Safelight Filters for Infrared-Sensitive Photographic Elements
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Europaisches Patentamt J European Patent Office © Publication number: 0 615 143 A1 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 93103812.9 int. ci.5: G02B 5/22 @ Date of filing: 10.03.93 @ Date of publication of application: © Applicant: MINNESOTA MINING AND 14.09.94 Bulletin 94/37 MANUFACTURING COMPANY 3M Center, © Designated Contracting States: P.O. Box 33427 BE DE GB IT St. Paul, Minnesota 55133-3427 (US) @ Inventor: Williner, Mario 3M Italia S.p.A. 1-17016 Ferrania (Savona) (IT) © Representative: Checcacci, Giorgio PORTA, CHECCACCI & BOTTI s.r.l. Viale Sabotino, 19/2 1-20135 Milano (IT) © Safelight filters for infrared-sensitive photographic elements. © A safelight filter for infrared-sensitive silver halide photographic elements, said safelight filter comprising in superimposition a dye filter layer which absorbs visible light up to a wavelength of about 470 nm, a dye filter layer which absorbs visible light and infrared radiation over the wavelength range of from about 530 to about 850 nm and a flexible, transparent reflective sheet material having on one surface thereof a transparent metal coating which reduces transmission of near infrared radiation. The safelight filter effectively reduce transmission in the visible portion of the spectrum (from about 380 to 760 nm) and the near infrared radiation (from about 760 to 1500 nm) and transmits light only in the wavelength range of from about 470 to about 530 nm, thus providing sufficient visible light for darkroom working combined with minimum photographic effects on the sensitive silver halide photographic element. CO CO Rank Xerox (UK) Business Services (3. 10/3.09/3.3.4) EP 0 615 143 A1 FIELD OF THE INVENTION This invention relates to photographic safelight filters and more particularly to photographic safelight filters suitable for use in the handling and processing of infrared-sensitive photographic elements in 5 conjunction with safelight lamps. BACKGROUND OF THE INVENTION It is well known that silver halide photographic elements can be spectrally sensitized to infrared w radiation. See Mees and James, The Theory of Photographic Processes, 3rd edition, The MacMillan Company, 1966, pages 198 and 199. Silver halides are intrinsically sensitive only to light in the blue region of the spectrum. Therefore, when silver halides are to be exposed to other wavelengths of radiation, such as green light, red light or infrared radiation, a spectral sensitizing dye is required to render silver halides sensitive to such radiation. As known in the art, silver halides having adsorbed on the grains spectral 75 sensitizing dyes are made sensitive to radiation of a wavelength other than the intrinsic blue sensitivity. There are numerous references to dye structures for infrared sensitizing dyes. Examples of patents describing such dyes are listed in US Pat. No. 4,01 1 ,083. With the advent of lasers, and in particular solid state laser diodes emitting in the infrared region of the spectrum (e.g., 750 to 1500 nm), the interest in infrared sensitive materials has greatly increased. Many 20 different processes and articles useful for exposure to laser diodes have been proposed. These include CAT. (Computer Assisted Tomography) scanners, graphic arts products and infrared sensitive false color- sensitized photographic elements as described in US Pat. No. 4,619,892. In this patent, photographic elements are described which are capable of providing full color images without exposure to corresponding visible radiation. These false address elements comprise at least three silver halide emulsion layers on a 25 substrate, each associated with different photographic color image forming materials and sensitized to three different portions of the spectrum, with at least two layers sensitized to different regions of the infrared region of the spectrum. For convenience in the handling and processing of infrared sensitive photographic elements, it is desirable to use a safelight source which emits light so there is sufficient visible light for handling and 30 processing, yet cause a minimum level of fogging due to safelight lighting. However, the light emitted by the readily available safelight lamps used as light sources consists of a continuous spectrum and accordingly must be used in combination with suitable light filters. Conventionally, safelight filters for panchromatic photosensitive materials have been used for such infrared-sensitive elements. Said safelight filters, however, allow traces of the visible spectrum (dark red) to be partially transmitted, and also allows a 35 large quantity of infrared radiation to be transmitted to cause fogging. It has been proposed, see for example GB 462,249, to produce infrared filters by combining known dye filters, which absorb the ultra- violet and the visible portions of the spectrum up to bright red, with dye filters including penta-, hepta-, nona- and undeca-carbocyanine dyes. Said dyes, however, are not satisfactory in practical use due to their low light- and heat-resistance. It has been also proposed to combine known dye filters, which absorb the 40 ultra-violet and the visible portions of the spectrum up to bright red, with heat radiation shields including a glass having dispersed therein inorganic compounds, e.g., FeO, which absorb in the near infrared region of from 800 to 2000 nm. Said glasses, however, strongly absorb light not only in the infrared region but also in the visible region to cause reduction in the inside illumination. The glasses also lack the flexibility required to wrap up safelight lamps and cause a higher cost for the resulting safelight filter. A photographic safelight 45 filter for handling and processing of silver halide color materials, which transmits light in the wavelength range of from about 570 to about 595 nm wherein the materials possess a pronounced minimum of photographic sensitivity, is described in GB 750,731. SUMMARY OF THE INVENTION 50 The present invention provides a safelight filter for infrared-sensitive silver halide photographic ele- ments, said safelight filter comprising in superimposition a dye filter layer which absorbs visible light up to a wavelength of about 470 nm, a dye filter layer which absorbs visible light and infrared radiation over the wavelength range of from about 530 to about 850 nm and a flexible, transparent reflective sheet material 55 having on one surface thereof a visible light transparent metal coating which reduces transmission of near infrared radiation. The safelight filter effectively reduce transmission in the visible portion of the spectrum (from about 380 to 760 nm) and the near infrared radiation (from about 760 to 1500 nm) and transmits light only in the 2 EP 0 615 143 A1 wavelength range of from about 470 to about 530 nm, thus providing sufficient visible light for darkroom working combined with minimum photographic effects on the sensitive silver halide photographic element. DETAILED DESCRIPTION OF THE INVENTION 5 The dye filter layer absorbing visible light up to a wavelength of about 470 nm for use in the composite safelight filter of the present invention is comprised of suitable dyes incorporated in colloid layers coated onto transparent supports. Said dye filter comprises yellow dyes having absorption maxima in the blue region of the visible spectrum. Examples of yellow dyes having absorption maxima in the blue region io include those having commercial names Thioflavine, Pyramine yellow, Aurophenine, Metanil yellow, Brilliant yellow, Methylene yellow, Acridine yellow, Curcumine, Oxyphenine, Kiton yellow, Mikado yellow, Auramine, Naphthol yellow, Chrysoidine and Tartrazine. The dye filter absorbing visible light and infrared radiation over the wavelength range of from about 530 to about 850 nm for use in the composite safety filter of the present invention is comprised of green, blue is and red-violet dyes in combination incorporated in colloid layers coated onto transparent supports. Examples of red-violet dyes include those having commercial names Acid violet, Gentian violet, Flexonil violet and Filter blau-grun. Examples of green dyes include those having commercial names Naphthol green, Diamond green, Methyl green, Light green, Acid green and Lumiere green. Examples of blue dyes include those having commercial names Patent blue, Methylen blue, Eosin bluish, Victoria blue and Alkali 20 blue. The dye filters may be made of any hydrophilic colloid known in the art. Gelatin is the preferred hydrophilic colloid for use in the present invention. However, other water-soluble colloidal substances or mixtures thereof can also be used. Exemplary hydrophilic colloidal substances include gelatin derivatives, such as phthalated gelatin and acetylated gelatin, cellulose derivatives, such as carboxymethyl cellulose, 25 hydroxymethylcellulose, and cellulose sulfate, starch, casein, zein, synthetic hydrophilic colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of acrylic acid esters, acrylonitrile and acrylamides, etc. The amount of hydrophilic binder and the dyes used in practice depends upon the thickness and optical density required. The thickness of each dye filter is advantageously used in the range of from 10 to 50 micrometers, preferably 20 to 40 micrometers, and the optical dye density is advantageously at least 3, 30 preferably at least 4. The hydrophilic colloid layers of the dye filters are hardened with organic or inorganic hardening agents as known in the art. As hardening agents, use can be made of chromates