JPH0610735B2 - Near-infrared photosensitive photographic element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention has a spectrum of 750 nm and above (preferably 750 nm).
To 1500 nm) in the near-infrared region and more particularly to photographic elements suitable for providing high quality recording media for laser diode scanning systems.

BACKGROUND OF THE INVENTION A widely used image processing technique is to convert the visible image into electronic information by encoding the intensities of a plurality of small adjacent areas of the visible image. Such electronic coding is advantageous for manipulating, transmitting and storing images, it is known to reconvert that electronic information into a visible image by means called a "scanner system", whereby a finely focused light beam. Is rapidly scanned across the tourist medium with adjacent raster scan lines in succession while modulating the light intensity to reproduce the required image density based on the electronic signal.

Lasers, especially those using argon, krypton, helium-neon or helium-cadmium mixtures as gas laser media, have been used as high intensity light sources for this imaging technique. However, each of these lasers suffers from the additional requirement of a complex device for modulating the emission intensity and of having a more or less large physical volume, mechanical fragility and manufacturing costs.

Semiconductor laser diodes are potentially well suited as light sources for Scanner systems, whose light output can be directly modulated by an electrical signal input, yet are very compact and physically durable.

However, at present, the only commercially available laser diode device that has an acceptably long operating life and can be manufactured cheaply is the near infrared (N) region of the spectrum 750 to 1500 nm.
It emits light in the (IR) part. Therefore, in order to use the laser diode scanner system for image formation, it is necessary to prepare a recording medium sensitive to light in the NIR range.

It is known to spectrally sensitize silver halide photographic emulsions to near infrared light with long-chain cyanine dyes: eg The Theory of the Photographic Process.
(The Theory of the Photorgraphic Process) 3rd edition (Macmillan, 1966) pp. 198-201.

NIR-sensitized photographic films, especially those having silver halide grains with an average diameter of less than about 0.4μ, are supported at the edge of a glassless holder and out of contact with other surfaces and 8
Wide spiral interference pattern when exposed uniformly from a laser diode-scanner system that emits light at 20 nm (hereinafter referred to as "non-contact skiner interference fringes")
Results in an image covered with. It is believed that these interference fringes result from the exposure light rays being reflected from the two interfaces between the film element and the ambient air. The path difference between the rays reflected from the top and bottom surfaces of the film is dominated by the film thickness at a given point, and the net phase difference causes either destructive or constructive interference, It reduces or increases the exposing light transmitted into the light-sensitive emulsion layer at a given point. Therefore, the fringes follow the contour lines of the microscopic thickness variations of the film element itself, and cover the entire image area with wide lines, often about a few cm long, usually about 1 mm apart.

Non-contact interference fringes have not previously been reported in the literature for silver halide emulsions. This development does not occur under normal exposure conditions with visible light. This is because the turbidity of the photosensitive emulsion layer is sufficient to scatter the reflections from the backside of the film element. However, because of its long wavelength, infrared light can pass through the fine grain photographic emulsion without severe scattering, yet the coherence of the laser diode output enhances the tendency to form interference patterns. Therefore,
Having silver halide grains having an average diameter of 0.28μ, 3 g /
Photographic emulsions with a silver coverage of m ² show detectable interference fringes. Reducing the grain size to 0.23μ or reducing the coverage produces a more pronounced pattern, with emulsions with an average grain diameter of 0.20μ or less exhibiting strong interference fringes after non-contact laser diode scanning.

Non-contact Scanner interference fringes significantly degrade the quality of Scanner images, especially those with continuous tones. Not only are they aesthetically problematic, they obscure important information represented by small density differences in the image. It is desirable to be able to use photographic emulsions having a grain size with an average diameter of less than 0.4μ, preferably less than 0.3μ. Fine grain emulsions having a grain size of less than 0.4μ are advantageous in that they allow high spatial resolution and, because they have high coating power, they can have a low silver coverage for a given maximum optical density and development. . Therefore, photographic elements for use with laser diode scanning systems must be capable of suppressing non-contact interference fringes.

This phenomenon of interference fringes is not known in the optical recording system.
A common problem when exposing a photographic film with a glossy surface to contact with another glossy surface, such as a glass support, halftone screen or contact printing negative, is the narrow spacing known as the "Newton ring". Concentric interference fringe pattern of the image is generated in the developed image: Encyclopedic Dixonary of Physics (E
ncyclopedic Dictionary of Physics), J. See Theuris Edition, Pergamon, London, 1961, p. 878. This interference fringe is caused by optical interference between the reflection from the top of the film and the reflection from the bottom of the contact support: the size of its local air gap determines the path difference between these two sets of rays, and thus their It is determined whether the retardation causes light or dark streaks that cause additional or depleted exposure in the emulsion layer. The Newton ring tends to form a pattern of isolated areas that radiate concentrically and radially from the contact point during exposure, with narrow stripe spacing that gradually narrows toward the periphery of each pattern. These are quite different in appearance from the broad spiral non-contact Scanner interference fringes which cover the entire image area with wide lines, which are usually about 1 mm and often several cm long.

It is known how to prevent the occurrence of the Newton ring.
For example, it is known to introduce matte particles on the outer surface of the film. Examples of known matte particles are silica, polymethylmethacrylate (PMMA), other polyvinyl compounds including copolymers, starch, inorganic salts and the like. This matte coating density is US Pat. No. 4,235,959,
Relatively small amounts of fairly large particles, typically 5-10 .mu.m in diameter, such as those disclosed in 4,022,622, 3,754,924, and 2,322,037 (e.g., 0.1 g / (applied below m ² ) to British Patent Specification Nos. 2,077,935 and 2,033,59
No. 6, and US Pat. Nos. 3,507,678 and 2,992,101, utilizing up to 1 g / m ² or more than 50% of the topcoat binder utilizing smaller particle sizes. The particle weight can vary.

Both emulsions produce particularly severe Newton Ring fringes when visible laser light is used as the illumination for contact screen exposures. U.S. Pat. No. 4,343,8
No. 73 discloses a photographic element designed to minimize such interference fringes, which photographic element has a light scattering layer through which the photosensitive layer is exposed to laser light. It The light-scattering particles have a wavelength of 50-
It has a diameter of 150%. The light-scattering layer may be coated as an outer layer on the photographic element or underneath other layers.

It is also known to use matting agents in photographic elements to obtain non-optical properties such as adhesion resistance, abrasion resistance, correctability, good sag in a vacuum frame, and reduced charging effects. There is. An example of the use of a matting agent is an infrared sensitive film as disclosed in U.S. Pat. No. 4,266,010, which has a size of 0.2-10 .mu.m in an acid-treated gelatin binder. Emulsion topcoats containing a range of PMMA have been described and stated to be suitable for all types of photographic materials including infrared films. Another example is US Pat. No. 3,695,888.
And a photographic emulsion sensitized to infrared light by a cyanine dye having a mesoalkylamino substituent and a specific supersensitizer are disclosed therein.
Such elements include matting agents such as starch, titanium dioxide, zinc oxide, silica, US Pat. No. 2,992,101.
Methacrylic acid-methyl methacrylate copolymer beads as disclosed in U.S. Pat. Polymer beads, including methyl methacrylate beads, can be included.

However, known types of layers used in photographic elements to suppress Newton's rings prevent the formation of non-contact interference fringes in photographic elements having near infrared sensitized fine grain size photographic emulsions. It turned out not to.

SUMMARY OF THE INVENTION According to the present invention, there is a support transparent to near infrared rays in the range of 750 nm or more, generally in the range of 750 to 1500 nm, and a particle size sensitized to the near infrared rays of 0.4 μm or less in average diameter. A photographic element comprising one or more layers of silver halide emulsion, further comprising (i) an outermost layer on the same side of the support as the photosensitive emulsion and a diffuse transmission layer for near infrared rays. A topcoat layer, (ii) a backing layer which is the outermost layer on the side of the support opposite to the photosensitive emulsion and is a diffuse reflection layer or absorption layer for near infrared rays, (iii) support And a photosensitive emulsion and have at least one subbing layer that is a diffuse transmission or absorption layer for near infrared rays, and thus is substantially non-existent by a laser scanning method for generating near infrared rays. Images can be formed without forming contact interference fringes. The photographic elements are provided, characterized and.

The photographic element of the present invention provides a laser diode NI despite the fact that the film and other surfaces are not in contact during exposure.
It is resistant to the generation of internal optical interference patterns that cover the unprotected near-infrared photosensitive fine grain film with wide spiral fringes when developed after scanning with the R light source.

We have invented three main approaches to prevent the formation of non-contact interference fringes. These techniques can be used alone or in combination.

It has been found that the microscopic surface roughness of photographic elements can play an important role in suppressing the formation of interference fringes. Microscopic surface roughness with 200,000 protrusions per mm ² significantly reduces the formation of interference fringes, and 1
The surface roughness of the backside of the film with 250,000 protrusions per mm ² eliminates the interference fringes substantially completely, resulting in 250,000 per mm ² on the top surface (preferably 450,
The same applies to the surface roughness having more than 000) protrusions.

A second technique for suppressing the formation of interference fringes is to provide a backing layer or an undercoat layer containing a dye that absorbs light in the wavelength range of the exposure light source. When such a layer is used alone as an interference fringe suppression layer in the means of the present invention, the layer should have a peak transmission optical density of at least 0.75; such a layer in combination with other interference fringe suppression means. Optical density of at least 0.3 significantly contributes to the reduction of interference fringes.

A third approach to reducing interference fringe formation consists of a binder containing particles having a high reflection index, substantially preferably particles having a high reflection index greater than or equal to 0.3 greater than that of the binder ( The use of a backing layer and / or a topcoat layer (comprising desensitized silver halide grains in gelatin, for example).

The use of silver halide grains is advantageous because silver halide is removed during processing of the photographic element. The high reflection index layer is preferably removed after exposure, for example by applying a binder solvent.

It has been discovered that there are several types of structures in the near-infrared light-sensitive micrograph element that substantially completely suppress the generation of non-contact interference fringes. For example, non-contact interference fringes are suppressed in such photographic elements that embody one or more methods into the following structures: (1) on the side opposite the film-based photosensitive emulsion,
A backing layer comprising a binder containing a surface-roughening agent having an average particle size of 2 μm or less (generally in the range of 0.1 to 2 μm, preferably 0.2 to 2 μm).
^At least 30% of the individual diameters of the particles, or 0.2μ, from the mean horizontal plane of its surface, whichever is smaller, at least 250,00
It has an outer surface with a microscopic roughness such that it contains zero particles.

(2) On the same side as the film-based photosensitive emulsion,
Average particle size 1.5 μm or less (generally 0.1-1.
5 μ, preferably 0.2 to 1.5 μ) of a binder containing a surface-roughening agent, the top coat layer being in each mm ² of its outer surface from the mean horizontal plane of the surface of the individual particles. Only at least 30% of the diameter or only 0.2μ of microscopic roughness such that it contains at least 250,000, preferably at least 450,000, protruding particles, whichever is smaller. Has an outer surface.

(3) 750 nm or more, preferably 750 to 150 in wavelength range
Backing or subbing layer containing an antihalation dye absorbing 0 nm light and having a peak transmission optical density in that region of at least 0.75.

(4) 750 nm or more, preferably 750 to 150 in wavelength range
A roughening agent containing an anti-halation dye which gives a peak transmission optical density of at least 0.3 with respect to 0 nm light and having an average particle size of 2 μ or less, generally in the range of 0.1 to 2 μ, preferably 0.2 to 2 μ. The outermost backing layer containing, this layer being within each mm ² of its outer surface from the mean horizontal plane of that surface only at least 30% of the individual diameter of the particles or only 0.2μ, which It has an outer surface of microscopic roughness such that it contains at least 200,000 protruding particles, even if small, this layer optionally comprising two separate layers, namely a rough surface. It may be divided into an outermost backing layer containing an agent and an inner backing layer containing an anti-halation dye.

(5) 750 nm or more, preferably wavelength range 750 to 150
A backing layer having a peak transmission optical density of at least 0.3 for light of 0 nm; an average particle size of 2μ or less, generally in the range 0.1 to 2μ, preferably 0.2 to 2μ The outermost topcoat layer (this layer is in each mm ² of its outer surface at least 30% of the individual diameters of the particles from the mean horizontal plane of that surface or 0.2
Only μ has an outer surface of microscopic roughness such that it contains at least 200,000 protruding particles, whichever is smaller).

(6) Located between the photosensitive layer and the base, 750 nm or more,
Preferably an anti-halation layer containing an anti-halation dye which gives a peak transmission optical density of at least 0.3 for light in the wavelength range 750 to 1500 nm; an average particle size of 2 μm or less, generally in the range 0.1 to 2 μm, preferably 0. .1～2Myu, the diameter of the roughening agent most contains an outer backing layer or Totsupukoto layer (this layer is the average horizontal plane of the surface in each mm ² of the outer surface of individual particles thereof At least 30% or only 0.2μ, whichever is smaller, at least 200,
With an outer surface of microscopic roughness such that it contains 000 particles).

(7) Average particle size 2μ or less (generally in the range 0.1-2
μ, preferably 0.2 to 2 μ) of a surface-roughening agent (this layer being in each mm ² of its outer surface from the mean horizontal surface of the surface at least 30 of the individual diameters of the particles).
% Or only 0.2μ has an outer surface of microscopic roughness such that it contains at least 200,000 protruding particles, if either is small); the average particle size of 2μ or less (typically in the range 0.1～2Myu, preferably 0.2～2Myu) of backing layer (the layer containing the roughening agent of the surface in each mm ² of its outer surface Only at least 30% of the individual diameters of the particles from the mean horizontal plane, or only 0.2μ, out of the microscopic roughness such that they contain at least 200,000 protruding particles, whichever is smaller. A surface)); and, optionally, provided between the backing layer and the support to provide a peak transmission optical density of at least 0.3 for light in the wavelength range of 750 nm or greater, preferably in the wavelength range 750 to 1500 nm. Contains anti-halation dye Layer and that; a combination of.

(8) A backing layer and / or a top coat layer made of a binder containing particles having a reflection index substantially larger than that of the binder (for example, non-sensitized silver halide grains), the particles being less than 5 μm, preferably Is 0.2 to 3
having an average particle size of μ, the layer is removable during photographic processing.

It has been found that the microscopic roughness of photographic elements significantly affects the tendency of contactless fringe formation when the element is imaged by a scanning laser. In particular, an outer backing layer is provided to provide microscopic roughness having at least 250,000 protrusions / mm ² protruding from the horizontal surface of the surface, and the element is exposed from the opposite side to prevent interference fringe formation. It became clear. Similarly, at least 250,000 interference fringes are formed per mm ² , preferably 450,0.
This can be prevented by providing a top coat layer having a microscopic surface roughness that gives 00 projections. In this case the element shall be illuminated from the same side as this layer. This microscopic surface roughness is significantly different from that found in photographic elements with conventional matte layers: Generally, conventional matte layers result in less than half the number of protrusions required for this invention. There is a tendency, often 1 / of the number of surface protrusions used in the present invention.
It has a number of protrusions of less than 10.

Interference fringe formation can be substantially suppressed by using a backing or subbing layer containing an antihalation dye that imparts a peak transmission optical density of at least 0.75 in the 750 to 1500 nm range.

A combination of a roughening layer and an anti-halation layer may be used as described above, in which case the critical parameters of surface roughening and optical density of the individual layers are such that the effect of the layer combination is additive. Therefore, such layers may be reduced relative to those required when used alone as a means to reduce interference fringe formation. It has been found that a suitable microscopic surface roughness for the outer layer used in combination with another interference fringe suppression layer is 200,000 protrusions / mm ² .
The optical density required for the antihalation layer used in combination with the roughening layer is at least 0.3.

The grain-containing surface layer is preferably used on the backside of the photographic element, or on the outermost surfaces of both sides, rather than as a topcoat on the photosensitive emulsion side only. This is because, surprisingly, the suppression of non-contact laser scanner interference fringes by rough backing is superior to the suppression by a similar topcoat on the emulsion side. In this case, the exposure is performed from the emulsion side.

Roughening agents which are advantageous for use in such layers are particles of organic polymers, especially polymethylmethacrylate or particles of a developer-soluble polymer such as methacrylic acid / methacrylic acid ester copolymer (see, for example, US Pat. , 992, 10
No. 1)). Other suitable organic polymers when used in the particle size ranges and loadings required to impart the matte properties detailed above are other polyvinyl compounds or vinyl compound copolymers (e.g., British Patent Specification). Nos. 2,078,992 and 2,033,596, and US Pat. Nos. 4,287,299 and 3,079,257). Other suitable materials are silica or silica / polymer composites (eg, US Pat. Nos. 4,235,959, 3,920,45).
No. 6, No. 3,591,379 and No. 3,222,0
Hardened gelatin, water-soluble inorganic salts, or starch, dextran, and mixtures of these polymers (as described in British Patent Specification 2,077,935). It is).

One type of known matting agent generally consists of very small silica particles with a diameter of 0.1 μm or less. When dispersed in a coating binder such as water-soluble gelatin, these microparticles generally form tightly bound agglomerates with a diameter of 1 μm or greater, and they behave as if they were single particles. The matte properties required for the present invention may be achieved either by the use of single particles within the required size range or also by the use of agglomerates, the overall size being the same required range. to go into.

A suitable material with a high reflection index is a non-photosensitive silver halide crystal, which is easily manufactured to uniform size and yet removed by a photographic fixer. Silver halide is generally 2.
It has a reflection index in the range of 0 to 2.2. Other suitable high reflection index materials include zinc oxide and calcium carbonate.

Gelatin is a suitable binder for all these layers and has a reflection index of about 1.5.

When using small polymer particles or other particles to matte the binder layer and the surface when coated, the height of the protrusions from the average horizontal surface of the surface and the number of protruding particles are included in the layer. The weight of the particles present as well as the coating and drying conditions used. It is important to select the coating and drying conditions that produce the high degree of particle protrusion required by the present invention, and these parameters will be apparent to those skilled in the art. One technique that has been demonstrated to produce satisfactory surface roughness when using a suitable formulation is to wet the wet element immediately after coating at 13 ° C and 30% relative humidity.
The gel is solidified by passing through the cooling zone of 3 and dried at 30 ° C. and 30% relative humidity. It was found that the thin layer dried in 30 seconds to 1 minute.

In addition to the matte particles introduced for roughening according to the present invention, the photographic elements of the present invention include large particles having an average diameter of 5 μm or more to improve mechanical properties such as adhesion resistance and abrasion resistance. Small amount of polymer, silica and other matting agents (0.1
(less than g / m ² ).

The silver halide emulsions useful in the photographic elements of this invention are silver bromide,
It may consist of silver chloride, silver chlorobromide, silver bromoiodide, or silver chlorobromoiodide, for example Research Disclosure 17643 (December 1978), Stages II and II.
It can be made by any of the well known procedures such as those described in Section I. Emulsions less than 0.4μ, generally range 0.0
It has a particle size of 5 to 0.4 μ.

Emulsions are described using the dyes disclosed in European Patent Application Publication No. 0088595, or as described, for example, in The Theory of the Photographic Process, 3rd Edition, pages 198-199, by Mies and James. 750 to 1500 nm (preferably 750 to 900 nm)
It can be sensitized to the near infrared using any of the other spectral sensitizing dyes known in the art to impart sensitivity to electromagnetic waves of (nm).

The silver halide emulsions present in the photographic elements of this invention can be prevented from fog and can be stabilized against loss of sensitivity during storage. Suitable antifoggants and stabilizers are described, for example, in Research Disclosure 17643 (December 1978) Part VI.

The silver halide emulsions present in the photographic elements of this invention are, for example, Research Disclosure 17643 (1978).
December 2013) Optical brighteners as described in column V can be used.

The spectrally sensitized silver halide emulsions used in this invention can contain speed-increasing compounds such as those described in Research Disclosure 17643 (December 1978) stage XXI.

The layers of the photographic element are vehicles or binders such as colloids such as Research Disclosure 1764.
3 (December 1978), IX, IX. Such colloids can be hardened by various organic and inorganic hardeners, such as those described in Research Disclosure 17643 (December 1978) Stage X.

Photographic elements of this invention include antistatic or conductive layers, plasticizers and lubricants, surfactants such as Research Disclosure 17643 (December 1978) Stage XI, XI.
Stage I, and those as described in stage XIII can be included.

The photographic emulsions used in the present invention can be a wide variety of transparent supports such as Research Disclosure 17643.
(December 1978) those described in stage XVIII, can be coated.

The sensitizing dye and other emulsion additives can be prepared by a known method such as Research Disclosure 17643.
(December 1978) Method described in stage XIV,
Can be incorporated into the layers of the photographic element. Similarly, the photographic element can be coated on the photographic support by a variety of procedures. Supports and coating procedures are described, for example, in Research Disclosure 17643 (December 1978) No. XV.
Columns and stages XVII.

The sensitized silver halide emulsions used in the present invention are exposed to light to form a visible silver and / or dye image, such as Research Disclosure 17643 (1978 1
February) It can be processed by combining the silver halide with an aqueous alkaline medium in the presence of a developer as described in stage XIX.

Although the present invention is described in detail with respect to elements containing silver halide grains of 0.4 μm or less in diameter, this method of suppressing interference fringes is equally applicable to elements containing other light-sensitive silver halide emulsions. Yes, such a factor limits the formation of Skiener fringes due to low turbidity. In particular, the present invention is
Applicable to elements containing high aspect ratio tabular grains of silver halide having a diameter greater than 0.4 .mu.m: In particular, those grains are present in low proportion to the total silver halide grains in the element and the balance is fine grain. Applicable when

The photographic elements of the present invention are, for example, Research Disclosure 17643 (December 1978) Stages XXII, XXIII.
Stage, XXIV stage, XXV stage, XXVI stage, and XXVII stage, physical development system, image transfer system, dry development system, diffusion transfer system, printing and lithographic printing, printing and direct printing. Effective for printing method. Next, the present invention will be described with reference to examples.

Evaluation of samples in the examples was carried out as follows: Evaluation of samples by non-contact laser diode scanning,
And the measurement of interference fringes: The samples were evaluated by uniform exposure of the sample with a Scanner system such that the electromagnetic waves from a Hitachi HLP1400 laser diode emitting at 815 nm were focused on the sample surface with a circular spot of diameter 50μ. The focusing spot was scanned on the sample in a 200 / cm rafter pattern by a vibrating mirror in the path of the infrared beam. The exposure illuminance was stepwise increased to produce a minimum to maximum density scale on the sample after processing. The sample was then developed by an automated roller processor 3M type XP507 utilizing an Eastman Kodak RPX-O Matting solution. The fringe pattern was evaluated by visual inspection with the following ratings: No visible interference fringes 2. Interference fringes that are almost undetectable 3. Very weak, only seen under close examination 4. Diffusion pattern 5. Weak but clear interference fringes 6. Easy-to-see interference fringes 7. Clear interference fringe patterns The interference fringe patterns were evaluated quantitatively by following them on a Joice-Rable MDM6 microdensitometer using a small (2.0 x 0.25 mm) slit aperture. The maximum transmission optical density difference (OD) between the light and dark fringes thus measured is given in the examples. O. D. Was measured in areas scanned to give average optical densities of 1.0 to 2.0 in the range where the emulsions have contrast values of 2.5 to 3.0.

The measurement of the surface reflectance of the samples in the examples was carried out as follows: Measurement of the direct (positive) surface reflectance of the matte backside The sample physically removed the photosensitive emulsion layer prior to testing and its removal. Was prepared by providing an IR highly absorbing non-reflective layer. The surface of the sample opposite to the treated surface was then irradiated with a parallel beam of known energy with a diameter of 5 mm from a laser diode emitting at 815 nm at an angle of 10 ° to the normal. A radiation detector was used to monitor the reflected energy at all angles of 20 ° to the incident beam (Opttronics model 730A). The detector was placed 30 cm from the test surface and the light was passed through a circular aperture 1 cm in diameter.

Since both the incident energy and the reflected energy were evaluated using the same detector, the reflectance (%) could be obtained by a simple calculation. Care was taken in choosing the laser diode / sample film / detector arrangement to ensure that all external energy was rejected during the measurement.

Inspection of the matte surface of the samples in the examples was carried out as follows: Scanning Electron Microscopy (SEM) of the matte surface The film sample (about 1 cm ² ) was the surface to be inspected. I put it on the top with a pin. A gold coating of about 25 nm thickness was applied at 1.2 kV and 10 mA for 2 minutes using an International San Entwick Instruments (ISI) PS-2 coating unit. The sample was examined with an ISI Super IIIA Scanning Electron Microscope operating at 10 kV. The sample was placed at an angle of + 20 °. In each case, a photograph was taken with an internal scale at a print magnification of 5000x. Particle coefficient is 10μ × 10μ
In the grid representing the area of Particles were counted when they appeared protruding from the mean horizontal plane of the surface by at least 30% of their diameter or by 0.2μ, whichever was smaller. For samples where only large particles are scattered, the photo is 2000x
The following magnifications were taken and counting was done over a wider area.

The resulting report is the average of the coefficient values obtained from photographs of two different areas of each surface examined.

Example 1 Preparation of NIR-sensitive silver halide emulsions and their use in photographic elements for laser diode scanner testing: 64 moles of silver chloride and odor with cubic grains having an average grain size of 0.28μ and a narrow distribution curve. An emulsion containing 36 moles of silver halide was prepared by the double jet precipitation method described in Example 17B of European Patent Application Publication No. 0088595.

0.23μ, 0.20μ, 0.16μ, and 0.13
Similar emulsions with an average grain size of μ were similarly prepared by successively lowering the precipitation temperature. All of these emulsions are gold and sulfur sensitized and stabilized as usual, and further, NIR spectral sensitizing dyes, triphenylphosphine supersensitizers, wetting agents, and hardeners are European patents. It was added as described in the basic formulation in Example 18 of Application Publication No. 0088595. The emulsions were each coated onto a clear 0.18 mm subbed polyester base to give a silver coverage of 2.7-3.0 g / m ² . 2% of 100 mg of Superamide L9C, 0.15 ml of TAIPOL 610 wetting agent and formaldehyde hardener
A supercoat of 200 ml of 5% aqueous gelatin containing 4.5 ml of solution but no matting agent or filter dye was simultaneously applied to provide a top layer of 1.33 g / m ² of gelatin. The backside of the film base remained uncoated. Superamide L9C is a highly active lauric acid-diethanolamine condensate commercially available from Millmaster-Onix UK. Teipol 610
Is a sodium salt of a secondary alkyl sulphate commercially available from Ciel Chemicals UK.

The sample was evaluated as described above. The results are shown in Table 1.

This example demonstrates that the Scanner interference fringes increase sharply with decreasing silver halide grain size.

Example 2 Scanner interference fringe resistant photographic element of the invention having a backing layer containing PMMA grains An emulsion was prepared, NIR sensitized and coated as in Example 1. However, a gelatin binder (1.3 g / m ² ) was used for the 0.18 mm undercoated polyester base used.
Poly (methyl methacrylate) with an average diameter of 0.5μ
A backing layer containing particles 0.3 g / m ² is provided,
It was coated as in Example 1 from an aqueous solution that also contained Superamide L9C, Taepol 610 wetting agent and formaldehyde hardener. Immediately after coating on the film base, the wet backing layer was briefly passed through a cooling zone at 13 ° C. and 30% relative humidity to solidify the gel and then 3
Drying was done at 0 ° C. and 30% relative humidity, but the drying appeared to be complete within about 1 minute. The samples were tested on a laser diode scanner system as described above. The results are reported in Table 2.

A coating of the same grain size emulsion of Example 1 serves as a control.

Example 3 Photographic Element of the Invention with Backing Layer Containing Light-Insensitive Silver Halide Grains A 0.16μ silver chlorobromide emulsion was coated as in Example 1. However, the 0.18 mm polyester used was provided with a backing layer containing near infrared light insensitive silver halide grains in a gelatin binder (1.3 g / m ² ). The effect of different backing particle sizes and loadings on the Scanner fringes is reported in Table 3.

Example 4 Photographic Element with Backing Layer Containing Other Roughening Agent A 0.16μ chlorobromide emulsion was coated as in Example 1. However, the 0.18 mm undercoated polyester base used was particles of an alkali-soluble methacrylic acid-ethyl methacrylate copolymer (average particle size 0.5 to 2.0 μ) in a gelatin binder (1.3 g / m ² ). Having a backing containing, which was coated from an aqueous solution containing Superamide L9C or Taypol 610 wetting agent and a formaldehyde hardener as in Example 1 as in Example 1. The same sample was prepared except that the polymer particles were replaced by a low loading of silica particles with an average diameter of 5μ. These samples were tested against the unbacked ones. The results are reported in Table 4.

Conventional silica matting, where the particle coating is outside the scope of the present invention, does not prevent interference fringe formation.

Example 5 Effect of anti-halation backing on Scanner interference fringes Consisting of 5 g / m ^{2 of} gelatin containing an anti-halation dye (dye 29 of EP 0101646) which strongly absorbs at 750-900 nm and 0.40 at 820 nm.
A 0.16 micron silver chlorobromide emulsion was coated as in Example 1 on a 0.18 mm subbed polyester base with a backing having an optical density of. This was tested in comparison with the unbacked sample in a laser diode scanner system.
The results are reported in Table 5.

Example 6 Use of Silver Iodobromide Emulsion A 3% silver iodobromide emulsion having an average grain size of 0.21μ was prepared, chemically sensitized, stabilized and spectrally dispersed according to Example 17A of European Patent Application Publication No. 0088595. It was sensitized and coated on a clear 0.18 mm subbed polyester base. A topcoat of gelatin 1.3 g / m ² was applied simultaneously.

0.45, 0.8 at 820 nm consisting of up to 3 consecutive layers of gelatin (5 g / m ² ) containing a dye strongly absorbing at 750-900 nm (dye 29 of EP 0101646). , As well as a 0.18 mm polyester base with an anti-halation backing giving an overall optical density of 1.2. These coatings were tested on a laser diode scanner system. The results are reported in Table 5.

Certain anti-halation layers obviously help suppress interference fringes.

Example 7 Relationship between formation of Scanner interference fringes and regular reflectance and roughness of surface Gelatin binder containing a series of concentrations of PMMA particles (average diameter 0.5 μ) (1.3 g /
0.18μ with a backing layer coated in m ² )
A 0.16μ silver chlorobromide emulsion was coated as in Example 1 using the subbed polyester base. The effects on interference fringe formation when these samples are tested in a laser diode scanner system are reported in Table 6.

Example 8 Combination of antihalation dye coating and PMMA particle coating, (a) Antihalation dye and conventional matting agent only.

A silver chlorobromide emulsion having a grain size of 0.26 µ was prepared and sensitized by the method of Example 1. This emulsion was coated on a 0.18 mm polyester base with a silver coverage of 2.4 g / m ² and at the same time
A thin gelatin (1.3 g / m ² ) topcoat containing 0.036 g / m ² PMMA particles with an average diameter of 2.5 μ was applied. On the opposite side of the base, an infrared absorbing dye that absorbs infrared light at 750 to 900 nm (European Patent Application Publication No. 0101
No. 646 dye 17) and has an optical density of 0.8 at 815 nm.
Gelatin having 6 (5 g / m ² ) and P having an average diameter of 6 μ
MMA particles 0.065 g / m ² gelatin shoulder stop coat containing (1.3 g / m ²⁾ was (backing layer) are provided. The coating was tested with a laser diode scanner.
The results are reported in Table 7.

(b) Combination of antihalation dye and roughening agent according to the present invention 0.18 g / m ^{2 of} 0.5 μPMMA spheres was added to both the top and backside topcoat layers, (a)
The coating was repeated. This sample was tested with a laser scanner. The results are reported in Table 7.

Sample (a) produced clearly visible non-contact Scanner interference fringes, while sample (b) produced no non-contact Scanner interference fringes under the most severe conditions of the laser diode Scanner test.

Example 9 Photographic Element with Matte Outer Layer Containing Particles of Alkali-Soluble Copolymer Backing containing particles of alkali-soluble methacrylic acid / ethyl methacrylate copolymer in gelatin binder (1.3 g / m ² ). This is a 0.16 micron silver chlorobromide emulsion on a 0.18 mm polyester base with an aqueous solution containing Superamide L9C and Taypol 610 wetting agent and formaldehyde hardener as in Example 1. Was coated as in Example 1. The copolymer particles had an average diameter of 0.75μ, but a diameter of 2μ
It included a wide range of things. Samples containing various concentrations of this matting agent were tested for interference fringe formation in comparison with unbacked samples. The results are reported in Table 8.

The degree to which the interference fringes are suppressed depends on the type of protrusion as well as the surface density of the protruding particles formed by the matting agent.

Similarly, the same dispersion of 0.16μ silver chlorobromide emulsion and copolymer matting agent was used, except that 0.18 with an infrared absorbing antihalation layer on one side as in Example 5.
Another coating was made using a mm polyester base. The matte layer was applied directly on the antihalation layer and the light sensitive emulsion was applied on the opposite side of the film base.

The third set of coatings was the same silver chlorobromide emulsion coated as in Example 1 on an unbacked 0.18 mm polyester base, but a conventional emulsion supercoat was co-loaded as described above. It was replaced by a matte dispersion of coalesced particles.

Coatings with a matte backing on the antihalation layer and coatings with a matte supercoat on the emulsion were also tested with a laser diode scanner. The results are reported in Table 8.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03C 5/16 (56) References JP-A-59-22049 (JP, A) JP-B-62- 29786 (JP, B2) JP 61-38456 (JP, B2) JP 52-26125 (JP, B2) JP Hei 3-43613 (JP, B2) JP 57-9054 (JP, B2) US Patent 3523022 (US, A) US Patent 4172731 (US, A)

Claims (16)

[Claims] 1. A photographic element comprising a support transparent to near infrared rays and one or more layers of a silver halide emulsion sensitized to near infrared rays having a grain size of 0.4 μm or less in average diameter. And (i) a top coat layer which is an outermost layer on the same side as the photosensitive emulsion of the support and is a diffusion transmitting layer for near infrared rays, and (ii) a photosensitive emulsion of the support Is a backing layer which is the outermost layer on the opposite surface and is a diffuse reflection layer or an absorption layer for near infrared rays, (iii) is located between the support and the photosensitive emulsion, and is a near infrared ray. Since it has at least one undercoating layer that is a diffuse transmission or absorption layer for, it is possible to form an image by a laser scanning method that generates near infrared rays without substantially forming non-contact interference fringes. Photo element to be. 2. The element has a backing layer comprising a binder containing a surface-roughening agent having an average grain size of 2 μm or less,
The backing layer projects into each mm ² of its outer surface from at least 30% of the individual diameters of the particles or from 0.2 μ of the mean horizontal plane of the surface, whichever is smaller, at least 25. A photographic element according to claim 1 having an outer surface that is microscopically rough such that it contains 1,000 grains. 3. The element has a topcoat layer comprising a binder containing a surface-roughening agent having an average particle size of 2 μ or less, the topcoat layer having a surface within each mm ² of its outer surface. Of at least 30% of the individual diameters of the particles or only 0.2μ from the mean horizontal plane of the microscopic roughness, such as containing at least 250,000 protruding particles, whichever is smaller. A photographic element according to claim 1 having an outer surface. 4. The microscopic surface roughness is such that within each mm ² of its outer surface, at least 30% of the individual diameters of the particles from the mean horizontal plane of that surface or only 0.2 μ, whichever is smaller. The photographic element of claim 1 wherein said photographic element is such that it contains at least 450,000 protruding particles. 5. The element contains an antihalation dye that absorbs near infrared light and is at least 0.7 in that region.
A photographic element according to claim 1 having a backing or subbing layer having a peak transmission optical density of 5. 6. A backing layer which contains an antihalation dye which provides a peak transmission optical density of at least 0.3 for near infrared light and which contains a roughening agent having an average particle size of 2 .mu.m or less. This layer has, in each mm ² of its outer surface, protruding from the mean horizontal plane of that surface by at least 30% of the individual diameter of the particles or by 0.2 μ, whichever is smaller. At least 20
A photographic element according to claim 1 having an outer surface of microscopic roughness such that it contains 20,000 grains. 7. The element comprises a backing layer having a peak transmission optical density of at least 0.3 for near infrared light and a topcoat layer containing a roughening agent having an average particle size of 2 μm or less. At least 200% of the particles protruding into each mm ² of its outer surface by at least 30% or 0.2μ of the individual diameter of the particle from the mean horizontal plane of the surface, whichever is smaller Having an outer surface that is microscopically roughened such that the photographic element of claim 1; 8. The element comprises an antihalation subbing layer having a peak transmission optical density of at least 0.3 for near infrared light, and a backing layer or top containing a roughening agent having an average particle size of 2 μm or less. Coat layer (this layer protrudes into each mm ² of its outer surface from the average horizontal plane of that surface by at least 30% of the individual diameter of the particles or by 0.2 μ, whichever is smaller 200,
Photographic element having a microroughened outer surface such that it contains 000 grains). 9. The element comprises a topcoat layer containing a surface-roughening agent having an average particle size of 2 μm or less, the layer being on each of its outer surfaces.
At least 30% of the individual diameters of the particles, or 0.2 μ, whichever is smaller, from the mean horizontal plane of its surface into mm ² , at least 200,0
Having an outer surface with a microscopic roughness such that it contains 00 particles) and a backing layer containing a surface-roughening agent having an average particle size of 2 μm or less (this layer is Each mm ² contains at least 200,000 particles protruding from the mean horizontal plane of its surface by at least 30% of the individual diameter of the particles or by 0.2μ, whichever is smaller. Having an outer surface of microscopic roughness such that the subbing comprises an antihalation dye that provides a peak transmission optical density of at least 0.3 for near infrared light. May have layers,
A photographic element according to claim 1 characterized in that 10. A backing layer and / or topcoat removable during photographic processing wherein the element comprises a binder containing particles having an average particle size of less than 5 .mu. Having a reflection index substantially greater than that of the binder. A photographic element according to claim 1 having layers. 11. The element of claim 10 wherein said element is sensitive to electromagnetic waves in the wavelength range 750 to 900 nm.
Photo element of the paragraph. 12. A surface-roughening agent particle having an average particle size in the range of 0.2 to 2 .mu., And claims 1 to 3, and 5 to 9. The photographic element of any one of the preceding clauses. 13. A roughening agent is selected from the group consisting of polymethylmethacrylate and a copolymer of methacrylic acid and methyl or ethylmethacrylate, and claims 1 to 3. The photographic element of any one of paragraphs 5 through 9 and 12 above. 14. A photographic element according to claim 10 wherein the high reflection index material has an average grain size in the range of 0.2 to 3 microns. 15. A photographic element according to claim 14 wherein the high reflection index material is selected from the group consisting of silver halide, zinc oxide, and calcium carbonate. 16. A photographic element comprising a support transparent to near infrared rays and one or more layers of a silver halide emulsion sensitized to near infrared rays having a grain size of 0.4 μm or less in average diameter. And (i) a top coat layer which is an outermost layer on the same side as the photosensitive emulsion of the support and which is a diffuse transmission layer for near infrared rays, and (ii) a photosensitive emulsion of the support Is a backing layer which is the outermost layer on the opposite surface and is a diffuse reflection layer or an absorption layer for near infrared rays, (iii) is located between the support and the photosensitive emulsion, and is a near infrared ray. A photographic element which has one or more subbing layers that are diffuse transmission or absorption layers for, and which can be imaged by a laser scanning system that produces near infrared light without substantially forming non-contact interference fringes; Placed on the emulsion side of the photographic element without contact with other surfaces Exposed by near-infrared electromagnetic waves from the laser diode scanning system, then it consists of developing and processes the element, substantially method of recording an image without non-contact interference fringes.