KR930010215B1 - Photographic elements sensitive to near infrared - Google Patents

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Description

Photographic materials that are sensitive to near infrared

The present invention relates to photographic elements that are sensitive (photosensitive) to light emitted in the near infrared spectrum of at least 750 nm, in particular 750-1500 nm. In particular, it relates to a photographic material suitable for providing a high quality recording medium for a laser diode scanning system.

A widely used wound technique is to convert the visible image to electronic data by coding the brightness of adjacent small areas of the visible image. Such electronic encryption has advantages for image manipulation, transmission and storage. Also known is a method of converting data back into the visible image by a so-called "scanning system," whereby the focused rays are quickly scanned into adjacent raster lines through a light-sensitive medium, while modulating the intensity of the light The image is reproduced at the required intensity based on the electronic signal.

Lasers, in particular lasers using argon, krypton, helium-neon or helium-cadmium mixtures as gas-sustaining media, are used as high intensity light sources for this phase technique. All these lasers require additional complex devices to modulate the intensity of the emitted light, and have the disadvantage of requiring large physical bulks, large mechanical brittleness and large fabrication costs.

The semiconductor laser diode is very suitable as a light source for a scanning system in that the scanning light output is directly modulated by the electric signal input, and the scanning light is very durable.

However, currently available laser diode devices with long operating lifetimes and low manufacturing costs are those that emit light in the infrared (NIR) spectrum range of 750-150 nm. Therefore, there is a need to provide a light sensitive recording medium in the NIR range in order to use a laser diode scanning system for this purpose.

Halogenation using long chain cyanine dyes is known in Mees and James, The Theory of the Photographic Process (3rd edition, MacMillan 1966, pp. 198-201), that emulsions are sensitive to near infrared light. Reference is made to the present invention.

NIR photosensitive films, especially silver halides with an average diameter of 0.4 microns or less, are supported by the edges of non-glassy holders to contact other surfaces and are broadly exposed when uniformly exposed from a laser diode scanning system emitted at 820 nm. An image covered with a swirling interference pattern (hereinafter referred to as " non-contact scanning pattern ") is calculated. This breakdown is caused by the reflection of exposure light from two interferences of the film material with ambient air. The path difference between the light rays reflected from the top and bottom surfaces of the film is controlled by the thickness of the film at a given point, and the effective phase difference is due to offset or constructive interference, at which point It is caused by decreased or increased exposure to the light sensitive (photosensitive) emulsion layer. The pattern is therefore outlined by microscopic thickness variations in the film material and covers the field image with a wide line several centimeters long with a spacing of 1 mm.

Non-contact interference fringes have not been reported, as described above, in the literature relating to silver halide emulsion materials. Since the haze of the photosensitive emulsion layer scatters the reflected light from the back surface of the film material, the above phenomenon does not occur under normal exposure conditions exposed to visible light. However, because of the longer wavelengths, infrared light can pass through small particle photographic emulsions without severe scattering, and the coherence of the laser diode output is improved to form interference patterns. Thus, the emulsion shows a detectable pattern in the photograph of silver halide particles with a coating weight of silver of 3 g / m ² and an average diameter of 0.28 microns. Reducing the size of the particles to 0.23 microns or reducing the coat weight results in more patterns, so emulsions with particles of average diameter size of 0.20 microns or less show severe pattern after non-contact laser diode injection.

Non-contact scanning patterns degrade the quality of the scanned image, especially the image that has passed the continuous tone tone. The pattern is not only aesthetically beautiful but also interferes with important information conveyed by slight differences in density on the bed. Preference is given to using photographic emulsions having particles of average diameter size of 0.4 microns or less (preferably 0.30 microns or less). Microparticle emulsions having a particle size of 0.4 microns or less are advantageous in that they provide high resolution and yield maximum light density and optimum phenomena due to high coating power and low coating weight of silver. Thus, the photographic material used in the laser diode scanning system must be able to conceal the non-contact interference fringe.

Interference fringes are known in optical recording systems. When a bright surface photographic film is exposed in contact with other bright surfaces such as glass supports, dot screens or contact printing negatives, a common common problem is Newton's rings. The phenomenon of known concentric pattern of adjacent concentric patterns occurs (see Encyclopedic Dictionary of Physics, J. Thewlis, Ed., Pergamon, London, 1961, p378). This pattern is due to the optical interference between the upper surface of the film and the reflected light from the lower surface of the contact support, and the size of the spatial air gap is determined as the path difference between the two sets of rays, so this phase difference is transmitted into the emulsion layer. Form a bright or dark pattern that causes added or reduced exposure. Newton rings have a tendency to form a pattern of discrete regions, narrowly concentric, radially concentric from the contact point during exposure and becoming smaller toward the edge of each pattern. This is very different from the wide swirling non-contact scanning pattern that covers the field of vision with a wide line of several centimeters in length, approximately 1 mm apart.

Methods for preventing the formation of pneumatic rings are known in the art. For example, bonding matting particles to the outer surface of a film is a known method. Examples of known matting particles include silica, poly-methylmethacrylate (PMMA), polyvinyl compounds containing copolymers, starch or inorganic salts. The application of matting ranges from a small number of quite large particles (no more than 0.1 g / m ² ) having a diameter of 5-10 microns, as described in U.S. Patent Nos. 4,235,939, 4,022,622, 3,754,924 and 2,322,037, etc. Up to 50% or 1 g / m ² of larger particle weight of small particle size to pcoat binder as described in British Patents 2,077,935 and 2,033,956 and US Patents 3,507,678 and 2,992,101 Varies.

The use of visible laser light as illumination for the contact screen exposure of two emulsions results in particularly severe Newton tone ring fringes. U. S. Patent No. 4,343, 873 describes a photographic material for minimizing the pattern, which includes a light-scattering layer in which the photosensitive layer is exposed to laser light. Light scattering particles have a diameter with 50-150% wavelength for illumination lasers. The light scattering layer is coated on the photographic material as an outer layer or as a lower other layer.

The use of matting agents in photographic materials for non-optical properties such as adhesion, abrasion resistance, retouchability, good d raw-down in vacuum flames and reduced static effects is known. have. An example of the use of a matting agent is an infrared photosensitive film as described in US Pat. No. 4,266,010, which describes 0.2-10 micron PMMA for an emulsion protective film containing an acid treated gelatin binder. It claimed to be suitable for all kinds of photographic materials including infrared film. An example of the use of matting agents is U. S. Patent No. 3,695, 888, which describes a photoemulsion that is photosensitized in the infrared by cyanine dyes with specific sensitisers of meso alkylamino substituents. The material is prepared by Bau 1-4 micron size methacrylic acid-methylmethacrylate copolymer beads as specified in US Pat. No. 2,992,101 and emulsion polymerization as specified in US Pat. No. 2,701,24. It is claimed that polymer beads containing poly-methylmethacrylate beads of 1-20 micron size formed may contain matting agents such as silica, zinc oxide, titanium dioxide, and starch.

It has been found that a known kind of layer used on photographic materials to prevent the formation of Newton rings cannot prevent the formation of non-contact interference fringes on photographic materials with photographic emulsions of microparticles that are photosensitized in the near infrared. .

Thus, according to the present invention, a photographic material composed of one or more layers of silver halide emulsions having a support that transmits over 750 mm (typically 750-1500 mm) of infrared light, and particles of average diameter size of 0.4 microns or less that are exposed to infrared light Is provided, the photographic material is characterized by consisting of. In other words :

(i) forming a protective film layer on the same surface of the support as a photosensitive emulsion, a protective film layer which is a layer which transmits light to near infrared rays; A backing layer, which is a layer or light absorbing layer, and (iii) a subbing layer, which is located between the support and the photosensitive emulsion and which diffuses or absorbs near-infrared rays, and thus the photographic material of the present invention is non- The image is formed by a laser scanning system that emits near infrared rays without the formation of contact interference fringes.

The photographic material according to the present invention has an internal optical interference which allows the unprotected microparticle near-infrared film to be covered with a wide swirl pattern when it is developed after being scanned with a laser dyed NIR light source even though the film and other surface are in non-contact upon exposure. It is resistant to the formation of a pattern.

There are three ways to prevent the formation of non-contact interference fringes, which are used alone or in combination.

That is, the first method is that the microscopic (microscopic) surface roughness of the photographic material plays an important role in preventing the formation of the interference fringe. In the formation of the interference fringe by the microscopic surface roughness with 200,000 ridges per 1 mm ² , Significant reduction occurs and complete removal of the interference fringe can occur by surface roughness on the backside of the film with 250,000 ridges per mm ² , and also over 250,000 per 1 mm ² (preferably over 450,000) on the top surface The interference fringe is completely eliminated by the surface roughness with

A second method of preventing the formation of interference fringes is achieved by providing a back or inner layer containing a dye that absorbs light in the wavelength range of an exposed light source. When the layer is used alone as the interference fringe inhibiting layer of the present invention, the layer shows a light peak having a light density of at least 0.75, and the layer has a light density of at least 0.3 when used in combination with other means of interference fringe. By showing, a significant reduction of the interference fringe can occur.

A third method of preventing the formation of interference fringes is to use a backing layer or protective layer composed of a binder in gelatin containing a binder having a high reflectance greater than 0.3, such as non-photosensitive silver halide particles.

The use of silver halide particles gives the advantage that halides can be removed during the development of the photographic material. The high reflectivity layer can be removed after exposure by using the solvent of the binder.

It has been found that the near-infrared photosensitive material, which can almost completely suppress the formation of non-contact interference fringes, consists of several structures. Non-contact interference fringes, for example, are prevented in photographic materials incorporating one or more of the following structures. That is, the structure is:

(1) the back surface of the film substrate at a position away from the photosensitive emulsion, consisting of a binder containing a surface roughening agent having an average particle size of less than 2 microns (generally 0.1-2 microns, preferably 0.2-2 microns) As a layer, this outer back layer contains at least 250,000 particles protruding above the surface average level by 30% of each particle diameter, or by 0.2 micron or less, per 1 mm ² of the surface, and the outer surface is microscopically rough.

(2) A protective film layer on the same film base surface as a photosensitive emulsion, comprising a binder containing a surface roughening agent having an average particle size of 1.5 microns or less (generally 0.1-1.5 microns, preferably 0.2-1.5 microns) Each passivation layer contains at least 250,000 (preferably 450,000) particles per 1 mm ² of the surface, protruding above the average attention of the surface by at least 30% of each particle diameter, or 0.2 micron or less, so that the outer surface Microscopically rough

(3) A back or inner layer containing an antihalation dye that absorbs light in a wavelength range of at least 750 nm, preferably 750-1500 nm and exhibiting a light density light peak of at least 0.75 within said range.

(4) a wavelength of 750 nm or more, preferably 750-1500 nm

A surface roughener containing an antihalation dye that shows a light peak of at least 0.3 light density for a range of light and has an average particle size of 2 microns or less (typically 0.1-2 microns, preferably 0.2-2 microns) The outermost backing layer containing at least 30% of each particle diameter, or 0.2 micron or less, containing at least 200,000 particles protruding beyond the average attention of the surface per 1 mm ² of each surface of the outer surface. This microscopically rough, and further, layer can be optionally divided into two separate layers, the outermost backside layer containing the surface roughening agent and the inner backside layer containing the antihalation dye.

(5) a backing layer exhibiting a light density peak of at least 0.3 for light in the wavelength range of 750 nm or greater, preferably 750-1500 nm, and 2 microns or less (typically 0.1-2 microns, preferably 0.2-2 microns) A layer comprising a protective film layer containing a surface roughening agent having an average particle size of), wherein the layer comprises at least 200,000 particles protruding above the average level of the surface by at least 30% of each particle diameter, or by 0.2 micron or less. Is contained per 1 mm ² of each surface, and the outer surface is microscopically rough.

(3) A back or inner layer containing an antihalation dye that absorbs light in a wavelength range of at least 750 nm, preferably 750-1500 nm and exhibiting a light density light peak of at least 0.75 within said range.

(4) a wavelength of 750 nm or more, preferably 750-1500 nm

A surface roughener containing an antihalation dye that shows a light peak of at least 0.3 light density for a range of light and has an average particle size of 2 microns or less (typically 0.1-2 microns, preferably 0.2-2 microns) The outermost backing layer containing the outer surface comprising at least 30% of each particle diameter, or at least 200,000 particles protruding above the average perimeter of the surface by 0.2 micron or less per 1 mm ² of each surface of the outer surface. This microscopically rough, and further, layer can be optionally divided into two separate layers, the outermost backside layer containing the surface roughening agent and the inner backside layer containing the antihalation dye.

(5) a backing layer exhibiting a light density peak of at least 0.3 for light in the wavelength range of 750 nm or greater, preferably 750-1500 nm, and 2 microns or less (typically 0.1-2 microns, preferably 0.2-2 microns) A layer comprising a protective film layer containing a surface roughness agent having an average particle size of at least 300,000 particles protruding above the average level of the surface by at least 30%, or 0.2 micron or less, of each particle diameter. Containing 1mm ² of each surface, the outer surface is microscopically rough.

(6) an anti-halation layer positioned between the photosensitive layer and the substrate layer, with a light density light peak of at least 0.3 for light of wavelengths greater than 750 nm, preferably 750-1500 nm, and less than 2 microns (typically 0.1-2 micron , Preferably a combination layer of the outermost backing layer or protective layer containing a surface roughening agent of an average particle size of 0.2-2 microns), the layer being at least 30% of each particle diameter, or 0.2 microns The outer surface is roughly microscopically containing at least 200,000 particles per 1 mm ² of the surface protruding above the average level of the surface.

(7) contains a surface roughening agent having an average particle size of 2 microns or less (typically 0.1-2 microns, preferably 0.2-2 microns) and surface by at least 30%, or 0.2 microns or less, of each particle diameter At least 0.3 light for a layer of at least 750 nm, preferably at least 750 nm, preferably 750-1500 nm, with at least 200,000 particles per 1 mm ² of the surface protruding above the average level of the outer surface with a microscopically rough outer surface With particles of average size less than 2 microns (typically 0.1-2 microns, preferably 0.2-2 microns) combined with a layer located between the backing layer and the backing containing the antihalation dye, showing a density flood peak At least 200,000 particles containing a surface roughener and protruding above the average level of the surface by at least 30% or 0.2 micron or less in diameter of each particle are listed. 1mm ² of the outer layer is subjected to microscopic containing per overcoat layer.

(8) a backing layer or protective layer composed of a binder containing particles having a higher reflectance (less than 5 microns, preferably with an average particle size of 0.2-3 microns) than a binder such as non-photosensitive halogenated particles, the layer Can be removed during photo development.

It has been found that the microscopic roughness of the photographic material affects the properties of the material to form a non-contact pattern when forming the image with the scanning laser. In particular, assuming that radiation originates from the other side of the material, the formation of fringes is prevented by the presence of an outer backing layer that provides microscopic roughness with at least 250,000 ridges per mm ² above the average level of the surface. I learned that you can. Similarly, assuming that the material is radiated from the same plane as the layer, at least 250,000 (preferably 450,000) ridges per mm ² are provided so that formation of a pattern is suppressed by providing a protective film layer having a microscopic surface. . This microscopic surface roughness differs from that found in conventional photographic materials incorporating layers of matting agent. That is, in general, the conventional matting layer is present at about 1/2 of the elevation required by the present invention, and sometimes at about 1/10 of the number of elevations used in the present invention.

By using a backing layer or inner layer incorporating an anti-halation dye that exhibits a light density light peak of at least 0.75 in the 750-1500 nm range, the formation of a pattern can also be suppressed.

The combination of the rough surface layer and the anti-halation layer has an additional effect on the surface roughness and light density required when using the layer as a means for reducing the pattern formation since the combination of the layers adds an effect. It can be used as described above when the parameters of surface roughness and light density for each layer are reduced. It has also been found that a suitable microscopic surface roughness for the outer layer used in combination with the antipatterning layer is 200,0 00 ridges per mm ² . In addition, the required light density in the anti-halation layer used in combination with the surface roughness layer is at least 0.3.

The surface layer containing the particles described above is preferably used on the back surface of the material or on the two outer surfaces of the material rather than on the protective film of the photosensitive emulsion surface, which assumes that the exposure from the emulsion occurs rather than the protective film on the emulsion surface. This is because the suppression of the non-contact laser scan pattern is much better due to the rough back side.

Advantageous surface roughness agents used in this layer are polymers (eg, methacrylic acid-methacrylic esters) dissolved in organic polymer (particularly polymethyl methacrylate) particles or developer as described in US Pat. No. 2,992,1 01. Coalescence) particles.

Other suitable organic polymers used in the loads and particle size ranges necessary to impart the matting properties as described above are described in poly 2,078,992 and 2,033,596 and US Pat. Nos. 4,287,299 and 3,079,257. Vinyl compound or vinyl compound copolymer. Other suitable materials include composites of silica and polymers as described in US Pat. Nos. 4,235,959, 3,920,456, 3,591,379 and 3,222,037, or silica, light gelatin, water soluble as described in British Patent No. 2,077,935. Inorganic salts, starches, dextran and mixtures of these polymers.

Matting agents known in the art consist of very small silica particles having a diameter size of 0.1 micron or less. When dispersed in a coating binder, such as a water soluble gelatin, small particles form tightly bound deadlocks having diameters of 1 micron or less, which behave like single particles. The matting properties required for the purposes of the present invention can be obtained by using single particles in the range of the required size or by using a deadlock present entirely within the required size range.

Suitable materials with high reflectivity are non-photosensitive silver halide crystals that can be easily produced in uniform size or can be easily removed by photofixing agents. The reflectance of silver halides is generally 2.0-2.2. Other suitable materials with high reflectance are zinc oxide and calcium carbonate.

Gelatin is a suitable binder for all layers and has a reflectance of about 1.5.

When small particles or other particles, especially particles with an average diameter of 1 micron or less, are used to matte the layer surface of the binder upon coating, the number of protruding particles and the height of the protrusions protruding above the average surface level are contained in the layer. It depends on the weight of the particles and the coating and drying conditions used. It is important to select the coating and drying conditions such that the degree of protrusion of the particles is as required by the present invention, and these parameters are known to those skilled in the art. One method of providing a satisfactory surface roughness when used with a suitable formulation is to pass the wet material immediately after coating into a 13 ° C. cooling zone with 30% relative humidity to allow the gel to cure, 30% relative humidity and 30 ° C. It is to dry in. That is, the thin thin layer is dried for 30 seconds-1 minutes.

In addition to the addition of matting particles as described above introduced to roughen the surface in accordance with the invention, other matting agents with particles of average diameter of 5 microns or more, in order to improve mechanical properties such as adhesion and abrasion resistance, Larger polymers (0.1 g / m ² or less) or silica may be incorporated into the photographic material.

The silver halide emulsion used in the photographic material of the present invention is composed of silver bromide, silver chloride, silver chlorobromide, silver bromoidide or silver chlorobromoidide, Reserch Disclosure 17643 (December 1978), Part II and III. It may be prepared by known methods as described in. Emulsions have particles less than 0.4 microns (typically 0.05-0.4 microns).

The emulsion may be prepared using the dyes specified in European Patent Application Publication No. 0,088,595 or as described in The Theroy of the Photographic Process, 3rd edition, pp 198-199 by Mees and James, preferably 750-1500 nm (preferably 750 -8900 nm) is exposed to near infrared light using other spectral sensitizing dyes known in the art to be sensitive to radiation at wavelength.

The silver halide emulsion present in the photographic material of the present invention is protective against fog formation and safe against loss of photosensitivity during processing. Suitable antifog agents and stabilizers are described in Research Diseclosure 17643 (December 1978), Part VI.

The halogenated silver emulsion present in the photographic material of the present invention may use a brightening agent as specified in Research Disclosure 17643 (December 1978), Part V.

The photosensitive silver halide emulsion used in the present invention may contain a rate increasing compound as specified in Research Disclolsure (December 1978), Part XXI, and the like.

The photographic material layers may contain multiple cloroid materials as excipients or binders as described in Research Disclosure (December 1978), Part IX. Such colloidal materials can be cured by various inorganic and organic curing agents, as described in Research Disclosure 17643 (December 1978), Part X.

The photographic material of the present invention may contain an antistatic agent, a conductive layer, a plasticizer and a lubricant, and a surfactant as described in the Research Disclosure (December 1978) sections XI, XII and XIII.

The photoemulsions used in the present invention may be coated on several transparent supports as described in Research Disclosure 17643 (December 1978), XVIII.

Photosensitizers and other emulsion additives may be incorporated into the photographic material layer by several known methods in the art, as described in Research Disclosure (December 1978), XVL. Similar to the above, the photographic material may be coated on the photographic support by a number of methods. Supports and coating methods are described in research disclosure 17643 (December 1978), sections XV and XVII.

The photosensitive silver halide emulsions used in the present invention are characterized by the combination of silver halides and water-soluble alkaline media in the presence of a developer after exposure as described in Research Disclosure (December 1978), XIX. Form.

The present invention describes in detail a material containing silver halide particles having a diameter of 0.4 microns or less, and the method of inhibiting pattern formation is the same for other photosensitive silver halide-containing materials that can limit the formation of scan patterns due to low turbidity. Can be applied. In particular, the present invention is applied to materials containing thin particles having a high aspect ratio but larger than 0.4 microns in diameter, in particular low proportions of silver halide particles in the material and the remainder consisting of fine particles.

The photographic material of the present invention is a physical development system, phase transfer system, anhydrous development system, diffusion transfer system, printing as described in Research Disclosure (December 1978), XXII, XXIII, XXIV, XXV, XXVI and XXVII. And lithography, print-out and direct-print systems.

In the following examples, the evaluation of the samples is in accordance with the following methods: Evaluation of the sample and pattern measurement by non-contact laser diode scanning.

Samples are evaluated by uniform exposure in a scanning system that focuses radiation from a Hitachi HLP 1400 laser diode emitting at 815 nm to an origin with a diameter of 50 microns on the surface of the sample. The focused origin was scanned in a rafter pattern of 200 lines / cm on the sample by vibrating galvanometer mirror in the path of infrared. After development, the exposure intensity is sequentially increased so as to be calculated from the minimum density to the maximum density on the sample. The following samples are developed using a developer 3M type XP 507, automatically with Eastman Kodak RP X-Omat developer. Visually examine the pattern and evaluate it using the following rank numbers:

1.No pattern

2. A pattern almost undetectable

3. It is very faint, so pattern must be examined very closely.

4. Diffusion Pattern

5. Faint but distinct borders

6. Easily Observable Pattern

7. Very distinct pattern

The pattern is measured quantitatively by measuring with a Joyce-Loebl MDM6 mi crodensitomer using a small slit hole (2.0 × 0.25 mm). The maximum transmitted light density difference (O.D) measured between the light and dark fringes can be seen in the examples. O.D is measured in the region scanned with an average light density between 1.0 and 2.0 with an contrast ratio of emulsion in the region of 2.5 to 3.5.

The measurement of the surface reflectance of the sample in this example is performed according to the following method:

Direct surface reflectance measurement of matted black surfaces

Samples are prepared by physical removal of the photosensitive emulsion layer and by IR absorbing the antireflective layer at the location of the photosensitive emulsion layer prior to the experiment. The untreated side of the sample is irradiated with a 5 nm diameter from a laser diode emitted at 815 nm at a 10 ° angle to the vertical plane with a known collimation line of energy. A radiation detector is used to monitor the reflected energy at an angle of 20 ° to the incident line (Optronic s type 730A). The detector is placed at a distance of 30 cm from the test surface to introduce light through a circular hole of 1 cm in diameter.

By measuring the incident energy and the reflected energy using the same detector as described above, it is possible to simply calculate the percentage of reflectance. Careful selection of the laser diode / sample film / detector type should be taken to ensure that no extra energy is measured.

In this example the irradiation of the mated surface of the sample is done according to the following method:

Runner electron microscopy of matted surfaces (S. E. M)

A sample film (about 1 cm ² ) is placed on the top of the surface to be irradiated and bonded with a pin. Golden coatings were added to International Scientific Instruments Inc. (ISI) PS-2 coating unit is used to coat approximately 25 nm thick for 2 minutes at 1.2 kV and 10 mA. Samples are observed using an ISI Super IIIA scanning electron microscope operating at 10 kV.

The angle of the sample is + 20 °. In each case, pictures are taken at 500 0x magnification using an internal calibrator. Count particles in the grit by expressing a range of 10 microns x 10 microns. Particles are counted if they protrude at least 30% or 0.2 microns or less in diameter above the average surface level of the particles. Samples with large and rare particles are taken at 2000 or less magnification and counted over a wider area.

Record average measurements from photographs of two different parts of each irradiated surface.

Example 1

Preparation of NIR-sensitive silver halide emulsions and the use of photographic materials for laser diode scanning experiments

Cubic particles with an average particle size of 0.28 microns and a narrow distribution curve are emulsions containing 64 mol% of silver chloride and 36 mol% of silver bromide according to the precipitation method described in 17B in the practice of European Patent Application Publication No. 0,088,595. (double jet).

Emulsions similar to the above having average particle sizes of 0.23 microns, 0.20 microns, 0.16 microns and 0.13 microns are prepared using lower precipitation temperatures continuously.

All these emulsions are photosensitized and stabilized golden and yellow, and NIR photosensitizers, triphenylphosphine seconds photosensitizers, wetting agents and curing agents are added as described in the practice of European Patent Application Publication No. 0,088,595 as described in 18. The emulsions are each coated on a transparent 0.18 mm internal polyester substrate to yield a coating weight of 2.7-3.0 g / m ² . A top layer of 1.33 g / m ² gelatin is obtained by simultaneously coating 200 ml of 5% water soluble gelatin with 100 mg superamide and 0.15 ml Teepol 610 wetting agent and 4.5 ml 2% formaldehyde curing agent (no mating agent or filter dye). . The back surface of the film substrate is not covered. Superamide L 9C is a high activity lauric acid-diethanolamine concentrate commercially available from Millmaster-Onyx UK. Teepol 610 is a sodium salt of secondary alkali sulphate marketed by shell Chemicals UK Ltd.

The samples were evaluated as described above and the results are described in Table 1 below.

TABLE 1

Effect of Emulsion Particle Size on Scanning Patterns

In this embodiment, it can be seen that as the particle size of the silver halide decreases, the scan pattern becomes more severe.

Example 2

Photographic material according to the invention with a backing layer containing PMMA particles and resistant to scanning patterns

0.3 g / m ² poly (methyl) coated from an aqueous solution containing the superamide L9C and Teepol 610 wetting agent and formaldehyde curing agent of Example 1 and having an average diameter of 0.5 micron in the gelatin binder (1.3 g / m ² ). The emulsion is prepared according to Example 1 above, except that a 0.18 mm polyester substrate with a backing layer containing methacrylate) particles is used, photosensitized and coated with NIR. If wet immediately after coating on the film substrate, the layer is passed through a cooling zone with a relative humidity of 13 ° C. and 30 ° C. to cure the gel and dry at about 30 ° C. and 30% relative humidity for about 1 minute. The samples were tested in a laser diode scanning system as described above and the results are shown in Table 2 below.

The coating on the emulsion having the same particle size as in Example 1 was used as a reference.

TABLE 2

Effect on the backing layer of 0.5 micron PMMA particles

Example 3

Photographic material according to the invention with a backing layer containing non-photosensitive silver halide particles

0.16 micron chloro according to the method of Example 1 above, except that a gelatin binder (1.3 g / m ² ) was used with a 0.18 mm polyester substrate equipped with a backing layer containing silver halide particles not exposed to NIR light. Cover with bromide emulsion. The effect of the scanning pattern on the different particle size and the load of the back surface particles is shown in Table 3 below.

TABLE 3

Non-photosensitive silver halide backing layer

Example 4

Starting material with backing layer containing surface roughening agent

It was coated from an aqueous solution containing superamide L9C or Teepol 610 wetting agent and formaldehyde curing agent in Example 1, and alkali-soluble methacrylic acid-ethyl methacrylate particles (average particles) in gelatin binder (1.3 g / m ² ). A 0.16 micron chlorobromide emulsion was coated according to Example 1 above on a 0.18 mm polyester substrate having a back side containing size 0.5-2.0).

Alternatively, the same sample may be prepared by using polymer particles with lower loading silica particles with an average particle size of 5 microns.

The results of experiments comparing these samples to those without backing are shown in Table 4 below.

TABLE 4

Conventional silica matting outside the scope of the present invention in terms of particle coverage does not prevent fringe formation.

Example 5

Effect of anti-halation agent on scan pattern (0.16 micron chlorobromide emulsion)

0.18 mm polyester with backing layer consisting of gelatin (5 g / m ² ) containing an anti-halation dye (dye of European Patent Application Publication No. 0,101,646), which exhibits a light density of 0.40 at 820 nm and strongly absorbs at 750-900 nm. A 0.16 micron chlorobromide emulsion is coated on the substrate according to the method of Example 1 above. The results of experiments comparing this with samples not backed in a laser diode scanning system are described in Table 5 below.

Example 6

Use of Iodobromide Emulsion

A 3% iodobromide suspension with an average particle size of 0.21 microns was prepared according to the method of Example 17A of EP 0,088,595, chemically activated, stabilized and spectrally sensitized to give a transparent 0.18 mm It is coated on a polyester substrate. Apply a protective film of 1.3 g / m ² gelatin at one time. Consisting of three continuous gelatin layers (5 g / m ² ) containing dyes of 0.45, 0.8 and 1.2 at 820 nm and strongly absorbing dyes at 750-900 nm (dye 29 in EP 0,101,646). If it is anti-halation, the above coating is performed on a 0.18 mm polyester substrate having a layer. The results of experimenting with this coating in the laser diode scanning system are described in Table 5 below.

TABLE 5

Effect of anti-halation layer (AH)

It can be seen that the anti-halation layer clearly helps to prevent the formation of patterns.

Example 7

Surface Spectral Reflectance and Relationship between Surface Roughness and Scanning Pattern Formation

The method of Example 1 above on a 0.18 micron polyester substrate with a backing layer coated with a gelatin binder (1.3 g / m ² ) as in Example 2 and containing PMMA particles of serial concentration of 0.5 micron average diameter size Coat 0.16 micron chlorobromide emulsion accordingly. These samples were tested in a laser diode scanning system and the effects on pattern formation are described in Table 6 below.

TABLE 6

Relationship between surface reflectivity and patterning reduction of surface matting effect of 0.5 micron PMMA measured by physically protruding particles

Example 8

Coating with anti-halation dyes and PMMA particles

(a) anti-halation dyes and conventional matting agents

A chlorobromide emulsion of 0.26 micron particle size was prepared and photosensitive according to the method of Example 1 above. The emulsion is coated on a 0.18 mm polyester substrate with a 2.4 g / m ² silver cover and simultaneously coated with a thin gelatin protective film containing 0.036 g / m ² PMMA particles (average diameter of 2.5 microns). The opposite side of the substrate has a gelatin protective film (1.3 g / m ² ) containing 0.065 g / m ² PMMA particles (back layer) with an optical density of 0.6 at 815 nm and a size of 6 micron average diameter. A gelatinous layer (5 g / m ² ) containing an infrared absorbing dye (dye 17 in European Patent Application Publication No. 0,101,646) having an infrared absorption of 750-900 nm is provided. This coating was tested in laser diode scanning and the results are shown in Table 7.

(b) anti-halation dyes and surface roughening agents according to the present invention;

The coating of (a) is repeated while adding 0.18 g / m ² 0.5 micron PMMA spheres to the front and protective layers. The samples were tested by laser scanning and the results are shown in Table 7.

TABLE 7

Sample (a) shows visible, non-contact scanning patterns, while sample (b) shows no non-contact scanning patterns under laser diode scanning experiments under the most stringent conditions.

Example 9

Photographic material having an outer matting layer containing alkali-soluble copolymer particles

Alkali-soluble methacrylic acid-ethyl methacrylate copolymer particles in a gelatin binder (1.3 g / m ² ) were coated from an aqueous solution containing superamide L9C and Teepol 610 wetting agent, formaldehyde curing agent as in Example 1 above. The 0.16 micron chlorobromide emulsion was coated on a 0.18 mm polyester substrate with a backing containing. Copolymer particles have a mean particle size of 0.75 microns but a wide range of diameters up to 2 microns. The results of experiments on the pattern formation comparing the samples containing different concentrations of matting agents with the backless samples are shown in Table 8.

TABLE 8

The degree of suppression in which fringe formation is suppressed depends on the surface density of the protruding particles produced by the matting agent and the type of structure. In addition, as in Example 5, coating was performed by a similar method using a 0.18 mm polyester substrate coated on one side with an infrared ray absorption anti-halation layer. The matting layer is applied directly to the anti-halation layer and a photosensitive emulsion is applied to the opposite side of the film substrate.

The same chlorobromide on the backside-free 0.18 mm polyester substrate as in Example 1 above was subjected to the third set of coatings as in Example 1 above, except that it was repeated by mating suspension of copolymer particles as described above instead of a commercial emulsion topcoat. It is carried out in an emulsion.

The coating with the backside matting on the anti-halation layer and the coating with the upper coating on the emulsion for the emulsion were tested in laser diode scanning and the results are shown in Table 8.

Claims (16)

(i) a protective film layer on the same outermost side of the support as a photosensitive emulsion and diffusely transmitting to near infrared rays, (ii) on the outermost side of the support away from the photosensitive emulsion and diffused or absorbed against a new infrared ray Consisting of one or more layers of a backing layer, (iii) an inner layer that is located between the support and the photosensitive emulsion and that diffuses or absorbs near-infrared light, and is almost non-contacted by a laser scanning system that emits near-infrared light. A photographic material comprising one or more halogenated silver emulsion layers having an average diameter of 0.4 micron or less, the photosensitive material being formed by a near infrared ray, and a support that is projected by near infrared rays. The method of claim 1, wherein the material contains at least 250,000 particles per surface of 1 mm ² protruding beyond the particle average surface level by 30% or 0.2 micron or less of each particle diameter so that the surface of the surface is microscopically rough. A photographic material comprising a backing layer comprising a binder containing a surface roughening agent having an average particle size of 2 microns or less. 2. The material of claim 1, wherein the material comprises at least 300,000 particles per 1 mm ² of layer surface protruding at least 30% of each particle diameter, or 0.2 micron or less, above the surface level, and the outer surface is microscopically rough. And a protective film layer containing a binder containing a surface roughening agent having an average particle size of 2 microns or less. The surface of claim 1 wherein the surface is microscopically rough so as to contain at least 450,000 particles per 1 mm ² of surface, protruding above the average level of the surface by at least 30% of each particle diameter, or by 0.2 microns or less. Photographic material made with. 2. The photographic material of claim 1, wherein the material comprises a backing or inner layer containing an anti-halation dye that absorbs in the near infrared and exhibits a light peak of at least 0.75 light density in the near infrared range. 2. The material of claim 1, wherein the material comprises a backing layer containing a surface roughening agent having an average particle size of less than 2 microns of an antihalation dye showing an optical density light peak of at least 0.3 with respect to near infrared light. Surface is microscopically microscopically containing at least 200,000 particles per 1 mm ² surface of each particle diameter protruding above the average level of the surface by 30% or 0.2 microns or less. The material of claim 1, wherein the material comprises a backing layer showing a light density light peak of at least 0.3 with respect to near infrared rays, and a protective film layer containing a surface roughening agent having an average particle size of 2 microns or less. And the surface is microscopically rough, containing at least 200,000 particles per 1 mm ² of surface, protruding beyond the average level of the surface by at least 30% of each particle diameter, or by 0.2 microns or less. 2. The material of claim 1 wherein the material comprises a backing layer or protective layer containing an antihalation inner layer exhibiting a light density light peak of at least 0.3 for near infrared light and a surface roughening agent having an average particle size of less than 2 microns. The outer surface of the back surface or the protective film layer is microscopically coarse, containing at least 200,000 particles per surface of 1 mm ² protruding above the average level of the surface by at least 30% of each particle diameter, or 0.2 micron or less. Photo material characterized by. The method of claim 1, wherein the material contains at least 200,000 particles per surface of 1 mm ² protruding beyond the average level of the surface by at least 30% or 0.2 microns or less of each particle diameter so that the outer surface is microscopically rough. A protective film layer containing a surface roughening agent having an average particle size of 2 microns or less, and at least 200,000 particles protruding above the average level of the surface by 30% of each particle diameter, or 0.2 microns or less, per 1 mm ² surface. A backing layer containing a surface roughening agent having an average particle size of 2 microns or less so that the outer surface is microscopically rough, and an inner layer containing an anti-halation dye exhibiting a light density light peak of at least 0.3 to infrared light. Photo material, characterized in that consisting of. The material of claim 1, wherein the material consists of a backing or protective layer comprising a binder containing particles having a reflectance substantially greater than that of a binder having an average particle size of 5 microns or less, the layer being photographic. Photographic material characterized in that it can be removed during. 11. The photographic material of claim 10, wherein the material is sensitive to radiation in the 750-900 nm wavelength range. 10. The photographic material of any one of claims 1 to 3 or 5 to 9, wherein the average size of the roughener particles is 0.2-2 microns. 10. The photograph of claim 1, wherein the roughening agent is selected from poly-methylmethacrylate and copolymers of methacrylic acid and methyl or ethylmethacrylate. material. 11. The photographic material of claim 10, wherein the average particle size of the material with high reflectance is 0.2-3 microns. 15. The photographic material of claim 14, wherein the material having a high reflectance is selected from halogenated, zinc oxide and calcium carbonate. Exposing the photomaterial of the preceding paragraph to near infrared from a laser diode scanning system located on an emulsion surface of the photo material without contact with another surface, and developing the material upward. Award recording method.