JP3402538B2 - Plate making method of lithographic printing plate - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for making a lithographic printing plate by applying a silver complex salt diffusion transfer method.

[0002]

2. Description of the Related Art A lithographic printing plate is composed of an oleophilic image-forming portion that accepts oil-based ink and an oil-repellent non-image-forming portion that does not receive ink. Generally, the non-image-forming portion is hydrophilic to receive water. It is composed of sex parts. In ordinary lithographic printing, both water and ink are supplied to the plate surface, the image area selectively receives the coloring ink, and the non-image area selectively receives water, and the ink on the image area, such as paper Printing is performed by transferring it to a printing medium.

Therefore, in order to obtain a good printed matter, the difference in lipophilicity and hydrophilicity between the image area and the non-image area is sufficiently large, and the image area is sufficient when water and ink are supplied to the plate surface. It is necessary to accept a certain amount of ink and not to accept ink in the non-image area.

A lithographic printing plate using a silver complex salt diffusion transfer method (DTR method), particularly a lithographic printing plate having a physical development nucleus layer on a silver halide emulsion layer is described in, for example, US Pat. No. 3,72.
No. 8,114, No. 4,134,769, No. 4,1
No. 60,670, No. 4,336,321, No. 4,
No. 501,811, No. 4,510,228, No. 4,621,041 and the like. The exposed silver halide crystals cause chemical development by DTR development to give a black color. It becomes silver and forms a hydrophilic non-image area, while unexposed silver halide crystals become a silver salt complex by the silver salt complexing agent in the developing solution and diffuse to the physical development nucleus layer on the surface to form nuclei. In the presence of the above, physical development is caused to form an image area mainly composed of ink-receptive physically developed silver.

As described above, in the planographic printing plate, gelatin-
Since the silver image deposited on the physical development nucleus layer on the silver halide emulsion layer is used as the ink-receptive image area, the image area is larger than that of a general lithographic printing plate (eg PS plate). There is a defect that the resistance to mechanical abrasion of the image part is insufficient, the image part is missing, and the ink receiving property of the image part is gradually lost.

If the hardness of gelatin is increased or the amount of physical development nuclei is increased in order to overcome this drawback, the stain resistance of the lithographic printing plate is remarkably reduced. Further, in the lithographic printing plate, the hydrophilicity of the non-image area is realized mainly by the hydrophilicity of the gelatin surface. However, this is compared with the hydrophilic surface of aluminum generally used in general lithographic printing plates. However, it has a drawback that the stain resistance is relatively easily reduced by printing.

The influence of the surface irregularities of the lithographic printing plate on the printability is well known in the field of PS plates, but it is also an important factor in lithographic printing plates using the silver complex salt diffusion transfer method. In particular,
In a lithographic printing plate using the silver complex salt diffusion transfer method, the non-image area is mainly composed of a gelatin film, and although it is originally highly hydrophilic, it may be modified by a matting agent used to improve the printing durability of the image area. It was general that the matte property of the surface was large (the surface unevenness was large). In recent years, JP-A-5-66564, JP-A-5-80517, JP-A-5-80518, JP-A-5-80520, and JP-A-5-100.
430 and 5-107765, there is a tendency to improve the stain resistance by setting the center line surface roughness Ra of the lithographic printing plate to 1.2 or less. To be

In the field of conventional plate making, due to the complexity of printed materials, the development of scanners, etc., bright room film is used in the returning process, and the final film (complete plate making) is collected from many film originals. Created. Usually, a PS plate is closely baked from this film and processed to be used as a printing plate. On the other hand, a lithographic printing plate using the above-mentioned silver salt diffusion transfer method is usually called direct plate making, and a complete plate on which a reflection original is stuck is photographed by a plate making camera having a reversing mirror to perform a diffusion transfer process. This is done and the lithographic printing plate is created directly. Compared to the film / PS plate system, it is characterized by low cost and time saving, but it has drawbacks such as printing durability of up to tens of thousands of sheets and deterioration of image quality due to optical system. ing. However, taking advantage of the above characteristics, it is used for small-lot printing, and in the case of medium-lot printing and large-lot printing, the PS plate is often used. Often used for small lot printing, in recent years
The demand for shortening the processing time is becoming stronger and stronger.

[0009] In the plate making method that has been realized for such a lithographic printing plate, an automatic plate making camera having a developing treatment tank and a stabilizing treatment tank (neutralization treatment tank) is used. However,
The plate-making process by this plate-making camera is not sufficient in terms of rapid processing, and maintenance is troublesome. Furthermore, from the perspective of environmental issues, there is little processing waste liquid,
Alternatively, there is a demand for the development of a platemaking processing system that does not exist, and is quicker and substantially maintenance-free. Further, a conventional developing method using a developing treatment tank is disclosed in, for example, Japanese Patent Laid-Open No.
Even when the development processing tanks described in JP-A-194935, JP-A-4-158360 and the like are made relatively small, a decrease in pH and a decrease in development speed due to continued processing, generation of silver sludge, and the like. There are many drawbacks such as the generation of a drag pattern due to the movement of the developer and the image deletion due to the flow of the silver complex.

On the other hand, JP-A-48-76603, JP-A-57-115549 and JP-A-4-307245.
Japanese Patent Laid-Open Publication No. 2003-242242 describes a method for plate-making by applying and supplying only a plate surface with a developer necessary for developing a lithographic printing plate. Further, in order to improve various drawbacks of these coating and developing methods, a dip coating method was proposed in Japanese Patent Application No. 5-334028. From the viewpoint of environmental issues, these are faster and substantially maintenance-free plate making processing apparatuses with little or no processing waste liquid, but technical development for adapting lithographic printing plates to such processing systems. Is being requested.

The above-mentioned lithographic printing plate making method using the silver complex salt diffusion transfer method (DTR method) is simple, reliable and quick, can be automated, and has high sensitivity, high resolution and high image reproducibility. The printing plate (PS, which has its own characteristics, has been realized from organic colloids such as diazo photosensitive materials.
The difference in lipophilicity and hydrophilicity between the image portion and the non-image portion was not sufficiently large as compared with the plate). In order to overcome such drawbacks, JP-B-48-29723, JP-A-58-127928 and the like show that a mercapto group compound acts on a silver image before printing to improve ink acceptability. . That is, the mercapto group or the like of the compound is adsorbed on the image silver, the hydrophobic region of the compound covers the image silver, and the difference in lipophilicity and hydrophilicity between the imaged portion and the non-imaged portion becomes relatively large. It is considered.

As described above, the ink receptivity can be improved by using the treatment liquid (starter) which acts on the silver image before printing the compound having the water-insoluble mercapto group or thione group. However, as the lithographic printing plate using the silver salt diffusion transfer method and the PS plate are used more and more in the large format field, it has been demanded to omit such processing at the start of printing in order to improve workability.
By treating with a diffusion transfer developer containing the compound having a mercapto group or a thione group, it is possible to improve the ink acceptability, but due to a decrease in liquid temperature during the treatment of the diffusion transfer developer, etc. However, there is a tendency that the effect of improving the ink acceptability cannot be obtained, and further improvement is desired.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a plate making method which shortens the processing time of a lithographic printing plate using a silver complex salt diffusion transfer method and has a small amount of processing waste liquid at the time of processing. Is.

One object of the present invention is to reduce the processing time of a lithographic printing plate using a silver complex salt diffusion transfer method, and to easily remove stains even when dry starting without processing with a starter. It is to provide a method of making a planographic printing plate using a transfer method.

Another object of the present invention is to provide a method for making a lithographic printing plate having improved adhesion.

An object of the present invention is to provide a plate making method capable of shortening the processing time of a lithographic printing plate using the silver complex salt diffusion transfer method and improving the ink acceptability.

Another object of the present invention is to shorten the processing time of a lithographic printing plate using the silver complex salt diffusion transfer method, and
An object of the present invention is to provide a plate making method capable of maintaining and improving printing durability.

[0018]

The above object of the present invention is to provide a light-sensitive material for a lithographic printing plate, which comprises a support on which at least one undercoat layer, a silver halide emulsion layer and a physical development nucleus layer are successively coated. In the plate-making method in which diffusion transfer development processing is performed within 10 seconds, a) the total gelatin amount on the emulsion layer side is 1 to 4 g / m ² , and b) the non-swelling latex is contained in the undercoat layer. It was achieved by using a light-sensitive material for a lithographic printing plate.

In the light-sensitive material for lithographic printing plate of the present invention,
The total gelatin amount on the emulsion layer side is 1 to 4 g / m ² , and the ink releasability improves as the gelatin amount decreases. 1
Below g / m ² , the film is weak and the printing plate is inferior.
When g / m ² or more, when the diffusion transfer development processing is performed within 10 seconds, the ink acceptability is poor, and the ink detachment is slow and the printing workability is poor.

The non-swelling latex for water used in the present invention is a latex having a low swelling property for water, and can be specified as follows. That is, a test coating liquid having the following composition was prepared, and a wet coating amount of 50 g was applied on a polyethylene terephthalate film which had been subbed.
/ M ^{2 was} applied to prepare a test sample. As a comparison, a comparative coating solution containing no test latex was prepared and applied in the same manner to prepare a comparative sample.

[0021]   <Test coating liquid>   40 g of gelatin   Test latex (solid content) 20g   Fuji Davidson Syroid (Grade 308) 6g   Carbon black dispersion (solid content 32%) 8g   Formaldehyde (30% aqueous solution) 2g   Gliogizar (30% aqueous solution) 4g   Add water to make 500 g.

These samples are dipped in 1N caustic soda for 1 minute, and the increase in weight is measured to obtain the amount of liquid absorption. The ratio of the amount of liquid absorbed between the test sample and the comparative sample is taken and called the swelling ratio. The non-swelling latex for water used in the present invention is a latex having a swelling ratio of 1.2 or less, preferably 1.1 or less.

The non-swellable latex used in the present invention includes, for example, styrene / butadiene latex, polybutadiene latex, polystyrene latex, styrene / isoprene latex.
The amount of non-swelling latex added is converted into solid content,
It is in the range of 0.2 to 5.0 g / m ² .

As disclosed in Japanese Patent Laid-Open No. 3-259655, a gelatin film has a swelling property in water and tends to slow ink / water responsiveness. This is a phenomenon that occurs when the gelatin film sucks the dampening water supplied to the plate surface until the gelatin film reaches the saturated swelling, so the dampening water does not work effectively on the plate surface. In addition, since dampening water is exchanged between the plate surface and the gelatin film at the same time, if the amount of gelatin is increased, the ink / water responsiveness becomes slower. On the other hand, a latex that is non-swellable with water hardly swells with dampening water, so that the ink / water responsiveness is less likely to be delayed. On the other hand, the thickness of the binder is required to reduce the matteness of the surface, and it is effective to use a latex that does not swell in water instead of gelatin in order to accelerate the ink / water response. Is.

In addition to the above-mentioned effects on the ink / water responsiveness, the layer having a non-swelling latex swells slowly in the developing solution, and the DTR developing activity is achieved in the case of small development such as coating development in a short time such as coating development. It turned out to be easy to keep. That is, it is presumed that the permeation of the developing solution (including the activating solution) into the undercoat layer is delayed, and the decrease in the pH in the film caused by the neutralization with gelatin at the initial stage of development is suppressed. Therefore, it is possible to obtain a plate having excellent adhesiveness without deteriorating printing durability after a short time development.

Further, the above object of the present invention, at least one undercoat layer and a silver halide emulsion layer and the lithographic printing plate photosensitive material comprising physical development nuclei layer are sequentially coated on a support
In the plate making method in which diffusion transfer development processing is carried out within 10 seconds after immersion in a developing solution and coating , a) the total gelatin amount on the emulsion layer side is 1 to 4 g / m ² , and b) the emulsion layer side. It was achieved by using a light-sensitive material for a lithographic printing plate in which the ratio of the amount of absorbed liquid to the total amount of gelatin in 1.7 is 1.7 or less.

In the light-sensitive material for lithographic printing plate of the present invention,
The ratio of the liquid absorption amount to the total gelatin amount on the emulsion layer side is 1.7.
It must be: The liquid absorption amount referred to in the present invention is
It is a value showing the change in weight per m ^{2 of the} lithographic printing plate after the lithographic printing plate was made into a plate and immersed in the following dampening liquid at 20 ° C. for 1 minute. When the ratio of the amount of liquid absorption to the total amount of gelatin on the emulsion layer side exceeds 1.7, the ink acceptability and the ink releasability deteriorate during diffusion transfer development processing within 10 seconds. The printing durability may be reduced.

[0028] <Moisturizing liquid>   O-phosphoric acid 10 g   Nickel nitrate 5g   Sodium nitrite 5g   Ethylene glycol 100g   Colloidal silica (20% liquid) 28g   Add water to make 2,000 ml.

Further, the above object of the present invention, at least one undercoat layer and a silver halide emulsion layer and the lithographic printing plate photosensitive material comprising physical development nuclei layer are sequentially coated on a support
In the plate making method in which diffusion transfer development processing is carried out within 10 seconds after immersion in a developing solution and coating , a) the total gelatin amount on the emulsion layer side is 1 to 4 g / m ² , and b) the emulsion layer side. It was achieved by using a light-sensitive material for a lithographic printing plate containing a compound represented by Chemical formula 1.

In the light-sensitive material for lithographic printing plate of the present invention,
The total gelatin amount on the emulsion layer side is 1 to 4 g / m ² , and the ink releasability improves as the gelatin amount decreases. 1
Below g / m ² , the film is weak and the printing plate is inferior.
When g / m ² or more, when the diffusion transfer development processing is performed within 10 seconds, the ink acceptability is poor, and the ink detachment is slow and the printing workability is poor.

In the light-sensitive material for lithographic printing plate of the present invention,
It is necessary to incorporate the compound shown in Chemical formula 1 into the emulsion layer side. The emulsion layer side of the lithographic printing plate light-sensitive material of the present invention means an undercoat layer, an emulsion layer, an overcoat layer, and an auxiliary layer which is provided as necessary, and is any one layer. The number of layers may be two, or it may span two or more layers.

[0032]

[Chemical 2]

In Chemical Formula 2, M ⁺ represents a hydrogen ion, an alkali metal ion or an ammonium ion. In the formula, R3, R
4, R5 and R6 are each a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a halogen atom, an alkoxy group, a hydroxy group, an amino group, a carboxy group, a sulfone group, an alkoxycarbonyl group, an acylamide group and a sulfone. Indicates an amide group. Also, R3, R4, R
5 and R6 may be connected to each other to form a ring.

As a specific example of the benzotriazole compound represented by the general formula 2 and used in the present invention,
~ Chemical formula 16 are illustrated, but the present invention is not limited to these.

[0035]

[Chemical 3]

[0036]

[Chemical 4]

[0037]

[Chemical 5]

[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

The addition amount of the benzotriazole compound of the general formula represented by Chemical Formula 2 used in the present invention depends on the compound and the layer structure, but is 8 × 10 ⁻³ mmol / m ² to
1.6 mmol / m ² , preferably 2.4 × 1
It is in the range of 0 ^-2 mmol / m ^{2 to} 0.4 mmol / m ² .

For the above-mentioned object of the present invention, it is preferable to use a plate-making method in which the photosensitive material for a lithographic printing plate is dipped in a processing solution and applied. A plate-making method of immersing in a processing solution and coating is described in, for example, Japanese Patent Application No. 5-334028, in which the lithographic printing plate photosensitive material is dipped in the processing solution and applied, that is, dip coating ( Dip
・ Coating). More specifically,
Rather than applying the processing liquid only to the photosensitive surface of the lithographic printing plate photosensitive material as in the prior art, the lithographic printing plate photosensitive material is dipped in the processing liquid for an extremely short time and the solution is stored on the photosensitive material. Is formed and the processing liquid is applied to the photosensitive surface.

In the present invention, the center line average roughness Ra value of the planographic printing plate is preferably 1.2 or less. When the center line average roughness Ra value of the planographic printing plate is larger than 1.2, the print image quality tends to deteriorate.

In the present invention, the centerline average roughness Ra value of the planographic printing plate can be measured by using a surface roughness profile measuring instrument, for example, Surfcom 500B manufactured by Tokyo Seimitsu Co., Ltd. From the roughness curve, a portion of the measurement length l is extracted in the direction of the center line, and the center line of the extracted portion is the X axis,
When the direction of longitudinal magnification is taken as the Y axis and the roughness curve is represented by y = f (x), the centerline average roughness Ra value is expressed in units of micrometers and can be calculated by the formula (1).

[0052]

[Equation 1]

The binder used in the present invention is
Gelatin, water-soluble gelatin, starch, dextrin, albumin, sodium alginate, hydroxyethyl cellulose, gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyacrylamide, styrene-maleic anhydride copolymer, polyvinyl methyl ether-maleic anhydride copolymer It is also possible to substitute one or more hydrophilic polymers such as polymers.

The lithographic printing plate which is the object of the present invention contains gelatin, and its containing layer may be an undercoat layer, an emulsion layer or a physical development nucleus layer. These gelatin-containing layers can be hardened with a gelatin hardener.
Examples of the gelatin hardener include inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde and glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, 2,3. Aldehydes such as dihydroxy-1,4-dioxane, 2,4-dichloro-6-hydroxy-
Compounds having an active halogen such as S-triazine salts and 2,4-dihydroxy-6-chloro-S-triazine salts, divinyl sulfone, divinyl ketone and N, N, N
-Triacryloylhexahydrotriazine, compounds having two or more ethyleneimino groups or epoxy groups in the molecule, which are active three-membered rings, one of various compounds such as dialdehyde starch as a polymer hardener, or Two or more kinds can be used.

The hardener can be added to all layers or to some or only one layer.
Of course, the diffusible hardener can be added to only one layer in the case of simultaneous coating of two layers. As an addition method, it may be added at the time of emulsion production or in-line at the time of coating.

In the present invention, it is preferable to use a matting agent having an average particle size of 0.3 to 5.0 μm in the constituent layer on the emulsion side of the lithographic printing plate. Examples of the matting agent used in the present invention include silica particles and organic particles such as styrene. In the present invention, silica particles having a small oil absorption amount disclosed in Japanese Patent Application No. 5-311932 are particularly preferable. Specific examples of such silica particles include Carplex (average particle size: 1.2 microns) manufactured by Shionogi Pharmaceutical Co., Ltd.

In the present invention, the matting agent is preferably contained in the undercoat layer between the support and the silver halide emulsion layer. The amount of the matting agent added varies depending on various conditions, but is 0.1 to 5% in the constituent layer on the emulsion side containing the matting agent.
The range is 0 g / m ² , preferably 0.3 to 3.5 g
The range is / m ² .

The undercoat layer may contain pigments such as carbon black and dyes for the purpose of preventing halation. Further, photographic additives such as developing agents can be included. Further, the undercoat layer is disclosed in JP-A-48-5503 and JP-A-48-10020.
3, such as those described in JP-A-49-16507.

The silver halide emulsion layer is, for example, silver chloride,
It comprises silver bromide, silver chlorobromide, and those containing silver iodide. The silver halide crystal may contain a heavy metal salt such as a rhodium salt, an iridium salt, a palladium salt, a ruthenium salt, a nickel salt and a platinum salt, and the addition amount is 10 ^-8 to 10 ^-3 per mol of silver halide. It is a mole. The crystal form of silver halide is not particularly limited, and may be cubic or tetradecahedral grains, or core-shell type or tabular grains. The silver halide crystal may be a monodisperse or polydisperse crystal,
The average particle size is in the range of 0.2 to 0.8 μm. One preferable example is a monodisperse or polydisperse crystal containing rhodium salt or iridium salt and having a silver chloride content of 80 mol% or more.

The silver halide emulsion can be sensitized in various ways as it is manufactured or coated. It is preferable to chemically sensitize by methods well known in the art, for example, with sodium thiosulfate, alkyl thiourea, or with a gold compound such as gold rhodanide, gold chloride, or a combination of both. The silver halide emulsions can also be sensitized or desensitized positively or negatively with dyes such as cyanines, merocyanines. There is no particular limitation on the wavelength range that can be sensitized or desensitized. Therefore, ortho sensitization, panchromatic sensitization, helium-neon laser sensitization, argon laser sensitization, LED sensitization, semiconductor laser sensitization can be performed, and UV sensitization and visible light desensitization for bright rooms. I can feel it.

The surface layer existing on top of the emulsion layer contains physical development nuclei. Physical development nuclei include fine particles of metal colloid such as silver, antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, rhodium, gold and platinum, and sulfides, polysulfides, selenides of these metals, or those. It may be a mixture or a mixed crystal. The physical development nucleus may or may not contain a hydrophilic binder, but gelatin, starch, dialdehyde starch, carboxymethyl cellulose, gum arabic, sodium alginate, hydroxyethyl cellulose, polystyrene sulfonic acid, sodium polyacrylate, vinyl. It may contain a copolymer of imidazole and acrylamide, a copolymer of acrylic acid and acrylamide, a hydrophilic polymer such as polyvinyl alcohol or an oligomer thereof, the content of which is 0.5 g / m 2.
It is preferably ² or less. Further, the physical development nucleus layer may contain a developing agent such as hydroquinone, methylhydroquinone and catechol, and a known hardener such as formalin and dichloro-s-triazine.

Each of the coating layers such as the undercoat layer, the silver halide emulsion layer and the physical development nuclei layer may contain some of anionic, cationic or neutral surfactants as coating aids. , Antifoggants, matting agents, thickeners, antistatic agents and the like.

As the support for the lithographic printing plate of the present invention,
Paper or a synthetic or semi-synthetic polymer film, a metal plate such as aluminum or iron, and the like can be used as long as they can withstand lithographic printing. The surface of the support may be coated on one side or both sides with one or more polymer films or metal thin films. The surface of these supports can be surface-treated in order to improve the adhesion with the coating layer.

Particularly preferably used supports are paper having both surfaces or one surface coated with a polyolefin polymer, a polyester film, a polyester film having a hydrophilic surface, a surface-treated aluminum plate, and the like.
These supports may contain pigments for preventing halation and solid fine particles for improving surface properties. The support may also be light transmissive so that backside exposure is possible.

The developing solution used in the present invention contains an alkaline substance such as sodium hydroxide or potassium hydroxide,
Lithium hydroxide, sodium triphosphate, etc., sulfites as preservatives, silver halide solvents, such as thiosulfates,
Thiocyanates, cyclic imides, 2-mercaptobenzoic acid, amines, thickeners such as hydroxyethyl cellulose, carboxymethyl cellulose, antifoggants,
For example, potassium bromide, the compounds described in JP-A-47-26201, developers, such as hydroquinones, catechol, 1-phenyl-3-pyrazolidone, development modifiers,
For example, a polyoxyalkylene compound and an onium compound can be included. Further, compounds such as those described in U.S. Pat. No. 3,776,728, which improve ink transfer of the surface silver layer, can be used in the developing solution.

The surface silver layer after development of the lithographic printing plate of the present invention can be converted into ink receptivity or the receptivity can be enhanced with any known surface treating agent. Examples of such treatment liquid include Japanese Patent Publication No. 48-29723 and U.S. Pat. No. 3,7.
21, 559 and the like. The printing method, or the desensitizing liquid, the dampening liquid, or the like to be used may be a commonly known method.

[0067]

EXAMPLES The present invention will be explained below with reference to examples, but of course the present invention is not limited thereto.

Example 1 Gelatin and styrene-butadiene latex were used in the amounts shown in Table 1 to prepare the following undercoating liquid, and the epoxy compound shown in JP-A-60-213942 was used for the purpose of hydrophilization. Coating is carried out as follows on an aqueous subbed polyester film support with the subbing composition contained.

[0069] <Undercoat liquid>   Gelatin Xg   20.0 g water   Fuji Davidson Syroid (grade 978, average   Particle size 2.5μ) 0.6g   Carbon black dispersion (solid content 32%) 0.8 g   Formaldehyde (30% aqueous solution) 0.2 g   Gliogizar (30% aqueous solution) 0.4 g   Mitsui Toatsu Chemicals Polylac 752A (styrene-butadiene   System latex, solid content 47.5%) Yg   Surfactant 0.6 ml   Water is added to bring the total amount to 50.0 g.

The coating amount was 50 g / m ² in terms of moisture coating amount. When the transmission density of this sample was measured, it was 0.5. When the swelling ratio by addition of Polylac 752A manufactured by Mitsui Toatsu Chemicals, Inc. was determined using the test method described in the present text, it was 1.08, which corresponds to the non-swelling latex for water referred to in the present invention. Was there. An ortho-sensitized high-contrast silver chloride emulsion was coated on these in an amount of 1.5 g / m ² in terms of silver nitrate (emulsion layer gelatin amount 1.
0 g / m ² ). After drying, it is heated at 50 ° C. for 2 days to obtain the light of Japanese Patent Laid-Open No.
8-21602, the nucleating coating solution described in Example 2 (the polymer contains a copolymer of No. 3 acrylamide and imidazole and contains 0.8 g of hydroquinone as a developing agent).
m ² ) was added to the compound of Chemical formula 4 of JP-A-6-332183 at 0.04 g / m ² to prepare and apply in the same manner. (Sample 1, Sample 2, Comparison a,
Comparison b)

Each of the above lithographic printing plates was subjected to image exposure only by a plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills, and the following development was carried out using the developing device described in the embodiment of Japanese Patent Application No. 5-334028. Each sample was dipped and processed in the diffusion transfer developing solution of No. 3 at 30 ° C., and developed by holding for 5 bars until neutralized by the stabilizing solution. Stabilization was carried out with a stabilizing solution having the following composition at 30 ° C. for 5 hours, followed by drying. For comparison, each lithographic printing plate was subjected to image exposure and development processing using a plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills. The development was carried out with the following diffusion transfer developer at 30 ° C. for 20 tons. Stabilization was carried out by treating with a stabilizing solution having the following composition at 25 ° C. for 20 seconds and drying.

[0072] <Diffusion transfer developer>   700g of water   18 g of sodium hydroxide   7 g of potassium hydroxide   Anhydrous sodium sulfite 50g   2-mercaptobenzoic acid 1 g   Uracil 10g   2-methylaminoethanol 30g   5-phenyl-2-mercapto-1,3,4-oxadiazole 0.1 g   Potassium bromide 1g   Add water to bring the total volume to 1,000 ml.

[0073] <Stabilizing liquid>   Water 600g   Citric acid 10g   Sodium citrate 35g   Colloidal silica (20%) 5g   Ethylene glycol 5g   Add water to bring the total volume to 1,000 ml.

AB Dick 350CD (AB
Ink release property and printing durability were evaluated using a Dick offset printing machine trademark). The ink releasability was represented by the number of sheets in which background stains disappeared by dry-starting without etching, placing the entire surface of the ink in a state where stains were generated, and using the following dampening liquid while feeding water.
Further, the printing durability was judged by the following evaluation criteria, based on the number of printed sheets when the image was skipped due to the missing of the silver image portion and could not be used for printing. (A) 20,000 sheets or more (B) 10,000 to 20,000 sheets (C) 5,000 to 10,000 sheets (D) 2,000 to 5,000 sheets (E) Less than 2,000 sheets printed The results are shown in Table 1.

[0075] <Moisturizing liquid>   O-phosphoric acid 10g   Nickel nitrate 5g   Sodium nitrite 5g   Ethylene glycol 100g   Colloidal silica (20% liquid) 28g   Add water to make 2,000 ml.

Regarding the adhesiveness, the plate after plate making was scratched, immersed in dimethylformamide for 1 minute at 20 ° C., and then rubbed with absorbent cotton to evaluate the state of film peeling. (A) No peeling at all (B) Occurrence of partial film peeling (C) Complete peeling of film

[0077]

[Table 1]

As is clear from Table 1, Comparative b containing no polylac 752A, which is a styrene-butadiene latex, was inferior in printing durability and adhesiveness after 5 seconds development, and the total amount of gelatin on the emulsion side was The comparative a of 4.5 g / m ² is inferior in the ink releasing property and the printing durability, while the sample 1 and the sample 2 of the present invention are the ink releasing property, the printing durability,
Excellent adhesion. Further, by using the developing device described in the embodiment of Japanese Patent Application No. 5-334028, a plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills Co., Ltd.
It was possible to reduce the amount of waste liquid to 1/7 as compared with the case of using.

Example 2 On a polyester film support aqueous subbed with an undercoating composition containing an epoxy compound disclosed in JP-A-60-213942 for the purpose of hydrophilization, according to Table 2, as shown below. Apply a subbing layer. Moisture application amount is 60
It was g / m ² .

[0080] <Undercoat liquid>   Gelatin Xg   20 g of water   Shionogi Pharmaceutical Co., Ltd. Carplex (FPS-101) Yg   Water 10g   Carbon black dispersion (solid content 32%) 0.8 g   Formaldehyde (30% aqueous solution) 0.4 g   Gliogizar (30% aqueous solution) 0.4 g   Surfactant 0.6 ml   Water is added to bring the total amount to 60 g.

Before adding an aqueous dispersion of Shionogi Pharmaceutical Co., Ltd. Carplex (FPS-101), which is silica particles having an average particle size of 1.2 μm, to this, an ultrasonic disperser was used to After dispersing for a minute, it was added to the gelatin solution. On the above-mentioned undercoat layer, an ortho-sensitized high-contrast silver chloride emulsion was coated in an amount of 1.5 g / m ² in terms of silver nitrate (emulsion layer gelatin amount: 1.0 g / m ² ). After drying 5
After heating at 0 ° C. for 2 days, Example 2 of JP-A-58-21602
(1) The nuclei coating solution described in 1. (The polymer contains a copolymer of No. 3 acrylamide and vinylimidazole and contains hydroquinone as a developing agent at a rate of 0.8 g / m ^2. )
To 0.04 g of the compound of Chemical formula 4 in JP-A-6-332183
The added liquid was adjusted and coated in the same manner so that the amount became / m ² .

Thereafter, in the same manner as in Example 1, each of the above planographic printing plates was imagewise exposed and developed. The liquid supply amount of the planographic printing plate after plate making was measured, and the ratio of the liquid absorption amount to the total gelatin amount on the emulsion layer side was calculated and shown in Table 2. AB
Dick 350CD (trademark of offset printing machine manufactured by AB Dick Co., Ltd.) was used to evaluate ink receptivity, ink release property, and printing durability. Regarding the ink acceptability, after treating the plate surface with the following dampening liquid, printing was performed using the dampening liquid described in Example 1 and using New Champion Ink N manufactured by Dainippon Ink and Is represented by the number of sheets exceeding 80% of the saturated concentration. Ink detachability is 200
After printing the sheets, the water feed was stopped, and the entire surface was covered with ink to cause stains. The water feed was restarted to express the number of background stains. The printing durability was evaluated in the same manner as in Example 1.

[0083]

[Table 2]

As is clear from Table 2, in the 20-second development, Sample 3, Sample 4 and Comparative c both have acceptable ink receptivity and printing durability. It was found that Samples 3 and 4 were superior in ink receptivity and printing durability and in ink releasability as compared with Comparative c. Further, by using the developing device described in the example of Japanese Patent Application No. 5-334028, the amount of waste liquid is reduced to 1/7 as compared with the case where the plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills is used. Could be reduced.

Example 3 In the undercoating liquid of Example 2, formaldehyde was added in Table 3
A sample was prepared in the same manner as in Example 2, as shown in
Print evaluation was performed. The results are shown in Table 3.

[0086] <Undercoat liquid>   Gelatin 2.5g   20 g of water   Shionogi Pharmaceutical Co., Ltd. Carplex (FPS-101) 4.0 g   Water 10g   Carbon black dispersion (solid content 32%) 0.8 g   Formaldehyde (30% aqueous solution) Zg   Gliogizar (30% aqueous solution) 0.4 g   Surfactant 0.6 ml   Water is added to bring the total amount to 60 g.

[0087]

[Table 3]

As is clear from Table 3, when developed for 5 seconds, Samples 5 and 6 of the present invention are superior in ink receptivity, ink release property and printing durability as compared with Comparative d. It has been found. Further, by using the developing device described in the example of Japanese Patent Application No. 5-334028,
The amount of waste liquid could be reduced to 1/7 as compared with the case of using the plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills.

Example 4 The amount of gelatin and the benzotriazole compound of Chemical formula 4 were as shown in Table 4 in the following undercoating liquid, and the epoxy compound shown in JP-A-60-213942 was added for the purpose of hydrophilization. An undercoat layer is coated as follows on a polyester film support which has been subjected to an aqueous undercoating treatment with the above-mentioned undercoat composition.

[0090] <Undercoating liquid (A)>   Gelatin Xg   20 g of water   Fuji Davidson Syroid (Grade 308) 0.3g   Carbon black dispersion (solid content 32%) 0.8 g   Formaldehyde (30% aqueous solution) 0.2 g   Gliogizar (30% aqueous solution) 0.4 g   1-benzoylamino-5-phenyl-2-mercapto-   1,3,4-triazole 0.005 g   Compound 4 benzotriazole compound Yg   Surfactant 0.6 ml   Add water to bring the total volume to 50 g.

The coating amount was 50 g / m ² in terms of moisture coating amount. Fuji Davidson Syroid (grade 30
The average particle size of 8) was 3.5μ as measured by the Coulter counter method. An ortho-sensitized high-contrast silver chloride emulsion was coated on these in an amount of 1.5 g / m ² in terms of silver nitrate (emulsion layer gelatin amount 1.0 g).
/ M ² ). After drying, the mixture is heated at 50 ° C. for 2 days, and the temperature is reduced to 58 ° C.
21602, the nuclei coating solution described in Example 2 (containing a No. 3 acrylamide copolymer and a imidazole copolymer as a polymer, and 0.8 g / m ^{2 of} hydroquinone as a developing agent).
Of the compound of JP-A-6-332183 to 0.04 g / m ² was similarly prepared and applied.

Thereafter, in the same manner as in Example 1, each of the above lithographic printing plates was imagewise exposed and developed. Hereinafter, printing evaluation was performed in the same manner as in Example 1, and the results in Table 4 were obtained.

[0093]

[Table 4]

As is clear from Table 4, in the development for 20 seconds, the printing durability of Samples 7 and 8 is good, and the printing durability of Comparative e and Comparative f is within the allowable range, but 5 seconds. When developed, the printing durability of Comparative e and Comparative f is lowered to an unacceptable level. On the other hand, the printing durability of Sample 7 and Sample 8 of the present invention was as good as the development for 20 seconds. Ink releasability is inferior to Comparative e, but Samples 7 and 8 of the present invention, and
Comparison f was within tolerance. In addition, Japanese Patent Application No. 5-33402
By using the developing device described in the embodiment of No. 8, the plate-making camera processor CP-55 manufactured by Mitsubishi Paper Mills Co., Ltd.
Compared with the case of using 0II, the amount of waste liquid could be reduced to 1/7.

Example 5 A benzotriazole compound of Chemical formula 2 was used in place of the benzotriazole compound of Chemical formula 4 of Example 4, and a sample was prepared in the same manner as in Example 4 according to Table 5, and printing evaluation was carried out. . The results are shown in Table 5.

[0096]

[Table 5]

As is clear from Table 5, in the 20 second development, the printing durability of the sample 9 is good, and the printing durability of the comparative g and the comparative h is within the allowable range. And, the printing durability of Comparative h is lowered to an unacceptable level. On the other hand, the printing durability of Sample 9 of the present invention was as good as the development for 20 seconds. The ink releasing property was inferior in Comparative g, but Sample 9 of the present invention and Comparative h were within the allowable range. Further, by using the developing device described in the example of Japanese Patent Application No. 5-334028, the amount of waste liquid is reduced to 1/7 as compared with the case where the plate-making camera processor CP-550II manufactured by Mitsubishi Paper Mills is used. Could be reduced.

[0098]

EFFECTS OF THE INVENTION By using the present invention, a plate making method that shortens the processing time of a lithographic printing plate using the silver complex salt diffusion transfer method and is excellent in ink release property, printing durability and adhesiveness Can be provided.

Continuation of front page (56) References JP-A-5-107766 (JP, A) JP-A-6-324496 (JP, A) JP-A-5-313374 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) G03F 7/07 B41C 1/10 G03C 8/06 G03F 7/11

Claims (2)

(57) [Claims] 1. A lithographic printing plate light-sensitive material obtained by sequentially coating at least one undercoat layer, a silver halide emulsion layer and a physical development nucleus layer on a support is dipped in a developing solution and coated.
In the plate making method of performing diffusion transfer development within 10 seconds, a) the total amount of gelatin on the emulsion layer side is 1 to 4 g / m ² , and b) the amount of liquid absorption relative to the total amount of gelatin on the emulsion layer side. The ratio of 1.
A plate-making method comprising using a photosensitive material for a lithographic printing plate which is 7 or less. 2. A lithographic printing plate light-sensitive material obtained by sequentially coating at least one undercoat layer, a silver halide emulsion layer and a physical development nucleus layer on a support is dipped in a developing solution and coated.
In the plate-making method in which diffusion transfer development processing is performed within 10 seconds, a) the total amount of gelatin on the emulsion layer side is 1 to 4 g / m ² , and b) the compound represented by Chemical formula 1 is added on the emulsion layer side. A plate-making method comprising using a lithographic printing plate-containing photosensitive material contained therein. [Chemical 1] (In the formula, M + is hydrogen ion, alkali metal ion,
Indicates an ammonium ion. In the formula, R3, R4, R5 and R6 are each a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a halogen atom, an alkoxy group, a hydroxy group, an amino group, a carboxy group, a sulfone group or an alkoxycarbonyl group. , An acylamide group, and a sulfonamide group. Also, R3, R4, R5 and R6
May be connected to form a ring. )