic base, the excess alkaline solution still present on the base can be removed, preferably by guiding the foil into a pair of squeezing rollers.

The silver image thus obtained is then processed in a layer of physical development nuclei by treating the imaging element to remove all layers above the layer containing physical development nuclei. To appear.

According to a particularly preferred embodiment of the present invention, the silver image in the layer of physical development nuclei is exposed by washing away all layers above the layer containing physical development nuclei.

The temperature of the rinse water can vary widely, but is preferably between 20 ° C and 45 ° C.

The lithographic-based imaging surface can be subjected to a chemical treatment which increases the hydrophilicity of the non-silver image portions and the lipophilicity of the silver image.

This chemical aftertreatment is preferably carried out with a lithographic composition, often referred to as a fixer, which increases the ink-repellency and / or lacquer-receptivity of the silver image. A compound, and also at least one compound that improves hydrophilic-based ink-repellency properties.

Suitable components for the fixer are, for example, organic compounds containing a mercapto group, such as the hydrophobizing compounds mentioned above for alkaline solutions and 1 of the formula
The compound corresponding to the species is:

[0062]

[Chemical 4]

[In the formula, R ⁶ represents hydrogen or an acyl group, and R ⁵ represents alkyl, aryl or aralkyl].

A suitable fixer solution disclosed in US-A-4.563.410 is a composition comprising a solution of mercaptotetrazole in a solution of polyethylene oxide having a molecular weight of 4,000. Another suitable fixer is eg US
-A-4.062.682.

At the start of the process using the fixer,
The surface having the silver pattern may be dry or wet. In general, processing with fixers is short-lived, usually within about 30 seconds and it can be carried out immediately after the processing and emergence stage.

The fixer can be applied in various ways, for example by rubbing it with a roller, wiping it with an absorbent means, for example cotton or a sponge stopper, or by dipping the material to be treated in the fixer. . The image-hydrophobicizing step of the printing plate also passes the printing plate through an apparatus having narrow grooves filled with a fixer and transfers the printing plate to the end of the groove between two squeezing rollers to remove excess liquid. This can be done automatically.

Immediately after treating the hydrophilic base bearing the silver image with the fixer, it can be used as a printing plate.

According to the invention, the imaging element can be information-wise exposed in an apparatus depending on its particular application. A wide range of cameras for exposing the light sensitive silver halide emulsion is available on the market. Horizontal, vertical and darkroom type cameras and contact-exposure devices suitable for certain types of reprographic work are available. The imaging element according to the invention can also be exposed using, for example, a laser recorder and a cathode ray tube.

The imaging element for use in the invention to produce an offset printing plate comprises (i) a hydrophilic base, (ii) an image receiving layer containing physical development nuclei and (iii) in a specified order. It essentially comprises a light-sensitive layer containing a silver halide emulsion and low viscosity gelatin, the light-sensitive layer being in water-permeable relationship with the image-receiving layer.

The imaging element is preferably prepared by coating the different layers on the hydrophilic layer of the support.
Alternatively, different layers can be laminated to the image receiving layer from a temporary base supporting the layers in the reverse order as disclosed in US Pat. No. 5,068,165.

The hydrophilic layer of the support comprises a hydrophobic synthetic tetraalkyl orthosilicate crosslink containing a hydrophilic synthetic homopolymer or copolymer and coated onto a flexible hydrophobic base. It may be a cured hydrophilic layer that is cured with an agent. More preferably, the hydrophilic layer is part of the aluminum support.

The aluminum support of the imaging element used according to the invention may be made of pure aluminum or an aluminum alloy, the aluminum content of the alloy being at least 95%. The thickness of the support generally ranges from about 0.13 to about 0.50 mm.

The production of aluminum or aluminum alloy foils for lithographic offset printing comprises the following steps: granulation of the foil, anodization and optionally sealing.

Granulation and anodization of the foil are necessary to obtain a lithographic printing plate capable of producing high quality prints according to the present invention. Sealing is not necessary, but it may further improve the printed result.

Granulation of the aluminum surface can be carried out mechanically or electrolytically in a known manner. The roughness produced by granulation is measured as the centerline mean value expressed in μm, and preferably varies from about 0.2 to about 1.5 μm.

The anodization of the aluminum foil can be carried out in an electrolyte such as chromic acid, oxalic acid, sodium carbonate, sodium hydroxide, and mixtures thereof.
Preferably, anodization of aluminum is carried out in dilute aqueous sulfuric acid medium until the desired anodized layer thickness is reached. The aluminum foil can be anodized on both sides. The thickness of the anodized layer is most accurately measured by making a micrograph cut, but it can also be measured by dissolving the anodized layer and weighing the plate before and after the dissolution process. it can. Good results have been obtained with an anodization layer thickness of about 0.4 to about 2.00 μm.

After the anodizing step, the anode surface may be sealed. Sealing the pores of an alkyl oxide layer produced by anodization is a technique known to those skilled in the aluminum anodization industry. The anode surface of the aluminum foil can be rinsed with water or steam at 70-100 ° C. The sealing can also be performed by treating the surface of the anode with an aqueous solution containing phosphate ions or silicate. Preferably, the sealing is done with an aqueous solution containing carbonate as disclosed in EP 567,178. The sealing treatment renders the anode layer substantially non-porous and the resulting printing plate can be used for longer printing operations. As a result of the sealing, fogging on the non-printed part of the printing plate is substantially avoided.

Granulation, anodization and sealing of the aluminum foil can be carried out as described, for example, in US Pat. No. 3,861,917 and the references cited therein.

In order to increase the sharpness of the image and the resulting sharpness of the final printed copy, an anodized layer may be used as a whole, for example as described in Japanese Patent JA-Pu-58-14,797. It may be colored with an antihalation dye or pigment.

After the production of the hydrophilic layer of the support as described above,
The hydrophilic layer of the support can be immediately coated with a solution containing physical development nuclei, or can be coated with the solution at a later stage.

The image-receiving layer for use according to the invention preferably contains no hydrophilic binder, but in order to improve the hydrophilicity of the layer a small amount of hydrophilic colloid up to 80% by weight of the total weight of said layer. , For example, may contain polyvinyl alcohol.

Development nuclei suitable for use in accordance with the present invention are heavy metal sulfides such as antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver,
And zinc sulfide. Other suitable development nuclei are salts,
For example, selenides, polyselenides, polysulfides, mercaptans, and tin (II) halides. heavy metal,
Suitably silver, gold, platinum, palladium and mercury can be used in colloidal form. Further suitable development nuclei for use in accordance with the present invention are European Patent Application Publication No. 546,5.
98, especially the number of nuclei having a mean diameter of less than 6 nm and a diameter of greater than 4.5 nm is 1 of the total number of nuclei contained in the image receiving layer.
It is a heavy metal sulfide that does not exceed 5%. Particularly suitable development nuclei for the invention are palladium sulphides having an average diameter of less than 6 nm and no more than 15% of the total number of nuclei contained in the image-receiving layer having a diameter of more than 4.5 nm. It is the core.

To increase the sharpness of the image, the hydrophilic layer of the support can be provided with a very thin antihalation coating of the dye or pigment, or the image receiving layer can be provided with at least one antihalation dye or pigment. It can also be included.

The light-sensitive layer used in accordance with the present invention may be a layer comprising a hydrophilic colloid binder in water-permeable relationship with the image-receiving layer and at least one light-sensitive silver halide emulsion.

The layers that are in waterpermeable contact with each other may be layers that are continuous with each other or separated from each other by one or more water-permeable layers.
The nature of the water permeable layer is such that it does not substantially inhibit or restrain the diffusion of water or compounds contained in the aqueous solution, such as developers or complexed silver.

One or more photographic silver halide emulsions used in accordance with the present invention are described, for example, by P. Glafkides, "Photographic Chemistry and Physics (Chimie et al.
Physique Photographique), Paul Montell (Paul
Montel), Paris (1967), GF Duffin
`` Photographic Emulsion Chemistr
y) ”, The Focal Press, London (1966), and VL Zelikman (Zelikma)
n), "Making and C
oating Photographic Emulsion) ", The Focal
It can be prepared from soluble silver salts and soluble halides according to various methods as described by Press, London (1966).

For use in accordance with the present invention, the one or more silver halide emulsions preferably consist essentially of silver chloride, but with a silver bromide moiety of from 1 mol% to 40 mol%. It may exist in the range. Most preferably a silver halide emulsion containing at least 70 mol% silver chloride is used.

The average size of silver halide grains is from 0.10 to 10.
It can be in the range of 0.70 μm, preferably 0.25 to 0.45 μm.

Preferably during the precipitation stage iridium and / or
Alternatively, the rhodium-containing compound or a mixture of both is added. The concentration range of these added compounds is 10 ^-8 to 10 ^-3 mol, preferably 1 mol / mol AgNO _3.
The range is between 10 ^{−7 and} 10 ⁻⁶ mol per mol AgNO ₃ .

The emulsions can be chemically sensitized, for example, by adding sulfur-containing compounds such as allyl isothiocyanate, allylthiourea, and sodium thiosulfate during the chemical ripening step. Also reducing agents such as the tin compounds described in BE-A-493,464 and 568,687 and polyamines such as diethylenetriamine or aminoethane-sulfonic acid derivatives can be used as chemical sensitizers. Other suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This chemical sensitization method is described by R. Koslowsky, Z. Wiss. Photogr. Photophys. Photoc
hem., 46, 65-72 (1951).

Emulsions of DTR elements can be spectrally sensitized in response to the spectral radiation of the exposure source designed for the DTR element.

Sensitizing dyes suitable for the visible spectral region include, for example, FM Hamer, "The Cyanine Dyes and Related Compounds",
1964, John Willie and Sons (John
The methine dyes described by Wiley & Sons) are included. Dyes that can be used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly valuable dyes belong to cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

In the case of a general light source, for example, tungsten light, a green sensitizing dye is necessary. In the case of exposure with an argon ion laser, a blue sensitizing dye is added. In the case of exposure with a red-emitting source, such as an LED or HeNe laser, a red sensitizing dye is used. In the case of exposure with a semiconductor laser, a special spectral sensitizing dye suitable for near infrared rays is required. Suitable infrared sensitizing dyes are, for example, U.S. Pat. No. 2,095,854, 2,09
No. 5,856, No. 2,955,939, No. 3,482,97
No. 8, No. 3,552,974, No. 3,573,921,
No. 3,582,344, No. 3,623,881 and No. 3,695,888.

Blue sensitizing dyes, green sensitizing dyes, red sensitizing dyes and infrared sensitizing dyes suitable for the present invention are described in EP-A-554,585.

To increase the sensitivity in the red or near infrared region, so-called supersensitizers can be used in combination with the red or near infrared sensitizing dye. A suitable supersensitizer is Research Disclosur.
e) Vol. 289, May 1988, Item 28952. The spectral sensitizer can be added to the photographic emulsion in the form of an aqueous solution, a solution or dispersion in an organic solvent.

The silver halide emulsions can contain conventional emulsion stabilizers. Suitable emulsion stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxy or amino groups. This kind of compound is Z. Wiss. Photogr. Photophy of BIRR.
s. Photochem., 47, 2-27 (1952). Other suitable stabilizers are, for example, heterocyclic mercapto compounds.

According to the present invention gelatin is used as a binder in one or more layers of the light-sensitive silver halide emulsion. However, the gelatin can also be partly replaced by synthetic, semi-synthetic or natural polymers. According to the invention, the silver halide emulsion layer comprises a 10% by weight aqueous solution of gelatin at 36 ° C. and a pH of 6.
Cylinder 1000 rpm at shear rate of 000 s ^-1
And the trademark HAAKE ROTOV operated with a rotating cylinder capable of rotating at maximum shear rates of 44,500 s ^-1
It contains gelatin having a viscosity of less than 20 mPa.s as measured by a viscometer sold as ISCO Rheometer type M10. The low viscosity gelatin is preferably combined with a higher viscosity gelatin. The weight ratio of low viscosity gelatin to high viscosity gelatin is preferably 0.
Greater than 5.

Suitably, one or more gelatin layers are substantially uncured. Substantially non-hardened means coating such a gelatin layer on a subbed polyethylene terephthalate film base at a dry thickness of 1.2 g / m ² at 57 ° C. and 35% relative humidity. This means that when dried for 3 days and immersed in water at 30 ° C., more than 95% of the gelatin layer dissolves within 5 minutes.

The silver halide emulsions may contain pH adjusting ingredients. Preferably, the emulsion layer is coated at a pH value below the isoelectric point of gelatin in order to improve the stability properties of the coated layer. More preferably, the gelatin layer continuous with the intermediate layer is coated at a pH value above the isoelectric point of gelatin. Most preferably, all gelatin-containing layers are coated at pH values above their isoelectric point. Other ingredients such as antifoggants, development accelerators, wetting agents, and hardeners for gelatin may also be present. The silver halide emulsion layer can also comprise a light-screening dye that absorbs diffuse light and thus promotes image sharpness. Suitable light-absorbing dyes are, for example, US Pat. No. 4,092,
168, U.S. Pat. No. 4,311,787 and German Patent No. 2,453,217.

Further details regarding the composition, manufacture and coating of silver halide emulsions suitable for use in accordance with the present invention can be found in eg Product Licensing Index, Volume 92, December 1971, Document No. 9232, 197. See page 109.

In addition to the negative-working silver halide emulsions preferred for their high photosensitivity, direct positive silver halide emulsions which produce a positive silver image can also be used.

For example, European Patent Application Publication No. 36
Direct positive silver halide emulsions which primarily form an internal image as described in US Pat. No. 5,926 and US Pat. No. 3,062,651 can be used. Alternatively, prefogged direct positive halogenation with internal or preferably external electron traps as disclosed in EP-A 94201895 and EP-A-481,562. Silver emulsions are also suitable for use with the present invention.

Preferably, the imaging element comprises an intermediate layer between the hydrophilic base image-receiving layer and the photosensitive layer (packet) to facilitate removal of the layer (packet) and thereby process the imaging element. This causes the produced silver image to appear in the image receiving layer.

In one aspect, the interlayer is 0.01 as disclosed in European Patent Application Publication No. 410500.
To 2.0 g / m are coated with ² ratio and at least one non - proteinaceous hydrophilic film produced polymer becomes comprise antihalation dye or pigment by it and if include, for example, polyvinyl alcohol Water-swellable intermediate layer.

In another embodiment, the intermediate layer is a layer having a mean diameter of at least 0.2 μm and comprising hydrophobic polymer beads prepared by the polymerization of at least one ethylenically unsaturated monomer. is there. Preferably, the intermediate layer comprises the hydrophobic polymer beads in the dry state in an amount of up to 80% of its total weight. Further details are disclosed in EP-A-483415.

Additional intermediate layers which may be present between the silver halide emulsion-containing layer and the water-swellable intermediate layer or the intermediate layer comprising a hydrophobic polymer include one or more components such as antihalation dyes or pigments. , Developers, silver halide solvents, base precursors, and anti-corrosion agents.

When producing an imaging element by laminating a layer packet comprising a photosensitive layer onto an image receiving layer, 1
One or more intermediate layers, one or more photosensitive layers above, a water-swellable intermediate layer or 0.2μ.
It is applied to an intermediate layer having a mean diameter of m or more and comprising a hydrophobic polymer produced by the polymerization of at least one ethylenically unsaturated monomer.

The following examples illustrate the invention but do not limit it to them. All parts, percentages and ratios are by weight unless otherwise noted.

[0109]

【Example】

Example 1 (Comparative) A 0.30 mm thick aluminum foil (AA1050) was degreased by immersion in an aqueous solution containing 10% phosphoric acid and then in an aqueous solution containing 2 g / l sodium hydroxide. Etched. Foil then using alternating current 4
Electrochemically granulated in an aqueous solution containing g / l hydrochloric acid and 4 g / l hydrobromic acid at a temperature of 35 ° C. to produce a surface topography having a mean centerline roughness Ra of 0.6 μm. did. The aluminum plate was then decontaminated with an aqueous solution containing 30% sulfuric acid at 60 ° C. for 120 seconds. The foil is subsequently anodized in a 20% aqueous sulfuric acid solution to produce an anodized film of 3.0 g / m ² Al ₂ O ₃ .H ₂ O and 20 g / l NaHCO ₃
Was treated with an aqueous solution containing and then rinsed with deionized water.

1.1 mg of grained, anodized and sealed aluminum support as physical development nuclei
Silver containing PdS of / m ² - imaging element by coating with receptive monolayer was obtained.

A method wherein the resulting dry layer has a weight of 0.5 g of polymethylmethacrylate beads per m ² from the following aqueous composition over the silver-receptive monolayer drying intermediate layer. Applied: where the composition comprised: 50% Helioechtpapierrot 20% dispersion of polymethylmethacrylate beads having an average diameter of 1.0 μm in a mixture of equal volumes of water and ethanol. BL (trademark for dye sold by Bayer AG of Labelkuben D-5090, Germany) 2.5 g saponin 2.5 g nanaoleylmethyl tauride 1.25 g deionized water 300 ml (pH value: 5.6).

Finally, 1 mmol / mol of substantially uncured AgX 4-hydroxy-6-methyl-
Photosensitive negative-working cadmium-free gelatin silver chlorobromoiodide emulsion layer containing 1,3,3a, 7-tetraazaindene (97.98 / 2 / 0.02%)
Is coated on the intermediate layer, wherein the silver halide is supplied in an amount corresponding to 2.40 g of silver nitrate per m ² and the gelatin content of the emulsion layer is 1.58 g / m ² , which is 0.5. It consisted of gelatin with a viscosity of 21 mPa.s of 7 g / m ² and the remaining gelatin with a viscosity of 14 mPa.s.

The imaging element was exposed through a contact screen in a plate making camera and had the following common components at 24 ° C. but was used as shown in Table 2, but used as shown in Table 2, 1,2,4-triazolium- 3-Different thiolates 5
Immersion in one of the freshly prepared seed developing solutions A-E for 10 seconds: Carboxymethylcellulose 4 g Sodium hydroxide 22.5 g Anhydrous sodium sulfite 120 g Hydroquinone 20 g 1-Phenyl-3-pyrazolidinone 6 g Potassium bromide 0.75 g N -(2-Aminoethyl) ethanolamine 30 ml Ethylenediaminetetraacetic acid tetrasodium salt 2 g pH adjusted to 1000 ml with deionized water pH (24 ° C) = 13 Diffusion transfer initiated for 30 seconds was continued to form a silver image in the image receiving layer.

To remove the developed silver halide emulsion layers and interlayers from the aluminum foil, the developed monosheet DTR material was washed with a water jet stream at 20 ° C.
Rinse for 0 seconds.

Next, the aluminum foil imaged surface is coated with 15
It was guided into the fixer at 20 ° C. for seconds to increase the receptivity of the non-image areas and render the image areas lipophilic ink receptive. The fixer had the following composition: 10% aqueous n-hexadecyltrimethylammonium chloride 25 ml 20% aqueous solution of polystyrene sulfonic acid 100 ml potassium nitrate 12.5 g citric acid 20.0 g 1-phenyl-5-mercaptotetrazole 2. 0 g sodium hydroxide 5.5 g 1000 ml with water pH (20 ° C.) = 4 The printing plate thus produced was placed on the same offset printing machine (ROTOMATIC R-35) and under the same conditions. Used for printing. Florida Anchor / Risemuco
Commercial AQ sold by Incorporated
UA TAME 7035I was used as a wetting solution at a 5% concentration in an aqueous solution containing 10% isopropanol,
And K + E123W sold by Cast + Engel, AG of Germany was used as the ink. A compressible rubber blanket was used.

Ink receptivity was evaluated as follows: The number of copies that had to be printed before the white point disappeared in the ink receptive area.

The results are shown in Table 2 below.

Table 2 Developer Amount of compound added (mmol / l) Ink receptivity A 11 6.5 >> 200 B 12 6.5 >> 200 C Table 1: Compound 7 6.5 50-100 D Table 1: Compound 8 6 .5 50-100 E Table 1: Compound 3 6.5 100

[0119]

[Chemical 5]

Evaluation: From the above, D exposed as above
The TR imaging element was labeled with compound 11 or 12 (comparative 1,
When treated in a solution containing 2,4-triazolium-3-thiolates), the ink receptivity of the printing plates obtained was so poor that after 200 copies the copies were still completely white. I understand. By treating in a solution comprising compound 3, 7 or 8 of Table 1 (1,2,4-triazolium-3-thiolates according to the invention), the ink receptivity of the printing plates obtained is highly It was acceptable.

Example 2 An imaging element prepared as in Example 1 was exposed through a contact screen in a plate making camera and immersed at 24 ° C. in one of the developing solutions D or F for 10 seconds, Here, the composition of F is the same as that of D (Table 6.
5 mmol / l) and N- (2-aminoethyl) ethanolamine (30 ml / l) are replaced by anhydrous sodium thiosulfate (8 g / l).

The imaging element and printing plate were then further processed as described in Example 1. After printing 100 copies, the reproduction characteristics of the two plates were evaluated by measuring the difference in line width between the printed lines, which were non-printed lines on each plate and on the copy. The reproducibility of the plate obtained by developing the imaging element in solution D is much better than that obtained by developing the imaging element in solution E and the difference for the first plate is the printed line. Is about 5 μm for the non-printed line and about 1-2 μm for the non-printed line, the difference for the second plate is about 7-8 μm for the printed line.
And about 5 μm for non-printed lines.

The main features and aspects of the present invention are as follows.

1. On a hydrophilic surface of a support, (i) an image-receiving layer containing physical development nuclei and (ii) a silver halide emulsion and a 10% by weight aqueous solution were added at 1000 ° C. for 30 seconds at 36 ° C. and pH 6. 20 mPa at a shear rate of ^-1 .
imagewise exposing an imaging element comprising a light sensitive layer in water-permeable relationship with said image receiving layer containing gelatin having a viscosity lower than s, and (i) one or more developing agents. , (Ii) 1,2,4-triazolium-3-thiolate and (iii) applying an aqueous alkaline solution to the imaging element in the presence of one or more further silver halide solvents into said image-receiving layer. Forming a silver image and treating the imaging element to remove one or more layers on top of the image receiving layer, thereby exposing the silver image formed in the image receiving layer. A method for producing an offset printing plate by a silver salt diffusion transfer method, wherein the 1,2,4-triazolium-3-thiolate contains a C ₁ -C ₈ alkyl group and C ₄ -C containing at least three fluorine atoms. ₁₀ hydrocarbon group, and at least One of fluorine atoms and / or C
Manufacturing method characterized by being substituted with at least one substituent selected from ₄ -C ₁₀ comprising a hydrocarbon radical C ₁ -C ₈ group consisting substituted 4-amino group with an alkyl group .

2. A C ₁ -C ₅ alkyl group, C _{4 in which the} 1,2,4-triazolium-3-thiolate comprises at least one CF ₃ -group and / or at least two -CF ₂ -groups. -C ₈ hydrocarbon group or at least one of CF _3, - group and / or at least two -CF ₂ -
It is substituted with at least one substituent selected from the group, or C ₄ -C ₈ group consisting of substituted 4-amino group with a hydrocarbon group comprising a C ₁ -C ₅ alkyl group, and from 18 A method according to 1 above having a low total number of carbon atoms.

3. The 1,2,4-triazolium-3-thiolate is of the two following formulas I or II:

[0127]

[Chemical 6]

[In the formula, R ¹ represents a C ₁ -C ₅ alkyl group containing at least one CF ₃ -group and / or at least two -CF ₂ -groups, and R ² represents an alkyl group or an alkenyl group. Represents an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group, A ¹ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or-
NR ³ R ⁴ and R ³ and R ⁴ each independently represent hydrogen or an alkyl or aryl group, or R ³ and R ⁴ are bonded to each other to form a 5- or 6-membered ring. And where the total number of carbon atoms is 14
Fewer],

[0129]

[Chemical 7]

[In the formula, R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group, and A ² is an alkyl group, an alkenyl group. Group, alkynyl group,
A cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or —NR ⁷ R ⁸ ; R ⁷ and R ⁸ each independently represent hydrogen, an alkyl group or an aryl group;
Wherein at least one of the substituents R ⁵ , R ⁶ , R ⁷ or R ⁸ is a C ₄ -C ₈ hydrocarbon group and here the total number of carbon atoms is less than 14]. Method according to 2.

4. The 1,2,4-triazolium-3-thiolate comprises a CF ₃ — group in which R ¹ is at least one and / or
Or a C _1- comprising at least two —CF ₂ — groups
Formula I, which represents a C ₅ alkyl group and R ² and A ¹ each independently represent a C ₁ -C ₄ alkyl group, alkenyl group or alkynyl group, or R ⁵ and R ⁶ or R ⁵ and A ²
Alternatively, R ⁶ and A ² each independently represent a C ₁ -C ₄ alkyl group, alkenyl group or alkynyl group, and the third substituent is a C ₄ -C ₈ alkyl group, C ₄ -C ₈ alkenyl group, C
₄ -C ₈ alkynyl group, C ₅ -C ₈ cycloalkyl group and the total number of carbon atoms is equivalent to one of the smaller Formula II than 14, the method according to the above three.

5. The 1,2,4-triazolium-3-thiolate comprises a CF ₃ — group in which R ¹ is at least one and / or
Or a C _1- comprising at least two —CF ₂ — groups
Formula I, which represents a C ₅ alkyl group and R ² and A ¹ each independently represent a methyl or ethyl group, or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶ and A ² each independently represent a methyl group. or an ethyl group and the third substituent is C ₄ -C ₈ alkyl group, C ₄ -C ₈ alkenyl, C ₄ -C ₈
Expression for the alkynyl or C ₅ -C ₈ cycloalkyl group
A method according to 3 above, which corresponds to II.

6. The formula I, wherein the 1,2,4-triazolium-3-thiolate is such that R ¹ represents a CF ₃ CH ₂ — group and R ² and A ¹ each independently represent a methyl or ethyl group. Or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶
And a methyl or ethyl group A ² are each independently and the third substituent is C ₄ -C ₈ alkyl group or a C ₄ -
A method according to claim 3, which corresponds to formula II representing a C ₈ alkenyl group.

7. The method according to any of 1 to 6 above, wherein the another silver halide solvent is an alkanolamine or a thioether.

8. The method according to 7 above, wherein the alkanolamine is N- (2-aminoethyl) ethanolamine.

9. The above 1, 2 or 4, wherein the 1,2,4-triazolium-3-thiolate is present in the alkaline processing liquid.
A method according to any of 8.

10. The 1,2,4-triazolium-3-
A method according to any of 1 to 8 above wherein a thiolate is present in the imaging element.

11. The hydrophilic base is a granulated and anodized aluminum support, above 1-10.
How to follow either.

12. On the hydrophilic surface of the support, (i) an image receiving layer containing physical development nuclei in the order listed; and (ii)
20 mP of silver halide emulsion and 10% by weight aqueous solution at 36 ° C. and pH 6 at a shear rate of 1000 s ⁻¹
containing gelatin having a viscosity lower than a.
A imaging element comprising a photosensitive layer on the water permeable relationship with said image receiving layer, C ₁ -C ₈ alkyl group which said imaging element comprises at least three fluorine atoms, C ₄ -C ₁₀ At least one selected from the group consisting of hydrocarbon groups and 4-amino groups substituted by C ₁ -C ₈ alkyl groups comprising at least 3 fluorine atoms and / or C ₄ -C ₁₀ hydrocarbon groups The 1,2,4-triazolium-3-thiolate substituted with a substituent is added in an amount of 0.1 to 10 mmol / m ²
An imaging element comprising an amount in between.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jiyan-Marie Dewankele Belgian Bee 2640 Maltsel Septestrat 27 Agfua-Gevert Nammrose Fuennaught Sheep (72) Inventor Marcel Montbariu Belgian Bee 2640 Moltocell Septestraat 27, Aghua-Gevert Namulose Fuennaught Sheep (56) Reference JP-A-6-59454 (JP, A) JP-A-58-196547 (JP, A) JP-A-4-282295 (JP, A) JP 7-209871 (JP, A) JP 7-209870 (JP, A) JP 7-77804 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) G03F 7/07 G03C 8/06 G03C 8/36 G03F 7/32

Claims (6)

(57) [Claims] 1. On a hydrophilic surface of a support, (i) an image receiving layer containing physical development nuclei and (ii) a silver halide emulsion and a 10% by weight aqueous solution at 36 ° C. and p.
20 mPa.s at a shear rate of 1000 s ^-1 at H6
Imagewise exposing an imaging element comprising a light sensitive layer in water-permeable relationship with said image receiving layer containing gelatin having a lower viscosity, (i) one or more developing agents, (Ii) 1,
2,4-triazolium-3-thiolate and (ii
i) applying an aqueous alkaline solution to the imaging element in the presence of one or more additional silver halide solvents to form a silver image in said image-receiving layer and treating said imaging element to the top of the image-receiving layer. removing one or more layers of the above, whereby a manufacturing method of an offset printing plate according to the silver salt diffusion transfer process comprising the step of exposing said silver image formed in said image receiving layer, A C ₁ -C ₈ alkyl group wherein the 1,2,4-triazolium-3-thiolate comprises at least 3 fluorine atoms,
C ₄ -C ₁₀ hydrocarbon groups, and C ₁ -C ₈ alkyl groups and / or C ₄ containing at least 3 fluorine atoms
A method of being substituted with at least one substituent selected from the group consisting of 4-amino groups substituted with -C ₁₀ hydrocarbon groups. 2. A C ₁ -C ₅ alkyl group, C ₄ wherein the 1,2,4-triazolium-3-thiolate comprises at least one CF ₃ — group and / or at least two —CF ₂ — groups. -C ₈ hydrocarbon group or at least one of CF _3, - substituted with comprising group C ₁ -C ₅ alkyl or C ₄ -C ₈ hydrocarbon group - group and / or at least two -CF ₂ Substituted with at least one substituent selected from the group consisting of 4-amino groups, and 1
The method of claim 1 having a total number of carbon atoms less than 8. 3. The 1,2,4-triazolium-3-thiolate is represented by the following two formulas I or II: [In the formula, R ¹ is at least one CF ₃ - C ₁ -C ₅ comprising a group - group and / or at least two -CF ₂
Represents an alkyl group, R ² is an alkyl group, an alkenyl group,
An alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group, A ¹ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or -NR ³ R ⁴ and R ³ and R ⁴ each independently represent hydrogen or an alkyl or aryl group, or R ³ and R ⁴
May combine with each other to form a 5- or 6-membered ring, where the total number of carbon atoms is less than 14], [Wherein R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group, and A ² is an alkyl group, an alkenyl group, an alkynyl group. Group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group or -N
R ⁷ represents R ⁸ , R ⁷ and R ⁸ each independently represent hydrogen or an alkyl group or an aryl group, wherein the substituent R
^{5. At} least one of ⁵ , R ⁶ , R ⁷ or R ⁸ is a C ₄ -C ₈ hydrocarbon radical and the total number of carbon atoms is less than 14]. . 4. The 1,2,4-triazolium-3-thiolate is a C ₁ -C in which R ¹ comprises at least one CF ₃ -group and / or at least two -CF ₂ -groups.
₅ represents an alkyl group and C ₁ -C ₄ alkyl radical R ² and A ¹ are each independently, formula I represents an alkenyl or alkynyl group, or R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶ and A ² is each independently a C ₁ -C ₄ alkyl group,
An alkenyl group or alkynyl group, the third substituent is C ₄ -C ₈ alkyl group, C ₄ -C ₈ alkenyl, C ₄ -
The method according to C ₈ alkynyl group, C ₅ -C ₈ claim 3 represents a cycloalkyl group and the total number of carbon atoms is equivalent to one of the smaller Formula II than 14. 5. The 1,2,4-triazolium-3-thiolate is a C ₁ -C in which R ¹ comprises at least one CF ₃ -group and / or at least two -CF ₂ -groups.
_{5 is} an alkyl group and R ² and A ¹ are each independently a methyl or ethyl group, or R ⁵ and R ⁶
Or R ⁵ and A ² or R ⁶ and A ² each independently represents a methyl or ethyl group and the third substituent is C ₄
-C ₈ alkyl group, C ₄ -C ₈ alkenyl group, the formula II representing the C ₄ -C ₈ alkynyl or C ₅ -C ₈ cycloalkyl group
The method according to claim 3, which corresponds to 6. The formula I, wherein said 1,2,4-triazolium-3-thiolate has R ¹ representing a CF ₃ CH ₂ — group and R ² and A ¹ each independently represents a methyl or ethyl group,
Alternatively, R ⁵ and R ⁶ or R ⁵ and A ² or R ⁶ and A ² each independently represent a methyl or ethyl group and the third substituent is a C ₄ -C ₈ alkyl group or a C ₄ -C ₈ alkenyl. A process according to claim 3 corresponding to formula II representing a group.