JP2812935B2 - Materials for the preparation of lithographic printing plates containing a glass support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a material for making a lithographic printing plate comprising a thin glass support.

[0002]

BACKGROUND OF THE INVENTION Lithographic printing is specially made where some areas of its surface can accept lithographic printing ink (oleophilic areas), while other areas do not accept ink (oleophobic areas). This is a method of printing from the surface. The oleophilic area forms the printing area, while the oleophobic area forms the background area.

[0003] Two basic types of lithographic printing plates are known. According to a first type, the so-called wet printing plate, both water or an aqueous dampening solution and ink are applied to the printing plate surface containing hydrophilic and hydrophobic areas. The hydrophilic areas are moistened with water or dampening liquid, thereby rendering them oleophobic, whereas the hydrophobic areas receive ink. A second type of lithographic printing plate works without the use of dampening liquids and is driographic.
phy) called a printing plate. This type of printing plate contains areas of high ink repellency and lipophilic areas. Generally, the high ink repellent area is formed by a silicon layer.

Conventional supports for use in lithographic printing plates are, for example, metal supports, especially polished and anodized aluminum, or paper or plastic provided with a hydrophilic layer, preferably a cross-linked hydrophilic layer. A support containing a substrate such as a film.

In lithographic printing plates, it is important to use a support that has high dimensional stability and high resistance to chemical influences. Glass is a support with very high dimensional stability and is highly insensitive to chemical action. It would therefore be the support of choice for lithographic printing plates if it were thin and flexible enough.
European Patent Application 942 filed on December 5, 1994
03517, having a thickness of less than 1.2 mm, preferably less than 0.8 mm, having a breaking stress (under tensile stress) of 1 × ^{10 7} Pa or more and an elastic modulus (Young's modulus) of ¹⁰ × ^{10 10} Pa or less It discloses that thin glass can be advantageously used as a support for silver halide photographic materials and dry imaging materials. In that document it is disclosed that lithographic printing plates can have such a support very universally. Various types of lithographic printing plate precursors, i.e., having a glass support that is useful for all types of lithographic printing plate precursors, are known in the art, as are materials that enable the preparation of lithographic printing plates. Is desirable.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithographic printing plate precursor having a support having high dimensional stability and excellent resistance to chemicals.

Another object of the present invention is to obtain high quality, preferably without the need for solvent development, or with a more ecologically acceptable solvent, to achieve high dimensional stability and It is an object of the present invention to provide a heat mode recording material as an alternative for making a driographic printing plate comprising a support having excellent resistance to chemicals.

It is yet another object of the present invention to provide a lithographic printing plate having excellent printability, the DT on a support having high dimensional stability and excellent resistance to chemicals.
R (diffusion transfer) material.

Further objects of the present invention will become clear from the description hereinafter.

It is an object of the present invention to include a surface which can be differentiated into an ink receiving area and an ink repelling area according to an image pattern on a glass support, said glass support having a thickness of 0.5 mm or less, at least 10 mm or less. ^This is achieved by providing a material for making a lithographic printing plate characterized by having a breaking stress of ⁷ Pa, a Young's modulus of less than 10 ¹¹ Pa and a rounded edge.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The use of glass as a support for materials intended for making lithographic printing plates is based on the fact that most methods of applying additional layers to a glass support are discontinuous processes. Has been hindered by Difficulties in applying layers to glass supports in a discontinuous process have been cited in various literatures, US-P 4,033,290,
US-P 5,254,447 is the clearest.

It has been found that if it is necessary to apply a layer on a glass support thinner than 1.2 mm, the glass support can be supplied on a roll. This offers the great advantage that such supports can be coated in any continuous coating equipment for coating layers on plastic films. It has been found that when the glass is less than 1.2 mm thick, it can be provided in roll form and thus can be wound and coated as a web in a continuous coating machine. The glass support is ¹⁰ × ^{10 10} Pa
The following is particularly so when it has an elastic modulus (Young's elastic modulus) of preferably less than 7 × ^{10 10} Pa. Said glass further 1x10 ⁷ Pa or more, preferably when with higher failure stress (under tensile stress) 4x10 ⁷ Pa, it give a roll form is more readily. If the glass fulfills these conditions, depending on its thickness, the glass can be provided on a roll wound on a core, the core having a diameter of 0.1 m to 3 m.

When the glass support is thinner than 1.2 mm,
x10 less than ¹⁰ Pa, preferably having a modulus of less than 7x10 ¹⁰ Pa (Young's modulus), if having a higher fracture stress (under tensile stress) 4x10 ⁷ Pa, it is depending on the thickness of 0. It has also been found that it can be provided on a roll wound on a core having a diameter of 1 m to 1.6 m. The glass support has an elastic modulus (Young's elastic modulus) of less than ¹⁰ × ^{10 10} Pa, preferably less than 7 × ^{10 10} Pa
And a fracture stress higher than 4 × 10 ⁷ Pa (under tensile stress)
And if less than 0.8 mm thick, it is 0.1
It can be provided on a roll wound on a core having a diameter of m to 1.2 m.

[0014] The glass support of the present invention must have a rounded edge. All glass-coating methods give relatively unlimited edges. This end is in fact always cut off and removed, resulting in a right angled end. It was found that the edge could be a starting point for microcracks and fractures. Furthermore, it was found that the rounded ends did not have the disadvantage. The radius of the rounded end is preferably less than half the thickness of the glass support.

For use as a lithographic printing plate precursor, ie a support in a material for making a lithographic printing plate,
The glass support must be less than 0.5 mm thick.

It is possible to produce a flexible material for preparing a lithographic printing plate which has a surface on a glass support which can be differentiated into an ink receiving area and an ink repelling area according to an image pattern. Was found. The glass support for such materials is 0.5 mm
It is preferably less than the thickness and has a breaking stress of at least 10 ⁷ Pa and a Young's modulus of 10 ¹¹ Pa or less.

In one embodiment of the present invention, the material further comprises a hydrophilic layer formed from a cross-linked hydrophilic polymer. Particularly suitable crosslinked hydrophilic layers can be obtained from hydrophilic binders which have been crosslinked with a crosslinking agent such as formaldehyde, glyoxal, polyisocyanate or hydrolyzed tetra-alkyl orthosilicate. Hydrolyzed tetra-orthosilicate is particularly preferred. Hydrophilic (co) polymers such as vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide, homopolymers or copolymers of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, or maleic anhydride / vinyl as hydrophilic binder Methyl ether copolymers can be used. The hydrophilicity of the (co) polymer or (co) polymer mixture used should be equal to or higher than the hydrophilicity of the polyvinyl acetate hydrolyzed to at least 60% by weight, preferably to the extent of 80% by weight. preferable.

The amount of crosslinking agent, especially tetraalkyl orthosilicate, is at least 0.2 parts by weight, preferably 0.5-5 parts by weight, more preferably 1.0 parts by weight per part by weight of hydrophilic binder. Preferably it is 3 parts by weight.

The crosslinked hydrophilic layer of the present invention preferably also contains a substance which improves the mechanical strength and porosity of the layer. Colloidal silica can be used for this purpose.
The colloidal silica used can be in the form of any commercially available water-dispersion of colloidal silica, for example having an average particle size of up to 40 nm, for example 20 nm. In addition, inert particles of larger dimensions than colloidal silica, for example J.I. Colloid and Inter
face Sci. , Vol. 26, 1968, pag
Particles having an average diameter of at least 100 nm, which are silica or alumina particles, or particles of titanium dioxide or other heavy metal oxides prepared according to Stoeber described in es 62-69, can be added. The insertion of these particles gives the surface of the crosslinked hydrophilic layer a uniform rough texture consisting of microscopic hills and valleys, which serves as a reservoir for water in the background area. The thickness of the crosslinked hydrophilic layer can vary from 0.2 to 25 μm, preferably from 1 to 10 μm.

A more specific example of a cross-linked hydrophilic layer suitable for use according to the present invention is EP-A 60124.
0, GB-P-1419512, FR-P-23003
54, US-P-397660, US-P-4284
705 and EP-A 514 490.

A very suitable material for the preparation of a lithographic printing plate comprises a surface on a glass support which can be differentiated into an ink receiving area and an ink repelling area according to the image pattern, i. A material having a thickness of 5 mm or less, a breaking stress of at least 10 ⁷ Pa and a Young's modulus of 10 ¹¹ Pa or less; ii) the material further comprising a photosensitive layer.

Further preferred materials for the preparation of a lithographic printing plate comprise on a glass support a surface which can be differentiated into an ink receiving area and an ink repelling area according to the image pattern, i) the glass support being no more than 0.5 mm Ii) a breaking stress of at least 10 ⁷ Pa and a Young's modulus of 10 ¹¹ Pa or less; ii) the material further comprises a hydrophilic layer formed from a cross-linked hydrophilic polymer; iii) an ink receiving area; A material characterized in that the surface capable of being differentiated into an ink repellent region contains a photosensitive layer.

The light-sensitive layer of the present invention can comprise any suitable light-sensitive composition from which an ink-receiving image on the hydrophilic surface of the support of the imaging element can be obtained. Examples of such photosensitive compositions used herein include those containing diazo compounds; UK Patent No. 1,
Including azide compounds as disclosed in US Pat.
72,528 and 4,072,527 containing photo-crosslinkable photopolymers, and in particular those described in more detail below.

Among these photosensitive compositions, those which are preferably used include those containing diazo compounds, which are those which preserve the photosensitive layer; developability, eg development latitude; imageability, eg This is because they are synthetically superior in various properties such as image quality; printability, for example, ink receptivity and water resistance; and low possibility of causing environmental pollution of the developer used.

Photosensitive compositions containing diazo compounds can be broadly divided into two groups: negative-working type and positive-working type.

The negative working photosensitive composition containing the diazo compound comprises a photosensitive diazo compound and preferably a polymer compound. As the photosensitive diazo compound, any of conventionally known compounds can be used, and a preferable example thereof is an organic solvent-a salt of a soluble diazo resin, for example, p-type.
Condensates of diazodiphenylamine with formaldehyde or acetaldehyde and salts of hexafluorophosphate, and salts thereof with 2-hydroxy-4-methoxybenzophenone-5-sulfonate.

On the other hand, examples of the above-mentioned polymer compounds which are preferably used include acrylic acid or methacrylic acid copolymers; crotonic acid copolymers; itaconic acid copolymers, maleic acid copolymers, cellulose derivatives having a carboxyl group in the side chain thereof, and the like. A polyvinyl alcohol derivative having a carboxyl group in the side chain; a hydroxyalkyl (meth) acrylate copolymer having a carboxyl group in the side chain; and an unsaturated polyester resin having a carboxyl group.

As the diazo compound used in the positive-working photosensitive composition, any conventionally known compound can be used, typical examples of which are o-quinonediazide and preferably o-naphthoquinonediazide. Particularly preferred are o-naphthoquinonediazidosulfonic acid esters of various hydroxyl compounds or
-Naphthoquinonediazidocarboxylic acid esters; and o-naphthoquinonediazidosulfonic acid amides or o-naphthoquinonediazidocarboxylic acid amides of various aromatic amine compounds. Examples of such phenols include phenol, cresol, resorcinol and pyrogallol; examples of such carbonyl-containing compounds are formaldehyde, benzaldehyde and acetone. Examples of preferred hydroxyl compounds are phenol-formaldehyde resin, cresol-formaldehyde resin,
Includes pyrogallol-acetone resin and resorcin-benzaldehyde resin.

A typical example of an o-quinonediazide compound is
Esters of benzoquinone- (1,2) -diazidesulfonic acid or naphthoquinone- (1,2) -diazidocarboxylic acid with phenol-formaldehyde or cresol-formaldehyde resins; U.S. Pat. No. 3,635,70
No. 9, esters of naphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid and pyrogallol-acetone resin; and Japanese Patent Publication No. 55-76.
No. 346, naphthoquinone- (1,2)-
Includes esters of diazide- (2) -5-sulfonic acid and resorcinol-pyrogallol-acetone copolycondensate.

Examples of other useful o-quinonediazide compounds include polyesters esterified with o-naphthoquinonediazidosulfonyl chloride having a terminal hydroxyl group disclosed in Japanese Patent Publication No. 50-117503; Homopolymer of p-hydroxystyrene esterified with o-naphthoquinonediazidosulfonyl chloride or its copolymer with other copolymerizable monomers disclosed in JP-A-50-113305; Of bisphenol-formaldehyde resin and o-naphthoquinonediazidosulfonic acid; alkyl acrylate-acryloyloxyalkyl carbonate-hydroxyalkyl acrylate disclosed in U.S. Pat. No. 3,859,099. Condensates of acrylate copolymers with o-naphthoquinonediazidosulfonyl chloride; reaction products of copolymerization products of styrene and phenol derivatives with o-quinonediazidesulfonic acid disclosed in Japanese Patent Publication No. 49-17481; U.S. Pat. No. 3,759,
No. 711, an amide of o-naphthoquinonediazidosulfonic acid or o-naphthoquinonediazidocarboxylic acid and a copolymer of p-aminostyrene and a monomer copolymerizable therewith; and esters of polyhydroxybenzophenone and o-naphthoquinonediazidosulfonyl chloride Compound.

These o-quinonediazide compounds can be used alone for forming the photosensitive layer, but are preferably used as a mixture with an alkali-soluble resin.

Preferred alkali-soluble resins include novolak-type phenols, typical examples of which are phenol-formaldehyde, cresol-formaldehyde resins, and phenol-cresol-formaldehyde copolycondensation disclosed in Japanese Patent Publication No. 55-57841. Resin. The above-mentioned phenol resin is a phenol or cresol condensed with formaldehyde, which is substituted with an alkyl group having 3 to 8 carbon atoms, for example, Japanese Patent Publication Sho-50.
More preferably, it is used simultaneously with the t-butylphenol-formaldehyde disclosed in -125806.

Furthermore, an alkali-soluble polymer other than the above-mentioned alkali-soluble novolak phenolic resin can be optionally inserted into the photosensitive composition. Examples of such polymers are styrene-acrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer,
Alkali-soluble polyurethane resin, and alkali-soluble polyurethane resin disclosed in Japanese Patent Publication No. 52-28401.
Soluble vinyl resin and alkali-soluble polybutyral resin.

The amount of the o-quinonediazide compound is preferably from 5 to 80% by weight, more preferably from 10 to 50% by weight, based on the total weight of the solid contents of the photosensitive composition. On the other hand, the amount of the alkali-soluble resin is preferably from 30 to 90% by weight, more preferably from 50 to 85% by weight, based on the total weight of the solid content of the photosensitive composition.

The photosensitive layer related to the present invention can be applied in the form of a multilayer structure. In addition, the photosensitive composition in the photosensitive layer or multilayer package may include optional components such as dyes, plasticizers, and components for providing printout properties (the ability to provide a visible image immediately after image-wise exposure). It can further include.

The coating amount of the photosensitive layer applied on the hydrophilic surface of the support is preferably 0.1 to 7 g / m ² ,
More preferably, it is in the range of 0.5 to 4 g / m ² .

The preferred photo-crosslinkable material in the present invention is based on a photo-crosslinkable polymer having a maleimide group in its side chain. To increase the photosensitivity, thioxanthones, benzophenone, Michler's ketone, anthraquinones, anthracene, chrysene, p-dinitrobenzene, 2-nitrofluorene, and JP-A-
62-294238, JP-A-2-173646, J
P-A-2-236552, JP-A-3-54566
And sensitizers such as those disclosed in JP-A-6-107718. (The term "JP-A" used in this specification is an "unexamined published Japanese patent application."
Means The photo-crosslinkable polymer having a maleimide group in its side chain is described, for example, in US Pat. No. 4,079,041 (JP-A
-52-988); West German Patent No. 2,62.
6,769; European Patent Nos. 21,019 and 3,552; Die Angewandte Mak
romolekulare Chemi, 115 (19
83), p. 163-181; JP-A-49-12
8991-JP-A-49-128993, JP-A-
50-5376 to JP-A-50-5380, JP-A
-53-5298 to JP-A-53-5300, JP-
A-50-50107, JP-A-51-47940,
JP-A-52-1907, JP-A-50-450
76, JP-A-52-121700, JP-A-50
-10844, JP-A-50-45087, JP-A
-58-43951; West German Patent 2,349,94.
No. 8 and No. 2,616,276.

Among these polymers, those having on average two or more maleimide groups in one molecule in their side chains and those having an average molecular weight of 1,000 or more are used in the present invention. Is preferred.

The image-forming element containing any of these polymers is preferably developed from the viewpoint of environmental safety by using an aqueous alkaline developer containing substantially no organic solvent. Accordingly, these polymers are preferably soluble or swellable in aqueous alkaline solutions. Therefore, it is preferable to obtain these polymers by copolymerizing a monomer having a maleimide group in its side chain with a monomer having an alkali-soluble group.

Preferred as alkali-soluble groups are:
An acid group having a pKa of 14 or less. Particular examples of such monomers having an alkali-soluble group are vinyl monomers having a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid;
A vinyl monomer having a CONHSO ₂ — group; —SO ₂ N
Vinyl monomers having an H-group; vinyl monomers having a phenolic hydroxyl group; vinyl monomers having a phosphoric acid group or a phosphonic acid group; and maleic anhydride and itaconic anhydride.

The alkali-soluble group-containing monomer and maleimide group-containing monomer are generally used in an amount of 10/90 to
70/30, preferably 20/80 to 60 /
Copolymerized at a ratio of 40, which readily provides a photo-crosslinkable polymer for use in the present invention. The polymer is 30-5
It preferably has an acid value of 00, particularly preferably 50 to 300.

Particularly useful among such photo-crosslinkable polymers are copolymers of N- [2-methacryloyloxy) alkyl] -2,3-dimethylmaleimide and methacrylic or acrylic acid, such as Die An
gewandte Makromolekulare
Chemie, 128 (1984) pp. 71-91
Are disclosed. When producing these copolymers, a vinyl monomer is further copolymerized as a third component, and a desired multi-component copolymer can be easily obtained. For example, the homopolymer can be copolymerized with an alkyl methacrylate or an alkyl acrylate having a glass transition temperature of room temperature or lower as a third component to obtain a flexible copolymer.

The photo-crosslinkable polymer for use in the present invention is preferably 1000 or more, more preferably 1 or more.
000-500,000, more preferably 20,
It has a weight average molecular weight of 000 to 300,000.

As described above, it is desirable to add a sensitizer to the photosensitive layer having the photocrosslinkable polymer. 300 nm
Or a triplet sensitizer having an absorption peak that ensures sufficient absorption at or above.

Examples of such sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives,
Includes ketocoumarin compounds, benzothiazole derivatives, naphthofuranone compounds, pyrylium salts and thiapyrylium salts.

Specific examples thereof are Micheller's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-methyl-1,3-diazo-1,9-
Benz) anthropiclamide, 5-nitroacenaphthene, 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorenone, 2-dibenzoylmethylene-3-methylnaphthothiazoline , 3,3-carbonyl-bis- (7-diethylaminocoumarin), 2,4,6-triphenylthiapyrylium perchlorate, 2- (p-chlorobenzoyl) naphthothiazole, and JP-B-45-88
32, JP-A-52-129791, JP-A-62
-294238, JP-A-2-173646, JP-
A-2-131236, EP 368,32
No. 7, JP-A-2-236552, JP-A-3-5
Sensitizers described in JP 4566 and JP-A-6-107718.

Among them, JP-A-2-23655
2, JP-A-3-54566 and JP-A-6-10
Sensitizers described in 7718; JP-A-6-1
One or more -COOH according to 07718,-
NHSO ₂ R ²⁰ , —CONHCOR ²⁰ and / or —CO
A sensitizer having NHSO ₂ R ²⁰ (where R ²⁰ represents an alkyl group, an aromatic group or an alkyl-aromatic group) is particularly preferred.

The amount of the sensitizer in the photosensitive layer is simply 1 to 20% by weight, preferably 2 to 20% by weight of the total amount of the composition in the photosensitive layer.
It is 15% by weight, more preferably 3 to 10% by weight.

In addition to the above photocrosslinkable polymer, it is desirable to add a diazo resin to the photosensitive layer. Examples of diazo resins include co-condensates containing aromatic diazonium compounds and aldehydes. Specific examples are JP-B-49-48001,
JP-B-50-7481, JP-B-5-2227,
JP-A-3-2864, JP-A-3-240061
And the diazo resin described in JP-A-4-274429.

Among them, diazo resins having a carboxyl group in the molecule, for example, diazo resins obtained by cocondensation with an aromatic compound having at least one carboxyl group such as those described in JP-A-3-240061 And diazo resins obtained by condensation with an aldehyde having a carboxyl group such as those described in JP-A-2864.

The amount of the diazo resin in the photosensitive layer is preferably 0.1 to 30% by weight based on the total amount of the composition in the photosensitive layer.
Preferably 0.5 to 10% by weight, more preferably 1 to 5%
% By weight.

Further, polymers having one or more polymerizable groups, such as JP-B-3-63740,
U.S. Pat. Nos. 3,376,138, 3,556,79
No. 3 can be added.

The above-mentioned polymers having one or more polymerizable groups are preferably soluble or swellable in aqueous alkaline developers, as are polymers having a maleimide group in the side chain. Accordingly, the polymer is preferably a copolymer comprising one or more monomers having, for example, an alkali-soluble group as described above.

In another embodiment of the invention, the material for making a lithographic printing plate is a DTR (diffusion transfer material) in both a two-sheet and a mono-sheet process. 2
In the case of a sheet DTR process, the sheet material comprising the silver halide material is image-wise exposed and then brought into contact with a second sheet material of the invention comprising an image receiving layer having physical development nuclei. The two-sheet sandwich is then processed,
During this process, silver ions migrate to the image receiving layer and precipitate on physical development nuclei. In the case of a mono-sheet DTR process, both the silver halide layer and the image receiving layer are in the same sheet material.

In the production of a two-sheet DTR material, an image receiving layer containing physical development nuclei is provided on the glass support of the present invention. The glass support is first provided with a layer containing a crosslinked hydrophilic polymer, and a layer containing physical development nuclei is provided on this hydrophilic polymer layer to form an image receiving layer. This image receiving layer is then used in a two-sheet DTR process. During the preparation of a lithographic printing plate, a substance is transferred image-wise to the surface of the material, which differentiates the surface into ink-receiving and ink-repellent areas according to the transferred image pattern.

The image-receiving layer containing physical development nuclei preferably does not contain a hydrophilic binder, but may have a maximum of 3
A small amount of 0% by weight of a hydrophilic colloid, for example, polyvinyl alcohol, can be included to improve the surface hydrophilicity.

Preferred development nuclei for use in accordance with the present invention are sulphides of heavy metals, such as sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver and zinc. Particularly suitable development nuclei in connection with the present invention are palladium sulfide nuclei. Other suitable development nuclei are salts such as selenides, polyselenides, polysulfides, mercaptans, and tin (II) halides.
Heavy metals, preferably silver, gold, platinum, palladium and mercury, can be used in colloidal form.

The glass support of the present invention is a monosheet DTR
It is well suited for the production of materials. Mono-sheet DTR materials for the preparation of lithographic printing plates can be realized in two forms. In a first realization, the DTR mono-sheet material for the preparation of a lithographic printing plate comprises a glass support according to the invention, and i) a hydrophilic polymer layer, which may optionally be crosslinked, ii) physical development nuclei. And iii) a silver halide photographic emulsion layer in the order shown. In the second realization, the DTR mono-sheet material for the preparation of a lithographic printing plate represents a glass support according to the invention and an image receiving layer comprising i) a photographic silver halide emulsion layer and ii) physical development nuclei. Including in the order that is being done.

The hydrophilic polymer layer useful in the first embodiment of the DTR mono-sheet material for making a lithographic printing plate can be a hydrophilic polymer layer as described above. The image receiving layer containing physical development nuclei useful in the mono-sheet DTR material of the present invention can be the same as the image receiving layers described herein above.

The support of this sheet material is the glass support of the present invention. In the case of a mono-sheet DTR material, the image receiving layer is provided with a photosensitive layer in water permeable contact with the image receiving layer. Layers in water-permeable contact with each other are layers that are continuous with each other or separated from each other only by a water-permeable layer. The nature of the water-permeable layer is such that it does not substantially inhibit or limit the diffusion of water or compounds contained in the aqueous solution, such as a developer or complexed silver.

The photosensitive material used with the material for making the lithographic printing plate of the present invention in both the mono-sheet DTR process and the 2-sheet DTR process comprises a hydrophilic colloid binder and at least one silver halide. It can be any layer containing an emulsion, and at least one of the silver halide emulsions is photosensitive.

The photographic silver halide emulsion used in accordance with the present invention is, for example, "Ch" by Glafkids
emie et Physique Photogra
phique ", Paul Montel, Paris
(1967). F. "Photographic Emulsion Ch" by Duffin
emiry ", The Focal Press,
London (1966); L. Ze
“Makingand” by likman et al
Coating Photographic Emu
lsion ", The Focal Press, Lo
As described in Ndon (1966), it can be prepared from soluble silver salts and soluble halides according to various methods.

For use in accordance with the present invention, the silver halide emulsion preferably comprises predominantly silver chloride, but from 1 mole% to
A proportion of silver bromide in the range of 40 mole% can be present. Most preferably, a silver halide emulsion containing at least 70 mol% of silver chloride is used.

The average grain size of the silver halide grains is 0.10 to
Can be in the range of 0.70 μm,
0.45 μm is preferred.

It is preferred to add the iridium and / or rhodium containing compound, or a mixture of both, during or after the precipitation stage. The concentration of these added compounds 1 mole per 10 ^-8 to 10 ^-3 mole of AgNO _3, preferably in the range of 10 ^-7 to 10 ^-5 mole per mole of AgNO _3.

The emulsions can be chemically sensitized during the chemical ripening stage by adding sulfur-containing compounds such as, for example, allyl isothiocyanate, allyl thiourea and sodium thiosulfate. Reducing agent, for example BE-P
Tin compounds as described in 493,464 and 568,687, and derivatives of polyamines such as diethylenetriamine or aminomethanesulfonic acid can also be used as chemical sensitizers. Other suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This method of chemical sensitization is described in KOSLOWSKY, Z. Wi
ss. Photogr. Photophys. Photo
ochem. 46, 65-72 (1951).

Apart from the negative-working silver halide emulsions which are preferred because of their high sensitivity, a direct positive silver halide emulsion which gives a positive silver image in the emulsion layer and a negative image on the image receiving layer is also used. Can be.

Suitable direct positive silver halide emulsions for use in accordance with the present invention are those which have been previously fogged or which mainly form an internal latent image.

The internal latent image-type silver halide emulsion which can be used according to the present invention is described, for example, in US Pat.
2,250,3,206,313,3,271,15
7, 3,447,927, 3,511,662, 3,7
37,313,3,761,276, GB-A 1,0
27,146, and Japanese Patent Publication No. 34,213 / 77.
No. However, the silver halide emulsion used in the present invention is not limited to the silver halide emulsions described in these documents.

Other types of direct positive silver halide emulsions, of the pre-fogged type, for use in accordance with the present invention can be prepared by exposing the silver halide emulsion to light and / or It can be produced by chemically fogging a silver halide emulsion. Chemical fog spec
s) can be formed by various methods for chemical sensitization.

Chemical fogging can be carried out by reduction or by compounds that are more electropositive than silver, such as gold salts, platinum salts, iridium salts, etc., or a combination of both. The reduction fog of silver halide grains is high p
H and / or low pAg silver halide precipitation, or see, for example, Wood J. et al. Photo. Sci. 1 (1953),
163 or by means of reducing agents such as tin (II) chloride, tin complexes and British Patent 1,
No. 209,050, tin (II) salts containing tin chelates of the (poly) amino (poly) carboxylic acid type, formaldehyde, hydrazine, hydroxylamine, sulfur compounds such as thiourea dioxide, phosphonium salts,
For example, it can be carried out by treatment using tetra (hydroxymethyl) -phosphonium chloride, polyamine such as diethylenetriamine, bis (p-aminoethyl) sulfide and its water-soluble salt, hydrazine derivative, alkali arsenite, amine borane and the like, or a mixture thereof. it can.

When fogging of silver halide grains is carried out using a reducing agent such as thiourea dioxide and a compound of a metal which is more positive than silver, particularly a gold compound, the reducing agent is used first, and the gold compound is subsequently used. Is preferred. However, the reverse order can be used, or both compounds can be used simultaneously.

In addition to the method described above for chemical fog, chemical fog is obtained by using the fog agent in combination with a sulfur-containing sensitizer, such as sodium thiosulfate or a thiocyanate compound, such as potassium thiocyanate. be able to.

The DTR-element silver halide emulsion is DTR
The element can be spectrally sensitized according to the spectral emission of the exposure source for which it is designed.

Suitable sensitizing dyes for the visible spectral region include those described by F.A. M. By Hamer “The Cyanin
e Dyes and Related Compou
nds ", 1964, John Wiley & So
methine dyes as described in ns. Dyes which can be used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, isopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

For conventional light sources, for example tungsten light, a green sensitizing dye is required. In the case of exposure with an argon ion laser, a blue sensitizing dye is inserted. For exposure with a red light emitting source, such as an LED or HeNe laser, a red sensitizing dye is used. In the case of exposure with a semiconductor laser, a special spectral sensitizing dye suitable for near infrared is required. Suitable infrared sensitizing dyes are, inter alia, US-P 2,0
95,854, 2,095,856, 2,955,93
9,3,482,978,3,552,974,3,5
73,921,3,582,344,3,623,88
1 and 3,695,888.

The preferred blue sensitizing dye, green sensitizing dye, red sensitizing dye and infrared sensitizing dye in connection with the present invention are EP-A5
54,585.

In order to improve the sensitivity in the red or near infrared region, a so-called supersensitizer can be used in combination with a red or infrared sensitizing dye. A suitable supersensitizer is R
search Disclosure Vol 28
9, May 1988, item 28952. The spectral sensitizer can be added to the photographic emulsion in the form of an aqueous solution, a solution in an organic solvent, or a dispersion.

The silver halide emulsions can contain the usual emulsion stabilizers. Suitable emulsion stabilizers are azaindenes,
Preferably tetra- or penta-azaindenes,
Particularly, those substituted with a hydroxy or amino group. Compounds of this type are described by BIRR in Z. Wiss. P
photogr. Photophys. Photoche
m. 47, 2-27 (1952). Other suitable emulsion stabilizers are, inter alia, heterocyclic mercapto compounds.

The silver halide emulsion layer usually contains gelatin as a hydrophilic colloid binder. Mixtures of different gelatins with different viscosities can be used to adjust the rheological properties of the layers. However, instead of or together with gelatin, one or more other natural and / or synthetic hydrophilic colloids, such as albumin, casein, zein, polyvinyl alcohol, arginic acid or their salts, cellulose derivatives such as carboxy Methyl cellulose, modified gelatin, for example, phthaloyl gelatin and the like can be used.

The material for preparing a lithographic printing plate according to the invention comprises a glass support according to the invention, and i) a hydrophilic polymer layer which may optionally be crosslinked, ii) an image receiving layer containing physical development nuclei. And iii)
For a mono-sheet DTR material comprising a silver halide photographic emulsion layer in the order shown, the gelatin layer is preferably substantially non-hardened. Substantially non-hardening means that such a gelatin layer is coated on a primed polyethylene terephthalate film base at a dry thickness of 1.2 g / m ² , at 57 ° C. and 35% R.C.
H. When dried for 3 days in water at 30 ° C,
This means that the gelatin layer dissolves in more than 95% by weight within 5 minutes.

The silver halide emulsion may contain a pH adjusting component. Preferably, at least one gelatin-containing layer is coated at a pH value above the isoelectric point of the gelatin to avoid interactions between the gelatin-containing layer and other (optional) layers. Most preferably, all gelatin containing layers are coated at a pH value above their isoelectric point. Other ingredients such as antifoggants, development accelerators, wetting agents and hardeners for gelatin can be present. The silver halide emulsion layer is a light-shielding dye (lig) that absorbs scattered light and thus improves the sharpness of the image.
ht-screening dyes). Suitable absorbing dyes are, inter alia, US-P 4,09
2,168, US-P 4,311,787 and DE-
P 2,453,217.

Further details regarding the composition, preparation and coating of silver halide emulsions suitable for use in accordance with the present invention can be found, for example, in Product Licensing.
Index, Vol. 92, December 19
71, publication 9232, p. 107
-109.

The material for preparing a lithographic printing plate according to the invention comprises a glass support according to the invention, and i) a hydrophilic polymer layer which may optionally be crosslinked, ii) an image receiving layer comprising physical development nuclei. And iii)
In the case of a mono-sheet DTR material comprising a silver halide photographic emulsion layer in the order shown, the material also comprises an interlayer between the image receiving layer and the photosensitive layer (packet) on the hydrophilic surface of the support. Preferably, the layers (packets) are removed, thereby facilitating exposure of the silver image formed on the image receiving layer by processing of the imaging element.

In one embodiment, the interlayer is 0.01
２．０2.0 g / m ² , comprising at least one non-proteinaceous hydrophilic film-forming polymer, such as polyvinyl alcohol,
A water-swellable intermediate layer containing an antihalation dye or pigment as described in P-A-410500.

In another embodiment, the intermediate layer is a layer containing hydrophobic polymer beads having an average diameter of at least 0.2 μm and made by polymerization of at least one elethynic unsaturated monomer. The interlayer preferably contains the hydrophobic polymer beads in an amount of up to 80% of its total weight in the dry state. For further details see EP-A-483415
Is disclosed.

The silver halide emulsion-containing layer and the water-swellable intermediate layer or a complementary intermediate layer which may be present between the intermediate layer containing hydrophobic polymer beads, include an antihalation dye or pigment, One or more components such as drugs, silver halide solvents, base precursors and corrosion inhibitors can be inserted.

In a further embodiment of the present invention, a driographic material for making a lithographic printing plate is provided. The driographic material comprises a glass support, which is at most 0.5 mm thick, has a breaking stress of at least 10 ⁷ Pa and a Young's modulus of 10 ¹¹ Pa or less. Any driographic material for the preparation of a lithographic printing plate on the glass support of the invention can be realized, which is described in EP-A 573091, the description of which is incorporated herein by reference. It is preferable to use a driographic material of
A major advantage of these driographic materials is the fact that the need for the use of organic solvents in development is avoided, or at least that ecologically more acceptable solvents can be used.

Thus, the driographic material comprising the glass support of the present invention is a heat-mode recording material. Such a material is imageable by laser ablation and includes, on the glass support, a first layer comprising a polymer and a second layer below the first layer, wherein the first and second layers are At least one is characterized by effective absorption of infrared radiation, wherein the first and second layers exhibit different affinities for printing fluids selected from the group consisting of inks and adhesives for the inks.
The material preferably comprises a polysiloxane in the first layer and is oleophobic. In another embodiment, the first layer of the driographic material comprises a conductive polymer layer, an infrared absorbing metal layer, or an infrared absorbing compound dispersed in a polymeric binder. In this case, a heat conversion substance is contained in the oleophobic surface layer. The heat mode recording material described herein above contains another heat mode recording layer containing a heat conversion material contained between the glass support and the oleophobic surface layer. Examples of substances that can convert radiation into heat are:
For example, carbon black, an infrared or near-infrared absorbing dye or pigment, a metal such as Bi, Sn, Te, or a combination thereof. Suitable infrared dyes are for example US-48
33124, EP-321923, US-479258
3, US-4942141, US-4948776, U
S-4948777, US-4948778, US-4
950639, US-4950640, US-4912
083, US-4955252, US-502499
0, U.S. Pat. No. 5,023,229. Suitable infrared pigments are, for example, Heubach Langelsh
HEUCODER metal oxide pigment available from eim. When a metal such as bismuth is used as the heat conversion material, the recording layer is preferably a vacuum deposited metal layer.

In the heat mode recording material on a glass support of the present invention, the thickness of the recording layer can be 3 μm or less to obtain a printing plate of acceptable quality, and the thickness is less than 2.5 μm. More preferably, there is. Typically, the recording layer preferably has a thickness of 15 nm to 1.5 μm. If the exposure takes place via a support, a maximum thickness of the recording layer of 3 μm is particularly important. The heat mode recording layer used in connection with the present invention comprises a binder such as gelatin, cellulose, cellulose ester such as cellulose acetate, nitrocellulose, polyvinyl alcohol, polyvinylpyrrolidone, a copolymer of vinylidene chloride and acrylonitrile, poly (meth) acrylate, It can contain polyvinyl chloride, silicone resin and the like. The recording layer can further include other components such as wetting agents, matting agents, antioxidants, and the like. The heat mode recording layer is
It preferably contains a polymer containing covalent chlorine. Alternatively, some or all of the polymer may be included in another layer located adjacent to the heat mode recording layer, most preferably between the support and the heat mode recording layer. The heat mode recording layer associated with the present invention can be hardened. For example, a nitrocellulose layer hardened with isocyanate can be used. It has been found that the speed of the recording material can be increased if the polymer containing covalent chlorine is contained in the heat mode recording layer of the recording material or in an adjacent layer.

The oleophobic surface layer of the present invention has at least 1.0
μm, preferably at least 1.5 μm
m is more preferred. The maximum thickness of the surface layer is not critical, but is preferably 5 μm or less, more preferably 4 μm or less. It has been found that the thickness of the oleophobic surface layer affects the printing durability, sharpness and resolution of the printing plate.

According to the present invention, the oleophobic surface layer preferably contains a hardened silicon coating. Silicon coatings contain one or more components, one of which
One is generally a linear silicone polymer terminated at both ends with chemically reactive groups and is preferably a polyfunctional component as a hardener. The silicone coating can be hardened by condensation hardening, additional hardening or irradiation hardening.

Condensation hardening can be carried out by using a hydroxy-terminated polysiloxane that can be hardened with a polyfunctional silane. Suitable silanes are, for example, acetoxysilanes, alkoxysilanes and silanes containing oxime functions. In general, condensation hardening is carried out in the presence of one or more catalysts, for example tin salts or titanium salts. In another case, the hydroxy-terminated polysiloxane is
For example, the film can be hardened using a polyhydrosiloxane polymer in the presence of a catalyst such as dibutyltin diacetate.

[0094] Addition hardening is based on the addition of Si-H to a double bond in the presence of a platinum catalyst. Silicone coatings that can thus be hardened according to the addition hardening include vinyl-containing polymers, platinum catalysts such as chloroplatinic acid complexes, and polyhydrosiloxanes such as polymethylhydrosiloxane. Suitable vinyl-containing polymers are, for example, vinyldimethyl-terminated polydimethylsiloxane and dimethylsiloxane / vinylmethylsiloxane copolymer.

Irradiation hardening coatings which can be used according to the invention include, for example, U.S. Pat. V. Hardening coating,
Or an electron beam hardening coating comprising a polysiloxane polymer containing (meth) acrylate groups.
The latter coating preferably also contains a multifunctional (meth) acrylate monomer.

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

1. A glass support having a surface that can be differentiated into an ink receiving area and an ink repelling area according to an image pattern, wherein the glass support has a thickness of 0.5 mm or less, a breaking stress of at least 10 ⁷ Pa and a Young of 10 ¹¹ Pa or less. A material for producing a lithographic printing plate having an elastic modulus.

2. Laser ablation
and a second layer beneath the first layer, the first layer containing a polymer and a second layer below the first layer, wherein at least one of the first and second layers is infrared-effective. 2. The material according to claim 1, characterized in that the first and second layers exhibit different affinities for a printing liquid selected from the group consisting of inks and adhesive liquids for the inks, characterized in that the first and second layers have different absorption properties.

3. The material of claim 2 wherein said first layer comprises a polysiloxane.

4. 4. The material of claim 2 or 3, wherein said first layer comprises a conductive polymer layer, an infrared absorbing metal layer or an infrared absorbing compound dispersed in a polymeric binder.

5. The material according to claim 1, further comprising a hydrophilic layer formed from a crosslinked hydrophilic polymer on the glass support.

6. Item 6. The material according to item 5, wherein the hydrophilic layer is formed from a hydrophilic polymer crosslinked using a tetraalkyl orthosilicate.

7. 2. The material according to claim 1, comprising a photosensitive layer on said glass support.

8. The above 1, wherein the surface capable of being differentiated into an ink receiving area and an ink repelling area includes a photosensitive layer.
7. The material according to any one of items 5 or 6.

9. Item 9. The material according to item 8, wherein the photosensitive layer contains a diazonium salt, a diazo resin, or a photocrosslinkable composition.

10. 7. The material according to the above item 5 or 6, further comprising a layer containing physical development nuclei on the hydrophilic layer.

11. 11. The material according to the above item 10, further comprising a light-sensitive layer containing a silver halide emulsion layer on the layer containing physical development nuclei.

12. The material of claim 1 comprising a photosensitive layer containing silver halide and an image receiving layer containing physical development nuclei on the glass support in the order shown.

13. Use of a material according to any of the above for the preparation of a lithographic printing plate.

14. The above 1 wherein the material is imagewise exposed.
Use described in item 3.

15. 15. The material of claim 14, wherein said image-wise exposure comprises scanning exposure using a laser.

16. 16. Use according to claim 14 or 15, wherein said image-wise exposure is carried out through said glass support of said material.

17. 14. The use according to claim 13, wherein a substance is image-wise transferred to the surface of the material, thereby differentiating the surface into an ink receiving area and an ink repelling area according to the transferred image pattern.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G03F 7/09 501 C03C 17/28 C03C 17/30 G03F 7/00 503

Claims (3)

(57) [Claims] 1. A glass support comprising a surface which can be differentiated into an ink receiving area and an ink repelling area according to an image pattern, wherein said glass support has a thickness of 0.5 mm or less, a breaking stress of at least 10 ⁷ Pa and a A material for producing a lithographic printing plate, having a Young's modulus of ¹¹ Pa or less. 2. A first layer which is imageable by laser ablation and contains a polymer, and a second layer under the first layer.
A layer on the glass support, wherein at least one of the first and second layers is characterized by effective absorption of infrared radiation, wherein the first and second layers are from the group consisting of ink and an adhesive for the ink. 2. The material according to claim 1, which exhibits different affinities for the selected printing liquid. 3. Use of the material according to claim 1 for preparing a lithographic printing plate.