JPS59201898A - Planographic printing plate - Google Patents

Abstract

PURPOSE:To improve water resistance and physical and mechanical strength, by using a raw paper laminated with an aluminum foil as a base, in a planographic printing plate to which a silver salt diffusion transfer system is applied. CONSTITUTION:An aluminum foil having a thickness of not smaller than 0.1mum is integrally laminated on a raw paper to obtain a base, and a hydrophilic colloid layer for supporting silver of an image printed by utilizing a silver salt diffusion transfer method is provided on the surface of the aluminum foil of the base. The colloid layer comprises a photosensitive silver halide emulsifier layer, a physical development nucleus layer, an anti-halation layer, an undercoat layer, an intermediate layer and the like, and preferably, one or more silane coupling agents such as a compound of formula I or II are incorporated into at least one of the layers. Accordingly, physical properties of the film as a planographic printing plate are improved, and the film will not be peeled off even when being used repeatedly for printing.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Commercial Use) The present invention relates to a flat printing ladle material with improved printing durability and plate elongation.

(rice promotion technology) As a lithographic printing material using the Tsukuda diffusion transfer method,
No. 6-10910, No. 46-42453 and No. 48-
30562, a method in which a physical development layer provided on a silver halide photographic emulsion layer is used as an ink receptive layer, or US Pat. No. 3,511.65.
No. 6, Specification No. 3,557,690 JP-A-57-44
As described in Japanese Patent No. 153, a silver halide photographic emulsion layer is provided on the physical development nucleus layer, and a printing image is formed by a diffusion transfer method, and then the upper halide emulsion layer is removed to form a printing plate. There are known ways to obtain it.

Various supports are used for the lithographic printing plates, depending on the purpose or use, such as aluminum plates, zinc plates, multilayer metal plates, plastic films, paper materials, etc. .

These supports are required from the viewpoint of printing durability, or from the viewpoint of printing properties, there is no white background smearing during printing, and there is also adhesion between the printing layer (printed image bearing layer) and the support. Appropriate supports are selected depending on needs, such as strength, manufacturing cost, and ease of handling.

In recent years, the demand for direct planographic printing plates that can be easily printed has increased significantly, and coating, coating,
It is easy to process such as cutting, has good flammability for waste disposal, and is inexpensive, so it is often used as a support and resting material.

In addition, the appropriate rigidity of the stamp support makes it suitable for use with modern automatic plate making machines and against printing erosion.

Many lithographic printing plates to which the tin salt diffusion transfer method of the present invention is applied use paper supports.

After exposing the lithographic printing plate to photograph important lines,
Transfer and develop with an alkaline processing liquid to form a printed image.

The image is then subjected to a development stop bath or six times of peeling treatment, and then the image is made hydrophobic with an oleophilic liquid, and then printed using an offset printing machine while supplying ink and dampening water.

In this way, in the case of lithographic printing plates that use the Kabanana diffusion transfer method, they are passed through a harsh alkaline bath or evening bath using the photographic method, and are constantly immersed in dampening water during printing. It goes through

Therefore, in order to print a large number of clear prints, the plate itself must have strong physical properties and mechanical strength during these processing steps. If this happens, the paper will expand and contract on the printing press cylinder, causing serious defects such as wrinkles and loss of flatness.

Therefore, when paper is used as a support for a lithographic printing plate, both sides of the paper are treated with water-resistant treatment, specifically a cold processing method using resin or the like, or a hydrophobic polymeric substance such as a polyolefin-based polymeric compound. So-called resin-coated paper, which has been subjected to grain treatment, has been widely used up to now.

However, compared to aluminum plates or plastic films, it is still difficult to use paper, so it cannot completely prevent the penetration of the processing liquid as described above. It is undeniable that they are inferior in terms of objective strength.

Further, the adhesion between the hydrophobic surface of the polyolefin polymer and the printed image-bearing layer is not necessarily sufficient, and peeling occurs during printing on a polyester sheet.

(Purpose of the present invention) With the background of such traditional technology, we can maintain the above-mentioned advantages and advantages of current paper supports, while maintaining the water resistance and physical properties that are most important for lithographic printing plates. , improving mechanical strength has been a technical challenge.

Therefore, the first object of the present invention is to achieve an improved planar diffusion transfer that does not cause expansion and contraction of the support (plate) or peeling of the printed image-bearing layer by penetration of a processing liquid during plate making and printing. It is to provide old lithographic printing materials according to the law.

The second object is to provide a lithographic printing paulownia material from which a large number of high-quality printed materials can be easily obtained.

(Structure of the Invention) The lithographic printing plate of the present Jomei is a support made of a base paper laminated with aluminum foil, and a hydrophilic colloid that supports silver is formed on the surface of the aluminum foil layer by an ink-receptive Kashitara diffusion transfer method. The structure is characterized by providing layers.

Further, a preferred embodiment can be obtained by incorporating a silane cupping agent into the hydrophilic colloid layer.

Aluminum foil laminated paper that can be used in the above-mentioned present invention is already known in the art. For example, in JP-A No. 58-24149, aluminum laminated base paper is used as a support for Shigeko photolithographic printing, In order to improve the properties, a structure in which fine powder of aluminum is combined is described.

On the other hand, silane fogging agents are also widely known for the purpose of improving adhesion or surface printing.For example, silane fogging agents were used in protein colloid layers coated on glass dry plates.
No. 3565, or JP-A Nos. 50-96231 and 56-7 used on electroconductive substrates for electrophotography or in photoconductive layers.
No. 2448, and JP-A-51-52002 in which o-naphthoquinone azide was used in a photosensitive layer.

All of these methods, both good and bad, are proposals aimed at strengthening the adhesion between the support and the coating layer, which is the same as the object of the present invention.

However, all of these conventional techniques relate to electrophotographic materials that are mainly organic solvent-based and non-aqueous liquids, or even if the coating liquid is swamp water-based, the support is The fact that it is a glass substrate is also a technical field outside the scope of the present invention, and the adhesion of the coating layer is largely controlled by the properties of the support surface and the composition of the coating liquid applied thereon. This information is provided by persons familiar with the relevant technical field.

The structure of the invention is to coat an aluminum foil laminated base paper support with a hydrophilic colloid layer that supports an image button having ink receptivity and formed using a silver width diffusion transfer method, thereby preparing a lithographic printing plate. Preferably, the hydrophilic colloid layer contains at least one kind of silane coupling agent to achieve the above-mentioned objects, and the surface of the aluminum foil layer and the silane coupling agent-containing hydrophilic layer In combination with this, it has an excellent effect that could not be predicted from the conventional technology.

The thickness of the aluminum foil of the aluminum foil laminate base paper support (hereinafter simply referred to as aluminum base paper) is 0.1.
The thickness is preferably 0.5 to 20 μm.

Since the lithographic printing plate of the present invention uses a laminated aluminum foil as a support, it has excellent barrier properties and durability because it is a five-plate plate, and is hydrophilic and has a silane sealing agent on its surface. Since it is provided with a sexual colloid layer, it has excellent film properties as a lithographic printing plate, and the intended purpose can be achieved without peeling even after repeated printing several times.

The compounds shown below are specific examples of silane coupling agents that can be advantageously used in the present invention.

Of course, non-invention is not limited to this.

(Exemplary Compounds) These compounds are commercially available as SH series or silane coupling agents from Toray Silicon Co., Ltd. (Hatchobori, Naka4-ku, Tokyo) or Chisso Corporation (Marunouchi, Chiyoda-ku, Tokyo). It is readily available.

The above-mentioned compound used in the present invention can be arbitrarily selected depending on the purpose, and is a water-visible colloid for use in the halogenated steel emulsion layer, antihalation layer, undercoat layer, etc. of the above-mentioned silver diffusion transfer type photographic element. It can be contained in at least one layer.

The amount used is, for example, 1 part dry gelatin as a hydrophilic binder.
It may range from 0.001 to 10 g/g, preferably 0.001 to 10 g/g.
A range of 0.01 to 1.0 g is preferable.

When used, it may be dissolved and dispersed in water or a hydrophilic bath medium such as methanol, and if necessary, it may be added in the form of a dispersion in a water bath liquid such as gelatin.

Further, an acid or alkaline agent may be used to adjust the pH of the aqueous solution to an appropriate level. It may be added to the constituent elements at any time during the plate manufacturing process, but preferably immediately before coating.

Of course, the compounds related to the present invention may be used alone, and the compounds related to the present invention may be used alone.
You may mix more than one species.

In addition, the cost of resin coating with α-olefin etc.
To improve and strengthen adhesion, the surface of the support is coated with a corona coating.
The passageway was used for preliminary treatments such as ultraviolet irradiation and flame treatment.

It is most effective to carry out these treatments immediately before forming the coating layer, but the process may cause light leakage during coating of the photosensitive silver halogen emulsion due to discharge, and the adhesion of dust due to charging. There was a problem.

By using the aluminum base paper according to the present invention, these preliminary treatments are no longer necessary, and in addition to eliminating troubles, the elimination of the need for various devices is an extremely advantageous advantage from a manufacturing perspective.

Hereinafter, to explain this pruritus in more detail, silver foil is placed on the surface of the aluminum foil on a support (aluminum base paper) that is made by laminating aluminum foil with a thickness of 0.1 micrometer or more onto base paper and attaching it to the base paper. A lithographic material is obtained by applying a hydrophilic colloid layer of lithographic printing using a diffusion transfer method using a conventional method.

An undercoat layer may be provided on the aluminum foil surface of the aluminum base paper for the purpose of strengthening the adhesiveness with the hydrophilic colloid layer.

There are no particular restrictions on the undercoat layer, and for example, various synthetic resin emulsions such as those shown below may be used. Preferably used synthetic resin emulsions include, for example, acrylic acid, methacrylic acid or their esters, vinyl group-containing monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, pucdiene, styrene, or the like. It may be a copolymer or an emulsion latex of an aqueous dispersion obtained by emulsion polymerization or emulsion copolymerization. Further, the back surface of the aluminum base paper, that is, the surface opposite to the aluminum foil layer, may be subjected to a commonly used water-resistant treatment.

The main resins used for water resistance treatment include the following, and it is preferable to apply the stiff resin as a layer of 0.1 to 10 microns.

For example, polyethylene terephthalate, polyimide, polycarbonate, polyacrylate, polymethyl methacrylate, polyvinyl alcohol, polyvinyl chloride, polyvinyl alcohol, polystyrene, styrene-butadiene copolymer, polymethanolylate, silicone resin, mound comb, epoxy Resins, pure and modified alkyd resins, polyethyl methacrylate, poly-n-butyl methacrylate, cellulose acetate, ketone resins, polyethylene 1, polypropylene, polyacrylonitrile, rosin derivatives, polyvinylidene chloride, nitrocellulose,
Phenol-formarethehyde tree, metacresol formaldehyde tree, styrene-maleic anhydride co-incorporated medium, polyacnolic acid-polyacrylic acid amide co-conjugate,
Useful examples include nytylene glycol thumarate copolymer, methinovinyl ether and maleic anhydride copolymer, acryloylglycine-vinyl lactate copolymer, polyvinylhydrolidone, polyvinyl alcohol, polyamide, and methylene halokenide.

The silver-carrying hydrophilic colloid layer of the printed image obtained by applying the diffusion transfer method according to the present invention includes a photosensitive halogenated emulsion layer, a physical development nucleus layer, an antihalation layer, an undercoat layer, an intermediate layer, etc. Point. The most preferable form of the layer structure is one in which an undercoat layer consisting of a hydrophilic colloid layer is provided between the aluminum foil layer and the aluminum foil layer, which provides safe ink receptivity for printing. In this form, a noration prevention layer is coated between the foil layer and the physical development nucleus layer, which has ink receptivity necessary for printing, and a halogen compound is coated on the upper layer.

The antihalation layer refers to a layer containing dye, pigment, or carbon black.

As the hydrophilic colloid (bainggu) of the constituent layer according to the present invention, it is preferable to use ceratin treated with acid or lime, and some hydrophilic molecular compounds such as polyvinyl ether, polyvinyl ether, etc. Acrylamide, Holly N-Hinylpyronodone, Polyvinyl Alcohol, Carboxymethyl Cellulose, Alginic Acid, Maleic Anhydride.
It can be held down with ethylene copolymer, etc.

The seeds of the photosensitive halide emulsion used in the present invention are selected from commonly used silver halogens, silver bromide, silver iodine, silver chloride, silver chloride, silver iodine, etc. Be it. The type of emulsion may be either negative or positive, or it may be a special type described in Ichikagaku No. 54-44844, which uses a photosensitive halogenated material and the solubilized non-photosensitive halogenated material. good. These silver halide emulsions can be subjected to sensitization or spectral sensitization, if necessary.

Further, the flash emulsion may be stabilized with azaindenes, and hardening agents commonly used in the art may be used alone or in combination in the parent wood colloid layer.

After imagewise exposure, the lithographic printing material in the present invention is developed with a halogen silver developing agent.

As the main developer, polyhydroxybenzenes and 3-pyrazolidinones are preferable, and they may be used in the form of so-called herbal medicines incorporated in the constituent layers of the main plate material.

The physical development nuclei of the physical development layer in the present invention may be those used in the known silver salt scattering transfer method, such as a mixture of colloids such as gold or silver, water-soluble salts such as palladium or zinc, and sulfides. metal sulfides etc. can be used. For details and manufacturing methods, see, for example, W, F, Berg,
Photographic Silver Halide
Diffusion Processes 1972
．． Focal Press.

After image formation, the lithographic printing phase material according to the present invention is processed in an alkaline processing bath in the presence of a halogenated developer. When a developer is included in the plate material in advance, only an alkaline treatment bath is required, or the developer may be included in some cases.

For the alkaline treatment bath, caustic soda, caustic potassium, sodium carbonate, potassium carbonate, etc. can be used as the alkaline agent, and the pH of the treatment bath is preferably between 8 and 14.

In addition, the halogenated silver solvents in the alkaline treatment bath include chromate salts such as sodium sulfite, sodium thiosulfate,
Examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, amino acids such as insulin and cysteine, thioureas, thioethers, and the like.

As described above, the present invention is a lithographic printing original plate using the silver salt transfer method for use on aluminum paper, and the advantages of Kitoaki can be summarized as follows.

(1) Since the elongation of the plate during printing is reduced, high-quality printed matter can be obtained.

[2] The printing durability is improved as a support for Senshio lithographic printing because the material treated during plate making or the dampening water during printing does not penetrate into the paper layer.

(3) Since the adhesion between the support and the hydrophilic colloid layer is excellent, the physical and mechanical strength of the coating film is improved.

[4] There is no need for corona exposure treatment, which can be done with conventional resin-coated paper.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 The back side (non-aluminum foil side) of an aluminum base paper made by laminating and integrating aluminum foil with a grain size of 10 microns onto a base paper having a weight of 130 g/m2 was water-proofed with the following liquid.

Polyvinyl alcohol (10% aqueous solution) 200 parts by weight S
BR latex (solid content 50%) 300 parts by weight Coating amount: 5 g/m3 On the aluminum foil surface of the obtained aluminum base paper, carbon black of the former with a transmission density of 1.5 or more, and hydroquinone and phenidone as developing agents were added. A 5% finished gelatin solution was prepared and applied as an antihalation layer.

In addition, this coating liquid contains the following exemplified compounds of the silane coupling agent according to the present invention as adhesion improvers.
After adding as shown in the table, the coating amount was 40 g/m2.

Next, as a matting agent, fine silica powder and Zyroid 308 [Fuji Daveyson University] were added to the ortho-sensitized medium-sensitivity silver chlorobromide emulsion (silver chloride 90 mol %, remaining silver bromine) as a matting agent per 1 g of gelatin. .2g of gelatin and 0.15g of formaldehyde were added to adjust the gelatin concentration to 5%, and the coating amount was 40g/m2.

Next, a gold colloid obtained by reducing chloroauric acid with sodium borohydride was applied as a physical development nucleus layer to the upper layer to obtain a lithographic printing material of the present invention at a concentration of 60 mg/m 2 as chloroauric acid.

Each layer contained a suitable amount of sodium octylsulfosuccinate as a coating aid. A sample of the resulting lithographic printing material was coated at 40°C and 40% RH for 30 minutes.
The adhesion of the coated layer to the support was examined after being left for ~5 days. The measurement was carried out using a continuous weighting type scratch strength measuring machine (SHINTOHEIDON-18; Shinto S
scientific Co. Ltd. After immersing the sample in water at 20° C. for 5 minutes, the gelatin film was scratched with a steel needle of 0.5 mil diameter, and the pressure (g) at that time was expressed.

The results obtained are shown in Table 1 below.

It can be seen from Table 1 that the printing material of the present invention has excellent adhesion between the support and the coating layer.

Example-2 The sample obtained in Example-1 was heated at 40°C and RH40% for 4 hours.
After leaving it for a day, automatic plate making (IPA manufactured by ITEC Corporation)
-300) for image exposure resource image processing and plate making. The compositions of the developer and stop bath used are as follows.

0 present solution (alkaline active bath) Caustic soda 40g Anhydrous soda sulfite 75g Sodium thiosulfate 3g Make up to 1 liter with water.

[30℃~30 seconds processing] O stop bath composition Citric acid 15g Sodium citric acid 30g Add water to make 1 liter.

[25°C - 30 seconds] After wiping off a lipophilic liquid (composition below) on the plate surface of the plate material obtained in this way, it was applied to offset printing (Gesnano Toner-200-Gestettner Co., Ltd.) and dampened. Printing was performed by supplying water.

0 oil viewing liquid composition 2-mercapto-5-n-octyloxadiazole
0.1g ethyl alcohol 30ml Make up to 100cc with water.

The printability obtained is as shown in Table 2 below, and the printing schedule in the table was determined by the following method.

Printing durability: When printing with continuous gauze, there will be some unevenness in the image, peeling of the printed image layer,
Evaluate based on wrinkles, etc.

◎: 5,000 or more sheets possible ○: 3,000 to 4,000 sheets ×: 1,000
Print quality: Paper feeding was started as soon as the ink roller came into contact with the printing plate, and the evaluation was based on the number of sheets until a beautiful print with high image quality was obtained.

◎: Less than 10 sheets ○: 10 sheets or more and less than 50 sheets ×: Poor ink adhesion Example-3 Back side (non-aluminum side) of Fulumi base paper with 7 micron thick aluminum foil laminated on 105 g/m2 shell nail
was water-proofed in the same manner as in Example 1, and then the following subbing layer was applied to the bare surface of the aluminum foil by a conventional method.

Three-component copolymer Vinylidene chloride 63% Methyl acrylate 35% Copolymer 1.8 g Acrylic acid 2% Hanaji ethylene 82 ml Phenol 15,1 Coating amount: 20 nl/1 m2 The obtained aluminum base paper was used as a support for the present invention. Created 1000-print printing materials. Note that the same hydrophilic colloid layers as in Example 1 were coated in multiple layers, except that a warping force imitating powder was also added to the antihalation layer as a matting agent.

For comparison, a sample was prepared in the same manner as the conventionally used resin-coated paper, using ordinary photographic base paper made of 130 g/m2 base paper coated with polyethylene.

Table 3 shows the printability of the obtained mold samples. The test conditions were exactly the same as in Example-2.

Also, the elongation of these original plates at the time of printing 5,000 sheets was measured.

The measurement method was to measure the elongation in the vertical and length directions of the 5,000th print from the 1st to the 5,000th print on which sufficient ink density was obtained, and use this as the elongation of the plate.

This Kashu is listed in Table 3. It can be seen from the table that the samples according to the present invention are excellent.

Claims (2)

[Claims] (1) A water-containing colloid layer that supports image silver formed by a silver salt diffusion transfer method and has ink receptivity is provided on the surface of the aluminum foil layer of a support made of base paper laminated with aluminum foil. Lithographic printing plate. (2) The tenth printing plate according to claim 1, wherein the hydrophilic colloid layer contains at least one silane coupling agent.