JPS60144744A - Silver salt lighographic printing plate - Google Patents

Abstract

PURPOSE:To eliminate plate elongation by coating at least one layer of ionomer resin layer which contains a compd. having at least <=2 epoxy groups and ethylene imino groups on the surface of an aluminum foil layer. CONSTITUTION:At least one layer of ionomer resion layer is coated on the surface of an aluminum foil layer. The ionomer resin is obtd. by crosslinking a copolymer of unsatd. hydrocarbon such as ethylene or butadiene and unsatd. carboxylic acid such as acrylic acid, methacrylic acid, maleic acid or the like by using metallic cation. A compd. having >=2 epoxy groups and/or a comps. having >=2 ethylene imino groups is incorporated into the ionomer resin layer. The compds. expressed by the formula I - the formula III are used for the compd. having >=2 epoxy groups and the compds. expressed by the formula IV the formula VI are used for the compd. having >=2 ethylene imino groups. The printing plate having excellent adhesion between a base and hydrophilic colloid layer and excellent printing resistance is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application) The present invention relates to a silver salt lithographic printing plate with improved printing durability and plate elongation.

(Prior art) As a lithographic printing plate using the silver salt diffusion transfer method,
-10910, 46-42453 and 8-3
A method using a physical development layer provided on a silver halide photographic emulsion layer as an ink receptive layer as described in Japanese Patent No. 0562, or US Pat. No. 3,511,656
No. 3,557,690 and JP-A No. 1987-
As described in Japanese Patent No. 44153, a silver halide photographic emulsion layer is provided on a physical development nucleus layer, and after a printing image is formed by a diffusion transfer method, the upper silver halide emulsion layer is removed. There are known methods for obtaining printing plates.

Various supports for these lithographic printing plates are used 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 characteristics, for example, there should be no white spots during printing, and there should be strong adhesion between the printing layer (printed image bearing layer) and the support. An appropriate support is selected depending on the necessity, such as material, manufacturing cost, or ease of handling.

In recent years, the demand for direct lithographic printing plates that can be easily printed has increased significantly, and the supports for these printing plates are easy to process, such as coating and cutting, and have appropriate flammability from the perspective of waste disposal. Paper is often used as the support material because it is both inexpensive and inexpensive.

Further, the moderate rigidity of the paper support makes it compatible with recent automatic plate making machines or automatic printing machines, which is another reason why it is often used.

Many lithographic printing plates to which the silver salt diffusion transfer method according to the present invention is applied also use paper supports.

The lithographic printing plate is used to photograph and expose the lines to be printed, and then
Transfer and develop with an alkaline processing liquid to form a printed image.

The image is then subjected to a development stop bath or surface 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 silver salt diffusion transfer method, they pass through a strong alkaline bath or an acidic bath in the photographic method, and then are constantly immersed in dampening water during printing. be.

Therefore, in order to print a large number of clear printed materials, the plate itself is required to have strong physical properties and mechanical strength during these processing steps.

Particularly during printing, when dampening water permeates into the paper layer, the paper expands and contracts on the plate cylinder of the printing press, causing serious defects such as plate wrinkles and loss of flatness.

Therefore, if it is necessary to use paper as a support for a lithographic printing plate, both sides of the paper should be treated with water resistance, specifically by coating with a resin or by applying a hydrophobic polymeric substance such as a polyolein-based polymeric compound. Until now, so-called resin-coated paper has been widely used.

However, with coated paper such as the one described above, it is impossible to completely prevent the penetration of the above-mentioned processing liquid.
Therefore, it is undeniable that it is inferior in terms of physical and mechanical strength, including printing durability.

In order to improve these drawbacks, the use of a plastic film as a support for a silver salt lithographic printing plate has been proposed, for example, in JP-A-57-100431. However, using a plastic film as a support is not only extremely expensive, but the inventors have found that it is so stiff that it takes time to attach it to a printing machine, and it is surprisingly difficult to use. Unlike paper, it cannot be easily incinerated, so how to dispose of it after use becomes a problem.

On the other hand, a technique using aluminum foil laminated paper as a support for a lithographic printing plate using electrophotography is disclosed in, for example, Japanese Patent Application Laid-Open No. 58-24149, and has also been put to practical use. In this way, printing plates using aluminum foil laminated paper as a support have little plate elongation, are inexpensive, and are said to be easy to use.

Therefore, regarding silver salt lithographic printing plates, which have sharper images, better halftone reproducibility, and better rigidity than h-electrophotographic printing plates, aluminum is used as a support for inexpensive printing plates without plate elongation. The advent of foil-laminated paper was desired.

However, no examples have yet been found where the method has been applied to laminated paper or silver salt lithographic printing plates as described above.

The reason for this is thought to be that the silver salt lithographic printing plate is processed in a strongly alkaline processing solution.

That is, when the above-mentioned printing plate is treated with a strong alkaline processing liquid, the adhesion between the aluminum surface and the hydrophilic binder layer provided thereon is severely damaged, and the binder layer is easily peeled off, resulting in the printing of a silver image. Even if the binder layer does not peel off as described above during processing, the hydrophilic binder layer carrying the silver image can be removed by printing only a few dozen sheets during the subsequent printing process. The aluminum foil layer may peel off, and depending on the processing conditions, the aluminum foil layer may be corroded by the alkaline processing solution.

(Object of the Invention) Therefore, an object of the present invention is to provide a silver-salt lithographic printing plate that is free from plate elongation, is inexpensive, and is easy to use.

(The purpose of the present invention is to develop an ink-receptive image formed on the surface of an aluminum foil layer of aluminum foil laminated paper by a silver salt diffusion transfer method. In the printing plate, at least one ionomer W oil layer is coated on the surface of the aluminum foil layer,
A compound in which the resin layer has two or more epoxy groups and/or
Alternatively, it can be achieved using a silver salt lithographic printing plate containing a compound having two or more ethyleneimino groups.

The present invention will be further explained in detail below.

The silver salt lithographic printing plate of the present invention has a support in which aluminum foil is laminated onto a base paper, and a hydrophilic colloid layer supporting an image silver formed by an ink-receptive silver salt diffusion transfer method is provided on the surface of the aluminum foil layer. It is composed of the following characteristics.

According to the present invention, at least an IN ionomer resin layer is coated on the surface of the aluminum foil layer. In one embodiment, the ionomer resin according to the present invention may be mixed in the hydrophilic colloid layer, or directly provided on the aluminum foil layer in the form of a middle layer between the hydrophilic colloid layer and the aluminum foil layer. It is preferable to coat the anchor as a single layer.

The ionomer resin according to the present invention is produced by crosslinking a copolymer of an unsaturated hydrocarbon such as ethylene or butadiene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or maleic acid using a metal cation. The resin obtained by
It is described in Publication No. 769.

The ionomer resin preferably used in the present invention is a copolymer of ethylene and methacrylic acid with metal cations bonded to it, and is available from DuPont, Mitsui Polychemicals, Mitsui Petrochemicals, etc., respectively. It is commercially available under trade names such as ``Surlyn'', ``Himilan'', or ``Chemipearl''.

It has already been mentioned above that it is preferable to directly apply this ionomer resin as an anchor layer to the aluminum foil layer, but it is also possible to apply it directly to the aluminum foil layer surface.
It is preferable to apply the coating in a state where it is less oxidized, and the coating amount may be 0.1 to 2-011/m and can be increased or decreased as necessary.

Next, according to the present invention, in the above-mentioned ionomer resin layer, two
Compounds having two or more epoxy groups and/or compounds having two or more ethyleneimino groups are included.

Typical specific examples of the above-mentioned compounds having two or more epoxy groups are described below.

(Exemplary compounds) (m=1-6) (m=2-10) (m=1-10) OOH,0 (1-16) OH0-OH, -0-OH, -0H-O
H.

\0' The compound according to the above example is commercially available from Nagase Sangyo ■ under the trade name "Bunacol", or is known in the photographic industry.

Next, typical examples of the compounds having two or more ethyleneimino groups according to the present invention will be described below.

(Exemplary Compounds N016 1 (2-7) N0ONH(OH*), NHO(IIJ
](2-8)0H317aONa(aH,), Naoo
N4””No 0NHC NHooNd (2-9) (2-10) [;Nooanc2〉ToC2≧←HN
OON (2-12) OHs'''1) Jooo(oH
t) @oaon(0H1(2-13) l:;Naom
aso, Naconl (2-15) 〉Nso, <aH
Mountain so, N<(2-17ノ [;NaH,aH,so,
al(,an,r:1(2-ls) U;noH!a
H, oooHlam, n<Jmu(@-QL) (Leb, p.

1 (2-22) 1-p-xgu 00,H.

(2-24) (pN-), p-ay-so, -IJ:
p(-J).

△ Input The compounds exemplified above are, for example, disclosed in Japanese Patent Publication No. 11i353-
It can be produced by the synthesis method described in No. 37'I0. The compound having two or more epoxy groups and/or the compound having two or more ethyleneimino groups according to the present invention can be dissolved in water or an organic solvent miscible with water, such as methanol, ethanol, fluorinated alcohol, etc. After that, it is preferably added to the coating solution of the ionomer resin, and the amount added is 0.02 g per 11 solids of the ionomer resin, preferably, < is 0.05, p -0,
The size is 3.9, but the amount can be increased if necessary.

In addition, these compounds according to the present invention may be used alone,
Two or more types may be mixed and used.

In addition to the above-mentioned compound according to the present invention, the coating solution of the ionomer resin according to the present invention contains f! l! Film agents, colloidal silica, pH1i adjusters, etc. can be added.

The aluminum foil laminated paper used as a support for the printing plate according to the present invention is disclosed in, for example, Japanese Patent Application Laid-Open No. 58-16892.
It can be manufactured by laminating a base paper with an aluminum foil having a thickness of 0.1 micron or more by the method described in Japanese Patent No. 58-17449 and No. 58-122896.

According to the present invention, the silver salt lithographic printing plate of the present invention includes a compound having two or more epoxy groups and/or a compound having two or more ethyleneimino groups on the aluminum foil laminated paper support. It can be produced by applying a single layer of the ionomer resin containing the ionomer resin anchor, and further applying a wood-philic colloid layer of a lithographic printing plate using a silver salt diffusion transfer method in accordance with a conventional method.

In the present invention, the compound having two or more epoxy groups or the compound having two or more ethyleneimino groups is added to the hydrophilic colloid layer, and the lower layer of the colloid layer is added at the time of coating or thereafter. An addition method in which the ionomer present in the ionomer is diffused into a layer may also be used.

The back surface of the aluminum foil laminated paper according to the present invention, 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 these are preferably applied as a layer of 0.1 micron to 10 micron.

Examples include polyethylene terephthalate, polyimide, polycarbonate, polyacrylate, polymethyl methacrylate, polyvinyl fluoride, polyvinyl chloride, polyvinyl acetate, keristyrene, styrene-butadiene copolymer, polymethacrylate, silicone resin, chloride comb, epoxy resin. , pure and modified alkyd resins, polyethyl methacrylate, poly-n-butyl methacrylate, cellulose acetate, ketone resins, polyethylene, polypropylene, polyacrylonitrile,
Rosin derivatives, polyvinylidene chloride, nitrocellulose, phenol-formaldehyde resin, metacresol formaldehyde resin, styrene-maleic anhydride copolymer, polyacrylic acid-polyacrylic acid esterimide copolymer, fumaric acid modified tyrene glycol copolymer , methyl vinyl ether-maleic anhydride copolymer, acryloylglycine-vinyl acetate copolymer, polyvinyl bisilidone, polyvinyl alcohol, polyimide, halogenated styrene, etc. are used.

Further, the water-resistant layer can be given matte properties by adding inorganic or organic fine powder.

Printed image using the silver salt diffusion transfer method according to the present invention The hydrophilic colloid layer supporting silver refers to a photosensitive silver halide emulsion layer, a physical development nucleus layer, an antihalation layer, an intermediate layer, and the like. The most preferred form of the layer structure is one with an intermediate layer consisting of a hydrophilic colloid layer between the ionomer resin layer and the physical development nucleus layer that provides ink receptivity necessary for printing, or one with an intermediate layer consisting of a hydrophilic colloid layer. In this form, an antihalation layer is coated between a physical development nucleus layer that provides ink receptivity necessary for printing, and a silver halide emulsion layer is coated on top of the antihalation layer.

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

The hydrophilic colloid of the constituent layer according to the present invention (the binder darts are preferably various types of gelatin treated with acid or lime, etc.)
For example, it can be replaced with polyvinyl ether, polyacrylamide, poly-N-vinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, alginic acid, maleic anhydride-ethylene copolymer, and the like.

The type of photosensitive silver halide emulsion used in the present invention is selected from commonly used silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodobromide, silver iodobromide, etc. . The type of emulsion may be either negative type or positive type, and there is also a special type described in JP-A-54-48544, which uses a photosensitive silver halide/chemical scissors and a non-photosensitive silver halide made difficult to dissolve. It may be. These silver halide emulsions can also be chemically or spectrally sensitized as required.

Further, the photosensitive emulsion may be stabilized with azaindenes. For the hydrophilic colloid layer, hardening agents commonly used in the art may be used alone or in combination, including aldehyde hardening agents, such as formalin, glyoxal, or N-methywal compounds such as ethylene urea. etc. are particularly preferred.

Further, by adding a silane coupling agent, more favorable results for adhesive properties can be obtained. Examples of the above-mentioned silane coupling agents are listed below.

(Exemplary compound) (3-3) OH,=OH-Si4-0000H,)s
Oh.

(35) k14HOH*OumaHHCOHx)sSIC
OOHs)sThe compounds exemplified above are commercially available from, for example, Toray Silicon ■.

The lithographic printing plate in the present invention is an image il! ! After being exposed to light, it is developed with a silver halide developing agent.

As the developing agent, polyhydroxybenzenes and 3-pyrazolidinones are preferred, and these herbal medicines may be used in the form of what is called a herbal medicine-containing type contained in the constituent layers of the plate material.

The physical development nuclei of the physical development nucleus layer in the present invention may be those used in the known silver lump diffusion transfer method, such as gold,
Colloids such as silver, metal sulfides prepared by mixing sulfides with water-soluble salts such as palladium and zinc, and the like can be used. For details and manufacturing methods of these, see, for example, W, IP, Be
rg@, Photography.

811ver Halide Diffusion P
rocesses 1972. VocalPress.

After the image is formed, the lithographic printing plate according to the present invention is processed in an alkaline processing bath in the presence of a silver halide 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.

In these alkaline treatment baths, caustic soda, potassium chloride, sodium carbonate, potassium carbonate, etc. can be used as alkaline agents, and the pH of the treatment bath is preferably between 8 and 14.

Silver halide solvents used in alkaline processing include sulfite salts such as sodium sulfite, sodium thiosulfate,
Examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, amino acids such as cystine and cysteine, thioureas, thioethers, and the like.

As described above, the present invention is a lithographic printing plate using a silver salt diffusion transfer method using aluminum foil laminated paper.The advantages of the present invention can be summarized as follows.

[1 piece: Because the elongation of the plate during printing is reduced, high-quality printed matter can be obtained.

[2) Since various processing liquids during plate making or dampening water during printing do not penetrate into the paper layer, printing durability is improved as a support for chain planographic printing.

[3] Since the contact between the support and the hydrophilic cotetraid layer is excellent, the physical and mechanical strength of the mold film is improved.

[4] This is done with conventional resin-coated paper; there is no need for discharge treatment.

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

Example 1 A single layer of anchor with a solid content of 1.09/g was coated on the surface of an aluminum laminated paper obtained by laminating a 10 micron thick aluminum foil onto a base paper having a weight of 13 op/rrl. did. The resin composition of this anchor layer and the added compounds are as shown in Table 1.

Next, a solution having the following composition was applied to the opposite side of the aluminum laminated paper (coating amount: 5 g/pinot) to make it waterproof.

On the single anchor layer of the obtained aluminum laminated paper, a halation Al17 soil layer containing carbon black and then a photosensitive silver halide emulsion layer were simultaneously coated in a multilayer manner.

However, as an antihalation layer, carbon black (manufactured by Toyo Ink, FX-
4236) is dispersed in gelatin, and in addition, fine silica powder (Fuji Davison Co., Ltd., Syloid 3Q) is used as a matting agent.
8) Contains hydroquinone and dimedone as developing agents and formalin as a hardening agent, and sodium octylsulfosuccinate is added as a coating aid, and the pH is adjusted to 4.
．． A coating solution adjusted to 7 was applied so that the amount of gelatin was 4.097 m.

The photosensitive silver halide emulsion is prepared by chemically sensitizing a silver chloride emulsion prepared by the usual double jet method, chemically sensitizing it with sulfur, ortho-sensitizing it with a photosensitive dye, and adding 4-4 as a stabilizer.
Human tetraxy-6-methyl-1,3,3L,? - Added an appropriate amount of tetrazaindene, further added fine silica powder and sodium isoamyl-n-decylsulfosuccinate as a coating aid, and adjusted the pH to 4.7, which is 1.09 in terms of silver. /, m'' coating amount.

Next, a palladium sulfide solution prepared from palladium chloride and sodium sulfide as physical development nuclei was coated on the emulsion layer by an air knife method after adding the same coating aid as above, to form a lithographic printing plate. A sample was obtained. The sample obtained above was left for 5 days under the conditions of 40°C and 50% RH.
After immersing each sample in 5% potassium hydroxide ice water solution for 30 seconds, the adhesion between each coated constituent layer and the support was examined.The measurement was performed after immersing the sample in fresh water or a strong alkaline aqueous solution, and then applying a knife to each sample. The coating was scratched with a cotton cloth and rubbed with a cotton cloth under a constant load, and evaluated based on the amount of load required to peel off the coated layer from the support. The details of the resin composition in the above table are as follows.

(A) Sample & 2 Movinyl 987 resin acrylic ester copolymer emulsion manufactured by Hoechst, published in JP-A No. 5
It was produced according to the technique disclosed in the Example of Publication B-36494.

(B) Resin mixture of sample A4 The following composition was applied according to the formulation disclosed in the Examples of JP-A-5'7-176Q63.

(0) Chemivar-based resins of samples A5 to 14 are the product names of Mitsui Petrochemical Industries ■, and various symbols are attached depending on the type of metal cation, particle size, viscosity, etc., and 25% to 40%
Used as an aqueous dispersion.

The symbols representing adhesiveness in the table are as follows.

As shown in the results in Table 1 above, the silver salt planographic printing plate sample of the present invention containing the ionomer resin layer on the aluminum foil layer or the exemplified compound according to the present invention was treated not only with fresh water but also with a strong alkaline aqueous solution. It can be seen that the adhesion between the support and the hydrophilic colloid layer is excellent even after drying.

Example 2゜In addition to the sample A4rA7+genus10゜A12 prepared in Example 1, a sample in which 25 to 25 of exemplified compounds (3-1,) per 1 g of gelatin were newly added to the antihalation layer of 412. Arashi 15 was prepared, and each of the above samples was subjected to image exposure, development, and
Stabilization treatment was performed. The composition of the treatment liquid used is as follows.

(Alkali activation bath) (Stabilizing bath) After wiping off the oleophilic liquid (composition below) on the plate surface of the plate material obtained in this way, it was applied to an offset printing machine (Gestera Toner 200, manufactured by Gestella Toner). , printing was performed by supplying dampening water.

(Leopophilization liquid composition) The printability obtained is as shown in Table 2 below, and the printing evaluation in the table was determined by the following method.

Printing durability: Evaluate from peeling, wrinkles, etc. of the printed image layer when printing continuously.

◎: Can print more than s, ooo sheets ○ Knee Can print 5,000 to 6,000 sheets X:
It is impossible to print more than 1,000 sheets.As is clear from the above table, tin salt planographic printing plate sample A7 according to the present invention. A
10, A12. All A15s have excellent rigidity,
In particular, sample shop 15, in which a silane coupling agent was added to the antihalation layer, was found to be even more excellent in printing durability.

(Effects of the Invention) A silver salt lithographic printing plate in which aluminum foil laminated paper is used as a support, an ionomer resin layer is provided on the upper layer, and the compound according to the present invention is added to the resin layer is hydrophilic to the support. It has become clear that the adhesive has excellent adhesion to the sexual colloid layer and also has excellent printing durability.

Representative Patent Attorney: Yoshichika Noda

Claims (1)

[Claims] An ink-receptive image formed on the surface of the aluminum foil layer of aluminum foil laminated paper by a silver salt diffusion transfer method.In a silver salt lithographic printing plate having a hydrophilic colloid layer supporting silver, at least one layer is formed on the surface of the aluminum foil layer. Silver salt Heisei printing characterized in that an ionomer resin layer of the layer is coated, and the resin layer contains a compound having two or more epoxy groups and/or a compound having two or more ethyleneimino groups. Edition.