JP4309485B2 - Material comprising a layer on a glass support - Google Patents

Description

[0001]
FIELD OF THE INVENTION
The present invention relates to a method for continuously applying layers on glass. In particular, the present invention relates to silver halide photographic materials coated on glass in a continuous manner.
[0002]
BACKGROUND OF THE INVENTION
For many applications of silver halide photographic materials, dimensional stability is most important. Photographic materials exhibiting good dimensional stability can be produced using plastic films based on polyester, but for special applications such as photomicrographs, some graphic arts applications, printed circuit board (PCB) photos For fabrication and the like, it is still preferred to use a silver halide photographic material coated on glass. Even in applications where the material must have high thermal stability, the use of a glass support is preferred over the use of a plastic film support. An example of an application where high thermal stability is required is the production of LCDs as described in EP-B 396 824 and EP-A 615 161. In the production of color filters for the production of color LCDs, the optical isotropy of glass is advantageous (most polymer films are optically anisotropic, ie exhibit birefringence).
[0003]
Application of layers on glass plates in a continuous process is described in EP-A 716339. The application describes that (i) the thickness of the glass support is less than 1.2 mm, and (ii) the glass support is 1 × 10 ⁷ Failure stress equal to or higher than Pa (under tensile stress) and 10 × 10 ^Ten Disclosed is a method of applying various layers to a glass support in a continuous application machine characterized by having an elasticity modulus (Young's modulus) equal to or lower than Pa. . However, the material still exhibits two significant drawbacks. First, the material cannot be safely wound on a small core enough to avoid premature failure, and secondly, the strength of the glass is low for use in the relatively large dimensions required for LCDs. Too much.
[0004]
Chemically tempered float glass having a strength greater than that of ordinary float glass is known. EP-A 286018 discloses a support made of chemically strengthened glass. However, the glass still breaks from the boundary cut. JP-58-208728 describes a liquid crystal color display between substrates each made from a borosilicate glass coated with a silica film. However, the glass still breaks from the boundary cut. JP-57-205343 discloses a tempered glass by subjecting the glass to heat treatment and ion exchange treatment at a constant rate of temperature rise and producing a metal film. However, the glass still breaks from the boundary cut. JP-58-156554 describes the prevention of deterioration of a thin film formed on the surface of a glass substrate by reducing the sodium oxide content in the surface layer of a borosilicate glass containing sodium oxide by ion exchange treatment. . However, the glass still breaks from the boundary cut. However, this document does not describe anything about the solution to the problem of winding glass around a small core.
[0005]
Furthermore, chemically cured glass still cracks at the glass boundaries.
[0006]
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an element having a layer on a glass support that can be wound on a small core.
[0007]
Another object of the present invention is to provide a light-sensitive material comprising a glass support produced in a continuous process that can be wound on a small core.
[0008]
Yet another object of the present invention is to provide a dry imaging material comprising a glass support made in a continuous process that can be wound onto a small core.
[0009]
Other objects and advantages of the present invention will become apparent from the following detailed description.
[0010]
According to the present invention,
(I) the thickness of the glass support is less than 1.2 mm,
(Ii) The glass support is 5 × 10 ⁷ Has a failure stress (under tensile stress) equal to or higher than Pa, and
(Iii) including a layer on the glass support, wherein the longitudinal sides have rounded boundaries with a radius on the order of magnitude of half the thickness of the glass support An element is provided.
[0011]
In a preferred embodiment, the glass support is unwound from a roll comprising a core having a diameter between 0.05 m and 1 m.
[0012]
Most preferably, the glass support has a thickness equal to or less than 0.8 mm, 10 × 10 ⁷ It is unwound from a roll comprising a core having a fracture stress (under tensile stress) equal to or higher than Pa and having a diameter between 0.05 and 0.80 m.
[0013]
Detailed Description of the Invention
The main advantage of glass as a support for any layer is the dimensional stability and recyclability of the glass support, the main drawback is the risk of breaking and as a result on a small core The glass cannot be wound. In many applications, there is a need for glasses having increased area without increasing weight. Therefore, there is a need for thinner glass. However, thinner glass supports are more sensitive to mechanical breaks such as fracture. We now have a thickness less than 1.2mm and 5x10 ⁷ The thickness of the glass support, preferably having a rounded boundary with a fracture stress equal to or higher than Pa (under tensile stress) and a radius on the order of half the thickness of the glass support. We have found that glass with longitudinal sides with rounded boundaries with less than half of the radius combine the advantages of high mechanical strength with the ability to wind on a small core. It is surprising that glass with such a high breaking stress can be produced in an economical way when the glass has a thickness of less than 1.2 mm. The demand for a support having a thickness of less than 1.2 mm is not special. For example, in the manufacture of LCD, it is recommended to use a thin glass support of about 0.7 mm. Particularly in this area, the use of thinner glass supports is highly desirable for both economic and weight reasons.
[0014]
Not only is thin glass desirable in the production of color filters for use in LCD production, but a thin glass support is desirable in all applications where high glass dimensional stability, transparency, etc. are desired compared to plastic films. . In photography, for example, graphic arts materials can be considered. Not only silver halide materials in which one or more photosensitive layers are coated essentially from a liquid coating solution, but also thermal imaging materials that use, for example, vacuum deposited metal layers (particularly bismuth layers) as image recording media are thin. Benefits are obtained from having a glass support. In fact, all imaging materials that require high dimensional stability benefit from application to a thin glass support. In all these applications, unwinding or winding the glass support from a small core means that for general coating or sizing and ease of use in packaging machines, for example transportation Is important for.
[0015]
5 × 10 ⁷ Equal to or higher than Pa, more preferably 10 × 10 ⁷ Equal to or higher than Pa, most preferably 20 × 10 ⁷ A glass support having a fracture stress (under tensile stress) equal to or higher than Pa can be obtained by using chemically strengthened glass. Chemically tempered glass is glass in which the original alkali ions are at least partially replaced in two surface layers by alkali ions having a larger radius. In practice, this means that for classical chemical strengthening, in sodium lime silica glass, potassium at least partially replaces sodium in the surface and in lithium lime silica glass, sodium replaces lithium in the surface. means.
[0016]
The chemically strengthened layer thickness is defined herein as the layer thickness at the surface of each side of the support where the substitution occurs by at least 25%. For economic reasons, the thickness of the chemically strengthened layer of the glass support is preferably less than ¼ of the total original glass thickness, more preferably less than 30 μm, most preferably Is thinner than 15 μm. Only the outer part of the surface of the glass support is replaced and the interior of the glass support that is not replaced remains (by far) the main part. Further details regarding the chemical strengthening of glass are given, for example, in “Glass Technology, Vol. 6, No. 3, page 90-97, June 1965, which is incorporated herein by reference.
[0017]
Preferably, the chemical strengthening of the glass is performed on-line with the manufacture of the float glass.
[0018]
The glass can be coated with a boro / silicate sol / gel coat, preferably having a thickness of at least 100 μm, more preferably 200 μm.
[0019]
The glass may be used in a sandwich or other combination with ordinary glass coated with a boro / silicate sol / gel coat having a thickness of preferably at least 100 μm, more preferably 200 μm. it can. The sandwich is used, for example, for LCDs.
[0020]
Application of the layer to the thin glass support can be effected, for example, by sputtering, physical vapor deposition, chemical vapor deposition, via the material comprising the layer, as disclosed in WO 87/00982 (optionally). This can be done by laminating the layer on the temporary support (via the adhesive layer) as well as by coating from a liquid coating solution.
[0021]
A wide and thin glass plate supported only by the edges (as done in a discontinuous way to coat the glass plate) will bend at the middle and cannot be easily and uniformly coated, The problem with coating one or more layers on a glass support that is the same or thinner than 0.7 mm in the discontinuous coating method is the problem with discontinuous coating on a relatively thick glass support. It becomes even more severe.
[0022]
It has been found that a glass support on a roll can be supplied when it is required to coat a layer on a glass support thinner than 1.2 mm. This has the great advantage that such a support can be coated in a continuous coating apparatus for coating layers on plastic films. When the glass is not thicker than 1.2 mm, it can take the form of a roll and as a result can be unwound and coated in a web-like continuous coating machine. This is especially true when the glass support is 10 × 10 ^Ten Equal to or less than Pa, preferably 7 × 10 ^Ten This is the case when it has an elastic modulus (Young's modulus) smaller than Pa. The glass is 5 × 10 according to the invention. ^Ten Equal to or greater than Pa, preferably 10 × 10 ^Ten When it has a failure stress (under tensile stress) greater than Pa, it can take the form of a roll on a small core. When the glass meets these conditions, it can be rolled into a core having a diameter between 0.05 m and 1 m, depending on the thickness.
[0023]
EP-A 716339, which is incorporated herein by reference, discloses a method for continuously coating glass on a roll in layers.
[0024]
The glass on the roll according to the invention for continuously coating the layers thereon will have a coating width of at least 5 cm. That is, the glass is at most 1.2 mm thick, but the width / thickness ratio of the glass roll according to the invention is at least 40.
[0025]
Prior to coating, the surface of one or two sides of the rolled glass can be pretreated, for example etched.
[0026]
The glass on the roll according to the present invention can be coated with any of the coating solutions currently applied to flat glass plates, such as filter layers, adhesive layers and the like. The glass on the roll is one of the continuous coating techniques used to coat the solution on the running web, such as dip coating, bar coating, blade coating, air knife coating, gravure coating, reverse roll coating, extrusion coating. It can be coated by slide coating and curtain coating. An overview of these coating technologies can be found in the book "Modern Coating and Drying Technology", Edward Cohen and Edgar B. Gutoff Editors, VCH publishers, Inc, New York, NY, 1992. Multiple layers can be coated simultaneously on the glass on the roll by known coating techniques useful for simultaneous coating of multiple layers, such as slide coating, curtain coating, and the like.
[0027]
Continuous layers can be applied not only by the coating described above, but also by vapor deposition, sputtering and lamination. The layer may be an imaging layer, for example a layer containing physical nuclei or a layer used for light resistance or for the printing plates mentioned below. The layer may be a non-image forming layer, such as a metal layer, preferably a selectively reflective metal layer, an adhesive layer, a magnetic layer, a hard coat layer, a layer applied by ink jet, an alignment layer, an ITO layer, electroplating And a photoplating layer, a pigment layer, a thermal adhesive layer and a thermoplastic layer.
[0028]
Discontinuous layers can be applied on glass by lamination, by ink jet, by electrophotography, by thermal sublimation, by printing, by vacuum evaporation through a mask, or the like. The layer can be an image-forming layer or a non-image-forming layer. Examples of such layers are given above.
[0029]
The continuous or discontinuous layers can also be combined and applied to one or both sides of the glass support. The layer can be used as a protective layer or as an auxiliary layer (metal, paper).
[0030]
The glass on the roll according to the invention can preferably be used as a support for the photosensitive or heat-sensitive layer.
[0031]
The glass on the roll according to the invention is particularly useful for the production of silver halide photographic materials on a glass support, wherein at least one hydrophilic colloidal aqueous solution comprising silver halide crystals is present on the glass support. Coated on top. Thin glass (less than 1.2 mm, preferably less than 0.8 mm) as a support for silver halide photographic materials because glass is a cheap, morphologically good and fully recyclable support Thickness) Use of glass is desirable. Glass in roll form is preferably a substitute for plastic film as a support for photographic materials when the thickness is 50-300 μm (0.05-0.3 mm). Such glass supports can be used in transparent or colored (gray, blue, etc.) form. The silver halide photographic material coated on the rolled glass according to the present invention can be of any type known in the art, such as black and white materials, color materials, materials designed for gravure arts, medical It may be a material for use in diagnosis, a movie material, a diffusion transition material in a dye diffusion transition method operated using a silver halide emulsion layer, and the like. The principles and aspects of silver image formation by DTR photography are described, for example, in the book "Photographic Silver Halide Diffusion Processes" by Andre Rott and Edith Weyde-The Focal Press London and New York (1972) and by dye diffusion transfer The principles and aspects of color imaging are described by C. Van de Sande in Angew. Chem. Int. Ed. Engl. twenty two (1983) p. 191-209.
[0032]
See, for example, Research Disclosure 17,643 of December 1978 and Research Disclosure 307,105 of November 1989 for the composition of the silver halide emulsion layers and auxiliary layers.
[0033]
The silver halide photographic material coated on the rolled glass according to the present invention may comprise a known hydrophilic binder or a mixture of hydrophilic and hydrophobic binders. Useful binders are, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, dextrans, synthetic clays, polyamides, etc., or mixtures of these binders. The emulsion can comprise a known polymeric latex.
[0034]
A silver halide photographic material coated on rolled glass can comprise one layer of silver halide emulsion or multiple layers of the same or different silver halide emulsions. Silver halide emulsions used in photographic materials coated on rolled glass can be any type of photosensitive silver halide, such as silver bromide, silver chloride, silver chloroiodide, silver bromoiodide or chlorobromo. It can also comprise silver iodide or mixtures thereof. The average particle size is preferably in the range of 0.01 to 1.2 μm. The size distribution of the silver halide grains may be homogeneous or heterogeneous.
[0035]
The crystal properties of the silver halide grains used in the silver halide photographic material coated on the rolled glass according to the present invention may be of any type known in the art. Silver halide grains can have a regular cubic or octahedral nature without twin planes. They can also have mixed cubic / octahedral properties without twin planes. The silver halide crystal grains used in emulsions coated on rolled glass may have one or more twin planes, for example DE 32 41 634 and DE 32 41 640. It may be tubular as disclosed in the above.
[0036]
Photosensitive silver halide emulsions are described, for example, by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1987), by GF Duffin in "Photographic Emulsion Chemistry", The Focal Press, London (1966), and Included in "Making and Coating Photographic Emulsion" by VL Zelikman, The Focal Press, London (1966) and "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968) Can be chemically sensitized. Photosensitive silver halide emulsions coated on glass rolls according to the present invention are spectroscopically analyzed using methine dyes such as those described by FM Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons. It can be sensitized. Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes belong to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. However, in the case of contact sunlight materials, the emulsions are preferably not spectrally sensitized in terms of sunlight stability.
[0037]
One or more silver halide emulsions coated on a glass roll according to the present invention are either internal or external sensitized types comprising a spectral sensitizer, such as pinacryptol yellow. A direct positive emulsion may be used.
[0038]
One or more silver halide emulsions coated on a glass roll according to the present invention may be used to prevent fogging or to stabilize photographic properties during manufacture or storage of photographic elements or during their photographic processing. The compound can comprise. Many known compounds can be added to the silver halide emulsion as fog inhibitors or stabilizers.
[0039]
The photographic material coated on the glass roll according to the present invention may further comprise various surfactants in the photographic emulsion or in other hydrophilic colloid layers. Suitable surfactants include nonionic reagents such as saponins, alkylene oxides such as polyethylene glycol, polyethylene glycol / polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters. Polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or alkyl amides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of sugars; for example, carboxy-, sulfo- Anionic reagents containing acid groups such as phospho-, sulfate- or phosphate ester groups, eg amino acids, aminoalkyls Sulfonic acids, aminoalkyl sulfates or phosphate esters, alkylbetaines, and amine-N-oxides, and cationic reagents such as phosphonium containing alkylamine salts, aliphatic, aromatic, or heterocyclic rings Or sulfonium salts are included. Such surfactants are used for various purposes, for example, as coating aids, as antistatic compounds, as compounds that improve sliding properties, as compounds that promote dispersion emulsification, as compounds that prevent or reduce adhesion and in photography. It can be used as a compound to improve properties such as higher contrast, sensitization, and development acceleration. Suitable surface-active coating agents are compounds containing perfluorinated alkyl groups.
[0040]
The color photographic recording material coated on the rolled glass according to the present invention generally has at least one silver halide emulsion for recording light in each of the three spectral regions red, green and blue. Comprising layer units. See Research Disclosure December 1989, no 308119 paragraph VII, which is incorporated herein by reference, for various possible embodiments of the color material coated on the rolled glass according to the present invention.
[0041]
Prior to coating the silver halide material according to the present invention on a glass roll, the glass support can be precoated with an undercoat layer to give good adhesion to the hydrophilic layer. Particularly suitable subbing layers for this purpose are those based on silicon compounds, such as those described in US Pat. No. 3,661,584 and British Patent No. 1,286,467. To improve adhesion, the compound can be added to the composition of the hydrophilic colloid layer adjacent to the glass support.
[0042]
Silver halide materials are both protective layers, filter layers, barrier layers, mordant-containing layers, backing layers, anti-curl layers, antistatic layers, as undercoats and as antihalation layers coated on the back of the materials The antihalation layer can also be contained.
[0043]
Glass in roll form is particularly suitable for use in the manufacture of multicolor liquid crystal devices comprising multicolor filters such as disclosed in EP-B 396 824 and EP-A 615 161, for example. In this case, the glass is coated with at least three emulsion layers, each sensitive to light in a specific wavelength range.
[0044]
The glass on the roll is not only well suited for the production of the multicolor filter described above, but also when the electronic components required for the multicolor liquid crystal display can be applied on the glass provided in roll form. It can be applied easily and with better quality. Silkscreen printing is used for the application of the electronic components on the glass sheet, but using glass on rolls uses faster and more reliable printing techniques such as offset printing. Can do.
[0045]
After coating and drying, the photographic material coated on the glass roll according to the present invention can be cut into sheet material, kept in roll form, etc.
[0046]
When using a silver halide photographic material on roll glass according to the present invention, it is necessary to keep the thin support flat and known means for keeping the photographic material coated on the film support flat. Can be used.
[0047]
As explained above, it is beneficial not only to apply a silver halide material to a glass support, but also to apply a dry imaging material to a thin glass support. The glass support according to the invention is also very well suited for use in dry imaging materials. Examples of dry imaging materials allow, for example, DRAW (direct reading after writing) or dry processable with high dimensional stability (ie latent images formed by radiation exposure to be visualized without using liquids) ) Recording element.
[0048]
Several types of dry imaging systems can be applied to the glass according to the invention.
[0049]
In one embodiment, the image recording layer in the recording element according to the invention is a photodelamination layer as described in Research Disclosure (RD) Item 22202 (Oct. 1982), p328-329.
[0050]
According to another embodiment, the image recording layer is a photochromic layer described below in Chapter 8 of KI Jacobson and RE Jacobson, Imaging Systems, Focal press (1976) p. 143.
[0051]
According to another aspect, the image recording layer is a thermal recording layer. An imaging element comprising a thermal recording layer as described, for example, in WO 94/18005 can be advantageously used to produce a lithographic plate for use in lithographic printing. The thermal recording layer can be made of various materials. An overview of metals suitable for use in DRAW thermal recording and suitable for use in accordance with the present invention is shown in US Pat. Nos. 4,499,178 and 4,388,400.
[0052]
Since the metal layers have a relatively high reflectivity, their ablation during thermal recording provides points with lower reflectivity. According to another embodiment, the increased transmission is heated with a laser beam by using a thermal recording layer that is initially poorly reflective on a transparent support but is ablated in the laser beam attack area. Obtained in the area. Such a layer produced from a low melting point metal intended for co-production and co-precipitated on a transparent support and a sulfide such as GeS or SnS is described, for example, in Journal of Applied Photographic Engineering, Vol. 9, No. 1, Feb. 1983, p. 12. For the manufacture of optical discs in which information is read in a reflective manner, a relatively high melting reflective support or layer, such as aluminum, on which the poor reflective thermal recording layer is carried by a support. Applied on the layer.
[0053]
In another embodiment, thermal recording is performed using an organic dye layer that does not contain a binder, as described, for example, in the periodical publication Philips Techn. T. 41, p. 338-346 by DJ Gravesteijn and J. van der Veen. To be implemented.
[0054]
Thin (typically less than 1 μm) layers of metals, alloys or dyes suitable for thermal recording are advantageously produced by vacuum evaporation.
[0055]
In a preferred embodiment of a thermal recording material applied on a glass support according to the present invention, a thin, vacuum-deposited layer of Bi provides energy for removal due to its low toxicity and due to melting or evaporation. It is used as a thermal recording layer because it is hardly required and can be easily formed by vapor deposition under vacuum conditions. Such a Bi (bismuth) layer is preferably protected by a protective layer, for example against scratches, dust and the like. In order to apply such a protective layer, several methods are suitable, such as coating from a liquid solution, spraying of the protective layer on the Bi layer, laminating of the protective layer on the Bi layer, and the like. A preferred method consists of laminating a protective organic resin layer in the form of a web with an adhesive layer and in the same vacuum environment as the Bi layer is vacuum deposited, said Bi layer being in accordance with the present invention. Vapor deposited on a glass support. Such a method is disclosed in detail in EP-B 384 041, which is incorporated herein by reference.
[0056]
In a particularly preferred embodiment of the present invention there is provided an imaging element for producing a lithographic printing plate using a glass support according to the present invention.
[0057]
A material for producing a lithographic printing plate having a surface that can be distinguished into ink-receptive and ink-repellent areas depending on the image pattern is unwound or wound on a small core with high mechanical strength. It has been found that it can be formed on a glass support according to the invention which can be taken or sandwiched on a small printing cylinder. The glass support for such materials was preferably less than 0.5 mm thick.
[0058]
In one embodiment of the invention, the material further comprises a hydrophilic layer made from a cross-linked hydrophilic polymer. Particularly suitable cross-linked hydrophilic layers are obtained from a hydrophilic binder cross-linked with a cross-linking agent such as formaldehyde, glyoxal, polyisocyanate or hydrolyzed tetraalkylorthosilicate. The latter is particularly preferred. As hydrophilic binders, hydrophilic (co) polymers such as vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate homopolymer and copolymer Polymers or maleic anhydride / vinyl methyl ether copolymers can be used. The hydrophilicity of the (co) polymer and (co) polymer mixture used is preferably at least 60% by weight, preferably 80% by weight, the same as the hydrophilicity of polyvinyl acetate hydrolyzed to the extent. Is or higher.
[0059]
The amount of crosslinking agent, in particular tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight, preferably between 0.5 and 5 parts by weight, more preferably 1 part by weight of hydrophilic binder. It is between 0.03 parts by weight.
[0060]
The cross-linked hydrophilic layer according to the invention preferably also contains substances that increase the mechanical strength and the porosity of the layer. Colloidal silica can be used for this purpose. The colloidal silica used may be in the form of any commercially available water-dispersion of colloidal silica having an average particle size, for example up to 40 nm, for example 20 nm. In addition, active particles larger in size than colloidal silica, such as silica or alumina particles or titanium dioxide produced according to the Stoeber method described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69, or Other heavy metal oxide particles that have an average diameter of at least 100 nm can be added. The addition of these particles provides a uniform rough texture consisting of microscopic irregularities that act as a reservoir for water in the background area on the surface of the crosslinked hydrophilic layer. The thickness of the cross-linked hydrophilic layer can vary within the range of 0.2 to 25 μm and is preferably 1 to 10 μm.
[0061]
Other specific examples of cross-linked hydrophilic layers suitable for use according to the invention are EP-A 601240, GB-P-1419512, FR-P-2300434, US-P-3971660, US-P-4284705 and EP- A 514490.
[0062]
A very suitable material for producing lithographic printing plates is
i) Thickness that the glass support is not thicker than 0.5 mm, at least 50 × 10 ⁷ Has a failure stress of Pa, and
ii) The material further comprises a photosensitive layer
It is a material comprising a glass support having a surface that can be distinguished into ink receptive and ink repellent areas according to the image pattern.
[0063]
More suitable materials for producing lithographic printing plates are:
i) Thickness that the glass support is not thicker than 0.5 mm, at least 50 × 10 ⁷ Having a failure stress of Pa,
ii) the material further comprising a hydrophilic layer made from a cross-linked hydrophilic polymer; and
iii) The surface that can be distinguished into ink receptive and ink repellent areas also comprises a photosensitive layer
It is a material comprising a glass support having a surface that can be distinguished into ink receptive and ink repellent areas according to the image pattern.
[0064]
The photosensitive layer according to the invention may comprise a suitable photosensitive composition from which an ink receptive image is obtained on the hydrophilic surface of the support of the imaging element. Examples of such photosensitive compositions used herein include those comprising diazo compounds, such as those disclosed in British Patents 1,235,281 and 1,495,861. And comprising a photo-crosslinkable photopolymer disclosed in US Pat. Nos. 4,072,528 and 4,072,527, as described in more detail below. It is what.
[0065]
Among these photosensitive compositions, those comprising a diazo compound are used in various properties such as storage stability of the photosensitive layer, developability, such as degree of development, printability, such as ink acceptability and abrasion resistance, and the like. They are preferably used because of their overall superiority in various properties such as low potential to cause environmental contamination of the developer.
[0066]
Photosensitive compositions containing diazo compounds can be roughly divided into two groups: negative-acting types and positive-acting types.
[0067]
A negative working photosensitive composition containing a diazo compound comprises a photosensitive diazo compound and a polymeric compound. As the diazo compound used in the positive working photosensitive composition, generally known compounds can be used and typical examples thereof are o-quinonediazides and preferably o-naphthoquinonediazide. A compound. These o-quinonediazide compounds can be used alone, but are preferably used in the form of a mixture with an alkali-soluble resin in order to form a photosensitive layer.
[0068]
The photosensitive layer relevant 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 comprises optional components such as dyes, plasticizers, and components to provide printability (the ability to provide a visible image immediately after image-wise exposure). May be.
[0069]
The coating amount of the photosensitive layer applied on the hydrophilic surface of the support is preferably 0.1 to 7 g / m. ² And more preferably 0.5-4 g / m ² Range.
[0070]
Photo-crosslinkable materials suitable in the present invention are based on photo-crosslinkable polymers having maleimide groups in their side chains.
[0071]
In another aspect of the invention, the material for making a lithographic printing plate is both a 2-sheet and mono-sheet process DTR (diffusion transfer material). In the 2-sheet DTR method, a sheet material comprising a silver halide material is imagewise exposed and then contacted with a second sheet material according to the present invention comprising an image receiving layer having physical development nuclei. The sandwich of the two sheets is then processed and during this process silver ions migrate to the image receiving layer and precipitate on the physical development nuclei. In the mono-sheet DTR method, the silver halide layer and the image receiving layer are present in the same sheet material.
[0072]
In the production of a 2-sheet DTR material, an image receiving layer comprising physical development nuclei is applied on a glass support according to the present invention. The glass support is first provided with a layer comprising a cross-linked hydrophilic polymer, and on top of this hydrophilic polymer layer is provided a layer comprising physical development nuclei, An image receiving layer is formed. This image receiving layer is then used in the 2-sheet DTR method. During the production of a lithographic printing plate, substances are transferred image-wise to the surface of the material, thereby distinguishing the surface as ink-receptive and ink-repellent according to the transferred image pattern.
[0073]
The image-receiving layer containing physical development nuclei preferably does not contain a hydrophilic binder, but improves the hydrophilicity of the surface with a small amount of hydrophilic colloid, such as polyvinyl alcohol, up to 30% by weight of the total weight of the layer. May be included to do.
[0074]
Development nuclei suitable for use in accordance with the present invention are heavy metal sulfides such as antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc sulfides. A particularly suitable development nucleus for the present invention is a palladium sulfide nucleus. 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.
[0075]
The glass support according to the invention is also well suited for the production of monosheet DTR materials. Mono-sheet DTR materials for producing lithographic printing plates can be considered in two forms. In the first idea, the DTR mono-sheet material for producing a lithographic printing plate is a glass support according to the invention as well as a hydrophilic polymer layer which may optionally be cross-linked in the order described, ii) physical An image receiving layer comprising development nuclei and iii) a silver halide photographic emulsion layer. In a second view, a DTR mono-sheet material for making a lithographic printing plate comprises a glass sheet according to the invention and an image receiving layer comprising i) a silver halide photographic emulsion layer and ii) physical development nuclei in the order described. Comprising.
[0076]
The hydrophilic polymer layer useful in the first embodiment of the DTR mono-sheet material for lithographic printing plate manufacture can be the hydrophilic polymer layer described above. The image receiving layer comprising physical development nuclei useful in the mono-sheet DTR material according to the present invention can be the same as the image receiving layer described above.
[0077]
This support of sheet material is a glass support according to the invention. In mono-sheet DTR materials, a photosensitive layer is applied to the image receiving layer in water permeable contact with the image receiving layer. Layers in water permeable contact with each other are layers that are in contact with each other or are separated only from each other by one or more water permeable layers. The nature of the water permeable layer is such that it does not substantially inhibit or limit the diffusion of compounds contained in water or aqueous solutions, such as developing agents or complexed silver.
[0078]
The photosensitive material used in both the mono-sheet DTR method and the 2-sheet DTR method together with the material for producing the lithographic printing plate according to the present invention is at least one of a hydrophilic colloid binder and a silver halide emulsion. May be a layer comprising at least one silver halide emulsion that is photosensitive.
[0079]
One or more suitable photographic silver halide emulsions are those described above. For use in accordance with the present invention, the silver halide emulsion or emulsions preferably consist essentially of silver chloride, but the silver bromide moiety is present in the range of 1 mol% to 40 mol%. May be. Most preferably a silver halide emulsion containing at least 70 mole percent silver chloride is used. Preferably during or after the precipitation stage iridium and / or rhodium containing compounds or a mixture of both are added. The concentration of these added compounds is 1 molar AgNO2. _Three 10 per hit ^-8 -10 ^-3 Mole, preferably 1 mole of AgNO _Three 10 per hit ^-7 -10 ^-Five A range between moles.
[0080]
A material for producing a lithographic printing plate according to the present invention comprises a glass support according to the present invention and i) an optionally cross-linked hydrophilic polymer layer in the order described, ii) a physical development nucleus. When comprising an image receiving layer and iii) a silver halide photographic emulsion layer, preferably the one or more gelatin layers are substantially not hardened. Substantially non-hardened means that 1.2 g / m of such a gelatin layer is applied on a primed polyethylene terephthalate film base. ² Means that the gelatin layer dissolves more than 95% by weight within 5 minutes when dipped in water at 57 ° C. and 35% relative humidity for 3 days and immersed in water at 30 ° C.
[0081]
The silver halide emulsion may contain a pH adjusting component. Preferably, at least one gelatin-containing layer is coated at a pH above the isoelectric point of gelatin to avoid interaction between the gelatin-containing layer and another (optional) layer. Most preferably, all gelatin-containing layers are coated at a pH not lower than the isoelectric point of the gelatin.
[0082]
A material for producing a lithographic printing plate according to the present invention comprises a glass support according to the present invention and i) an optionally cross-linked hydrophilic polymer layer in the order described, ii) a physical development nucleus. And iii) a silver halide photographic emulsion layer, this material preferably comprises an intermediate layer between the image-receiving layer and the photosensitive layer (packet) on the hydrophilic surface of the support. And promoting the removal of the layer (packet), thereby exposing the silver image formed in the image receiving layer by processing the imaging element. Examples of such intermediate layers are described in EP-A-410500 and EP-A-483415, which are incorporated herein by reference.
[0083]
In yet another aspect of the invention, a driographic material for making a lithographic printing plate is provided. The driographic material is at most 0.5 mm thick and at least 50 × 10 ⁷ It comprises a glass support having a breaking stress of Pa. Any driographic material can be supplied for the production of a lithographic printing plate on a glass support according to the invention, as described in EP-A-573 091, which is incorporated herein by reference. It is preferred to use a driographic material as described. The main advantage of these driographic materials is that the need to use organic solvents during development is avoided or at least morphologically more acceptable solvents can be used.
[0084]
Accordingly, the driographic material comprising the glass support according to the present invention is a thermal recording material. Such a material is imaged by laser ablation and comprises a first layer comprising a polymer on a glass support and a second layer underlying the first layer, the first layer comprising And at least one of the second layers is characterized by efficient absorption of infrared radiation and the first and second layers exhibiting different affinities for the printing fluid are ink and ink deposits Selected from the group consisting of sex fluids. Preferably, the material comprises polysiloxane in the first layer and is oleophobic.
[0085]
The following examples illustrate the invention without however limiting it thereto. Percentages shown are by weight unless otherwise noted.
[0086]
【Example】
2 × 10 ⁷ A classic glass support with a fracture stress of Pa (under tensile stress) and a thickness of 600 μm can only be wound on a core with a diameter of 2 m which is not suitable for practical use. 10x10 ⁷ Thermally tempered glass with a rounded border side of Pa failure stress (under tensile stress), 600 μm thickness and 300 μm radius can be wound on a core with a diameter of 100 mm, That is perfectly suitable for practical use.
[0087]
The main features and aspects of the present invention are as follows.
[0088]
1. An element comprising a layer on a glass support,
(I) the thickness of the glass support is less than 1.2 mm;
(Ii) The glass support is 5 × 10 ⁷ Has a failure stress (under tensile stress) equal to or higher than Pa, and
(Iii) The longitudinal side has a rounded boundary with a radius on the order of half the thickness of the glass support
element.
[0089]
2. The element of 1 above, wherein the glass support is a chemically strengthened glass.
[0090]
3. The glass support is 10 × 10 ⁷ The element according to 1 above, which has a fracture stress (under tensile stress) equal to or higher than Pa.
[0091]
4). The above two elements, wherein the thickness of the chemically strengthened layer on the surface of the support is less than ¼ of the total thickness of the original glass.
[0092]
5. 5. The element as described in 4 above, wherein the thickness of the chemically strengthened layer on the surface of the support is less than 30 μm.
[0093]
6). The element of claim 1 wherein the glass support is present in combination with ordinary glass coated with a boro / silicate sol / gel coat.
[0094]
7). 7. The elements 1 to 6 above, wherein a photosensitive layer or a heat-sensitive layer is applied on the glass support.
[0095]
8). A silver halide photographic material coated on a glass support,
(I) the thickness of the glass support is less than 1.2 mm;
(Ii) The glass support is 5 × 10 ⁷ Has a failure stress (under tensile stress) equal to or higher than Pa, and
(Iii) The longitudinal side has a rounded boundary with a radius on the order of half the thickness of the glass support
A photographic material characterized by that.
[0096]
9. A dry image forming material comprising a glass support and a dry image forming layer applied to the support,
(I) the thickness of the glass support is less than 1.2 mm;
(Ii) The glass support is 5 × 10 ⁷ Has a failure stress (under tensile stress) equal to or higher than Pa, and
(Iii) The longitudinal side has a rounded boundary with a radius on the order of half the thickness of the glass support
A dry image forming material characterized by the above.
[0097]
10. A material for producing a lithographic printing plate comprising a surface on a glass support which can be distinguished into ink-receptive and ink-repellent areas according to the image pattern, the glass support being thicker than 0.5 mm Not thickness and at least 5 × 10 ⁷ A material having a fracture stress of Pa and having a rounded boundary with a radius on the order of half the thickness of the glass support on the longitudinal side.
[0098]
11. 10. The material of claim 10, wherein the material is imageable by laser ablation and comprises a first layer comprising a polymer and a second layer underlying the first layer on the glass support. Wherein at least one of the first and second layers is characterized by an effective absorption of infrared radiation, and the first and second layers are selected from the group consisting of ink and an adhesive fluid for the ink Materials that have different affinities for printing fluids.
[0099]
12 11. The material as described in 10 above, further comprising a hydrophilic layer formed from a hydrophilic polymer crosslinked on the glass support.
[0100]
13. 10. The material as described in 10 above, comprising a photosensitive layer on the glass support.
[0101]
14 11. The material according to 10 above, wherein the photosensitive layer comprises a diazonium salt, a diazo resin or a photo-crosslinkable composition.
[0102]
15. 13. The material according to 12 above, further comprising a layer containing physical development nuclei on the hydrophilic layer.
[0103]
16. 16. The material according to 15 above, further comprising a photosensitive layer comprising a silver halide emulsion layer on top of the layer comprising physical development nuclei.
[0104]
17. 10. The material of claim 10 comprising a photosensitive layer comprising silver halide and an image receiving layer comprising physical development nuclei in the order described on the glass support.

Claims (17)

An element comprising a layer on a glass support,
(I) the thickness of the glass support is less than 0.7 mm;
(Ii) said glass support has a 5 × 10 7 ^Pa is comparable to or higher than failure stress (under tensile stress) and the (iii) said glass support extends along the longitudinal sides a, a side surface of the glass support element, characterized in that it have a boundary rounded with a radius of magnitude of half the thickness of the glass support.   The element of claim 1 wherein the glass support is a chemically strengthened glass. 2. Element according to claim 1, characterized in that the glass support has a failure stress (under tensile stress) equal to or higher than 10 x 10 < ⁷ > Pa. An element comprising a layer on a glass support,
(I) the thickness of the glass support is less than 0.7 mm;
(Ii) the glass support has a failure stress (under tensile stress) equal to or higher than 5 × 10 ⁷ Pa;
(Iii) said glass support has a side surface extending along the longitudinal direction, the side surface of the glass support has a border rounded with a radius of magnitude of half the thickness of the glass support ,
(Iv) the glass support is a chemically strengthened glass, and (v) the thickness of the chemically strengthened layer on the surface of the support is less than 1/4 of the total thickness of the original glass. An element characterized by being thin.   5. Element according to claim 4, characterized in that the thickness of the chemically strengthened layer at the surface of the support is less than 30 [mu] m. An element comprising a layer on a glass support,
(I) the thickness of the glass support is less than 0.7 mm;
(Ii) the glass support has a fracture stress (under tensile stress) equal to or higher than 5 × 10 ⁷ Pa;
(Iii) said glass support has a side surface extending along the longitudinal direction, the side surface of the glass support has a border rounded with a radius of magnitude of half the thickness of the glass support And (iv) an element characterized in that the glass support is present in combination with ordinary glass coated with a boro / silicate sol / gel coat.   The element according to claim 1, wherein a photosensitive layer or a heat-sensitive layer is applied on the glass support. A silver halide photographic material coated on a glass support,
(I) the thickness of the glass support is less than 0.7 mm;
(Ii) said glass support has a 5 × 10 7 ^Pa is comparable to or higher than failure stress (under tensile stress) and the (iii) said glass support extends along the longitudinal sides a, a side surface of the glass support photographic material characterized in that it have a boundary rounded with a radius of magnitude of half the thickness of the glass support. A dry image forming material comprising a glass support and a dry image forming layer applied to the support,
(I) the thickness of the glass support is less than 0.7 mm;
(Ii) said glass support has a 5 × 10 7 ^Pa is comparable to or higher than failure stress (under tensile stress) and the (iii) said glass support extends along the longitudinal sides a, a side surface of the glass support is dried image-forming material characterized in that it have a boundary rounded with a radius of magnitude of half the thickness of the glass support. A material for producing a lithographic printing plate comprising a surface on a glass support that can be distinguished into ink receptive and ink repellent areas according to the image pattern,
The glass support has a thickness not less than 0.5 mm and a breaking stress of at least 5 × 10 ⁷ Pa, and the longitudinal sides have a radius on the order of half the thickness of the glass support A material characterized by having a certain boundary. 11. A material according to claim 10, comprising a first layer imageable by laser ablation and comprising a polymer and a second layer underlying the first layer on the glass support. There,
Printing wherein at least one of the first and second layers is characterized by an effective absorption of infrared radiation and the first and second layers are selected from the group consisting of ink and an adhesive fluid for ink A material characterized by showing different affinity for fluids.   11. A material according to claim 10, further comprising a hydrophilic layer formed from a hydrophilic polymer cross-linked on the glass support.   11. A material according to claim 10, comprising a photosensitive layer on the glass support. Photosensitive layer diazonium salt, diazo resin or a photo - material according to claim 1 3, wherein in that it comprises a crosslinkable composition.   13. The material of claim 12, further comprising a layer containing physical development nuclei on top of the hydrophilic layer.   16. The material of claim 15 further comprising a photosensitive layer comprising a silver halide emulsion layer on top of said layer comprising physical development nuclei.   11. A material according to claim 10 comprising a photosensitive layer comprising silver halide and an image receiving layer comprising physical development nuclei on the glass support in the order described.