CN1011833B - Photographic elements sensitive to near infrared - Google Patents
Photographic elements sensitive to near infraredInfo
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- CN1011833B CN1011833B CN 85106475 CN85106475A CN1011833B CN 1011833 B CN1011833 B CN 1011833B CN 85106475 CN85106475 CN 85106475 CN 85106475 A CN85106475 A CN 85106475A CN 1011833 B CN1011833 B CN 1011833B
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Abstract
The present invention relates to a photographic material which can form images by a near infrared ray irradiating laser scanner, and cannot form interference fringes. The material comprises a film base supporting one or more layers of silver halide emulsion whose average particle diameter is smaller than or equal to 0.4 micrometer and one or more of the following coating layers: an upper layer which is an outermost layer on a film base where photographic sensitive emulsion exists, and is a diffuse transmission layer for near infrared ray irradiation, a back layer which is an outermost layer on a film base farther from the photographic sensitive emulsion, and is a diffuse reflection layer or an absorption layer for near infrared ray irradiation, and a bottom layer which is arranged between the film base and the photographic sensitive emulsion, and is a diffuse transmission layer or an absorption layer for near infrared ray irradiation.
Description
The present invention relates to from 750 nanometers with more than 750 nanometers, the material of taking pictures of the light sensitization of 750 to 1500 nm near-infrared spectral region emission particularly particularly is suitable for providing for the laser diode scanning system material of taking pictures of high-quality recording medium.
By the vicinity of visible image among a small circle luminance coding make visible image convert electronic data to, be a kind of widely used image processing technique, this electronic code is favourable to control, transmission and the storage of image.Knownly make electronic data convert visible image again to by so-called " scanning system ", utilize this scanning system, make the light beam of a branch of fine focus, pass light-sensitive medium, regulate light intensity according to electronic signal simultaneously and make the image density that reproduces needs with the grating line scanning of a succession of adjacency.
Laser instrument, particularly those use argon, krypton, helium-neon or helium-cadmium potpourri to be used as the high-intensity light source of this image processing technique as the laser instrument of gas laser medium.Yet all there is a kind of defective in all these laser instruments, need a kind of additional complex appts regulating the intensity of emission light, and what are because of big volume, mechanical equivalent of light fragility and high producing cost and be restricted.
Semiconductor laser diode may be suitable for the light source as scanning system to heavens, regulate because the output of their light can be imported directly by electric signal, and they is very small and exquisite and physically durable.
Yet, present unique satisfied long operation lifetime that has, and can the cheap laser diode device of producing large quantities of supplies be the laser diode of near infrared (NIR) spectral region of those emission from 750 to 1500 nanometers, therefore, in order to use laser diode scanning system, need provide a kind of recording medium to the sensitization of near infrared ray (NIR) scope light for developing.
Sensitization is known near infrared ray to use the long-chain cyanine dye to make the silver emulsion of taking pictures, and for example, sees the theory of developing of taking pictures of Mees and James work, 1966, and the list of references that MacMillan third edition 198-201 page or leaf and this paper quote as proof.
Find, film near infrared ray sensitization, particularly those silver halide particle mean diameters are less than 0.4 micron film, when not having the edge of the clamper of glass to support at one, to prevent and other surperficial contact, and when 820 nanometers give uniform blanket exposure by laser diode scanning system emission, obtain being coated with the image (this interference pattern this paper is called " contactless scanning striped " afterwards) of wide vortex interference pattern.These stripeds be considered to since from film condensation material and two interface exposure lights of surrounding air reflection produced.By the path difference between the reflection ray of film upper surface and basal surface, be subjected to domination at given position film thickness, simultaneously the pure phase difference neither causes harmful active influence that also do not cause, and neither reduces also not being increased in the exposure that this given position is sent to sensitive emulsion layer.Thereby striped is according to the profile of superfine little variation in thickness of film condensation material itself, and usually with 1 millimeter interval, length often is that several centimetres wide row covers whole image areas.
Contactless interference fringe is in the document of relevant silver halide emulsion agent material, do not report as yet in the past, this phenomenon is impossible under the normal condition with the visible light exposure, because the turbidity of sensitive emulsion layer is enough to make the reflection light diffusing that is come by film condensation material to fall behind.As seen, Infrared can be taken pictures emulsion and serious scattering not take place owing to its long wavelength by granule, and the coherence of the light of laser diode output has strengthened forming the tendency of interference pattern.Therefore, the silver halide particle mean diameter is 0.28 micron, and silver coating weighs 3 gram/rice
2The emulsion of taking pictures demonstrate can detected interference fringe.Make granularity be reduced to 0.23 micron or the more significant pattern of minimizing coating weight generation, and average particulate diameter is 0.20 micron or littler emulsion, after contactless laser diode scanning, demonstrates serious interference fringe.
Contactless scanning interferometer striped has seriously reduced the quality of scan-image, and particularly those have the quality of the scan-image of continuous tone level.They not only make the people disagreeable aesthetically, and make the important information that is transmitted by little density difference in image smudgy.Can use mean diameter less than 0.4 micron, preferably the emulsion of taking pictures less than 0.3 micron particles closes in requiring.Particle is 0.4 micron or less than 0.4 micron fine particle emulsion, is giving high spatial resolution, and high hiding rare is arranged, and giving lower silver coating weight is favourable to obtain given greatest optical density and development aspect.Therefore, the material of taking pictures that uses for the laser diode scanning system must can be eliminated contactless interference fringe.
The phenomenon of interference fringe is not the unknown in optical recording system.When the photographic film of iridescent surfaces with other iridescent surfaces (for example glass chip) luminous point screen or when contacting the contact exposure of printing egative film, a common problem is that the concentric stripe that is commonly referred to as the tight spacing of " Newton ring " in the image that develops (is seen physics encyclopaedia dictionary, J, Thewlis, Ed, pergaman, London, 1961, P, 878).These interference fringes are owing to produce from the optical interference between the next reflected light of the basal surface of film upper surface and contact chip base; The size in local air gap has determined the path difference between this two-beam line, thereby and determined whether their phase differential causes bright or dark interference fringe, causing increases or reduces the exposure that is sent to emulsion layer.Newton ring is tending towards forming the pattern zone of separation, and this zone is spread with one heart by contact position between exposure period, and this zone has narrow fringe spacing, and this interval becomes littler gradually to the edge of each pattern.Suitable with the contactless scanning interferometer striped of wide vortex in appearance different in these zones, these interference fringes are with about 1 millimeter spacing usually and often be the whole image area of wide row covering of several centimetre lengths.
Be known for the method that prevents to form Newton ring in the prior art.For example, known outside surface at film mixes the particle of delustring.The example of known delustring particle comprises silicon dioxide, polymethylmethacrylate (PMMA), other polyvinyl (comprising multipolymer), starch or inorganic salts.The density of delustring layer is from the relatively little value of larger particles (general diameter is 5 to 10 microns) (0.1 gram/rice for example
2) (disclosed) as US Patent specification № 4235959,4022622,3754924 and 2322037 to particle weight more greatly up to 1 gram/rice
2Or 50% upper strata bonding agent (as british patent specification № 2077935 and 2033596 and US Patent specification № 3507678 and 2992101 disclosed, these patents are used less granularity) change.
Use visible laser to produce the Newton ring interference striped of especially severe as the illumination of two kinds of emulsion contact half tones exposure.US Patent specification № 4343873 discloses a kind of material of taking pictures, and this material purpose is that this interference fringe is reduced to is minimum, and it comprises one deck light scattering layer, exposes under laser by this layer photographic layer.The diameter of optical scatter is the 50-150% of laser illuminator wavelength.This light scattering layer can be used as one deck skin be painted on take pictures above the material or other layer below.
For non-optical performance, as anti-stick property, wearing quality, the polishing ability, the good deciduous in the vacuum system, and the electrostatic effect that reduces, it also is known using matting agent in the material of taking pictures.One is used the example of matting agent is as US Patent specification № 4266010 disclosed a kind of infrared films, this instructions has been described a kind of emulsion upper strata, the PMMA of size in the 0.2-10 micrometer range in acid-treated gelatin adhesive contained on this upper strata, pointed out that this coating is applicable to all types material of taking pictures, comprise infrared film, another example is that US Patent specification № 3695888 is disclosed, it has described a kind of by the take pictures emulsion of the cyanine dye with internal compensation alkyl amino substituting group and special hypersensitizer to infrared ray sensitization, pointed out that this material can contain matting agent, as starch, titania, zinc paste, silicon dioxide, polymer beads comprises as the particle of US Patent specification № 2992101 disclosed 1-4 micron methacrylic acid-methylmethacrylate copolymers with as the US Patent specification № 2701245 disclosed 1-20 micron poly methyl methacrylate particles that generated by the emulsion polymerization.
Find that for eliminating Newton ring used known type coating on the material of taking pictures, the material of taking pictures that can not prevent to contain to the fine granularity emulsion of near infrared ray sensitization forms contactless interference fringe.
According to the present invention, a kind of material of taking pictures is provided, this material contains can be through being higher than 750 nanometers, the sheet base of general near-infrared radiation in the 750-1500 nanometer range, one or more layers silver emulsion, this emulsion contains the particle that mean diameter is no more than 0.4 micron, can be characterised in that this material comprises one or more to near-infrared radiation sensitization:
(ⅰ) one deck upper strata, this layer are the outermost layers on the sheet basal plane identical with photosensitive emulsion, and this upper strata is the diffuse transmission layer of near infrared radiation,
(ⅱ) one deck backing layer, this backing layer are that this backing layer is the diffuse reflector or the absorption layer of near infrared radiation at the outermost layer on photographic emulsion sheet base one side far away,
(ⅲ) one deck bottom, this layer is between sheet base and photosensitive emulsion, this bottom is the diffuse transmission or the absorption layer of near infrared radiation, thereby can make the material imaging by a laser scanning system irradiate near infrared rays radiation, and does not form contactless interference fringe basically.
Prevent the formation of internal optics interference pattern according to the material of taking pictures of the present invention; this pattern makes unshielded fine grain nearly red film when the laser diode near-infrared light source scans with post-flush; although this film is contactless with other surfaces during developing, covered by wide vortex streak.
For preventing the formation of contactless interference fringe, found three kinds of main technique, these technologies can separately or be used in combination.
Find that the imperceptible surfaceness of material can play a kind of vital role in the formation that suppresses interference fringe.Every square millimeter has the superfine microroughness of 200000 protrusions to make the formation of interference fringe significantly reduce, the surfaceness at the film back side is that every square millimeter of 250000 protrusion will be eliminated interference fringe basically fully, in the upper surface roughness greater than 25000 every square millimeter, more preferably greater than 450000 protrusions, also will eliminate interference fringe basically fully.
The second kind of technology that suppresses interference fringe formation provides one deck backing layer or bottom, this layer contains a kind of dyestuff that adsorbs exposure light source wavelength coverage light, when such one deck is used alone as the interference fringe inhibition layer of the inventive method, this layer will have at least 0.75 peak transmission optical density (OD); When such one deck and other interference fringe inhibition methods are used in combination, optical density (OD) at least 0.3 will be made significant contribution to the reduction of interference fringe.
The third technology that reduces striped formation is to use a kind of backing layer and/or upper strata of containing bonding agent, and the particle that this bonding agent contains has the refractive index of high index of refraction (more preferably greater than 0.3) greater than bonding agent.The desensitization silver halide particle in the gelatin for example.
It is favourable using silver halide particle, because halogenide can be removed when taking pictures the material flushing.This high refractive index layer can be removed after exposure satisfactorily, as the solvent by a kind of bonding agent of use.
Have been found that by some fine grained sense near infrared rays and take pictures forming of material that these materials will suppress the formation of contact interference fringe basically fully.For example can on such material of taking pictures, suppress contactless interference fringe with one or more following methods.
(1) at one deck backing layer on photographic emulsion sheet basal plane far away, this backing layer contains a kind of bonding agent, this bonding agent contains a kind of rough surface agent, this roughening agent particle mean size is no more than 2 microns, generally in the 0.1-2 micrometer range, be preferably the 0.2-2 micron, this outer backing layer has the outside surface of superfine microroughness, so consequently every square millimeter contains 250000 particles at least, be at least 30% of its single diameter on outstanding this surperficial average level of these particles, or 0.2 micron, no matter with any calculating, outstanding all less.
(2) one deck and photographic emulsion are with the upper strata on a slice basal plane, contain a kind of bonding agent, this bonding agent contains a kind of rough surface agent, the particle mean size of this roughening agent is not more than 1.5 microns, generally at the 0.1-1.5 micrometer range, be preferably the 0.2-1.5 micron, this upper strata has the outside surface of superfine microroughness, like this thus every square millimeter should the surface contain 250000 at least and preferably contain 450000 particles, outstanding this of these particles is at least 30% of its single diameter more than the surperficial average level, or 0.2 micron, no matter with any calculating, outstanding all less.
(3) one deck backing layer or bottom, this layer contain the above light of a kind of absorption 750 nanometers, preferably be absorbed in the anti-halo dye of 750-1500 nanometer wavelength range light and have at least 0.75 peak transmission optical density (OD) in this scope.
(4) contain a kind of outermost backing layer of anti-halo dye, this dyestuff to 750 nanometers with glazed thread, be preferably in the 750-1500 nanometer wavelength range, obtain at least 0.3 peak transmission optical density (OD), this backing layer also contains a kind of rough surface agent, the particle mean size of this roughening agent is not more than 2 microns, generally at the 0.1-2 micrometer range, be preferably the 0.2-2 micron, this one deck has the outside surface of superfine microroughness, so consequently every square millimeter should contain 200000 particles in the surface at least, these particles are given prominence at this more than surperficial average level, are at least 30% of its single diameter, or 0.2 micron, no matter, outstanding all less with any calculating.This one deck can be divided into two independent layers selectively, and one deck contains the outermost layer of rough surface agent and contains the interior backing layer of anti-halo dye.
(5) one deck backing layer and one deck outermost upper strata combine, this backing layer is for more than 750 nanometers, being preferably in light in the 750-1500 nanometer wavelength range has the peak transmission optical density (OD) and is at least 0.3, a kind of rough surface agent is contained on this outermost upper strata, this roughening agent particle mean size is not more than 2 microns, generally in the 0.1-2 micrometer range, be preferably the 0.2-2 micron, this one deck has the outside surface of superfine microroughness, so consequently every square millimeter should contain 200000 particles in the surface at least, and it is 30% of its single diameter at least that these particles are given prominence on this surperficial average level, or 0.2 micron, no matter, outstanding all less with any calculating.
(6) backing layer or the upper strata of one deck antihalation layer and one deck outermost combine, this antihalation layer is for more than 750 nanometers, being preferably in light in the 750-1500 nanometer wavelength range has the peak transmission optical density (OD) and is at least 0.3, this layer is between photographic layer and sheet base, a kind of rough surface agent is contained on this outermost backing layer or upper strata, the particle mean size of this roughening agent is not more than 2 microns, generally in the 0.1-2 micrometer range, be preferably between the 0.1-2 micron, this one deck has the outside surface of superfine microroughness, so consequently every square millimeter should contain 200000 particles in the surface at least, these particles are given prominence on this surperficial average level and are at least 30% of its single diameter, or 0.2 micron, no matter with any calculating, outstanding all less.
(7) one deck upper strata and one deck outermost backing layer combines, can also be the coating of one deck between backing layer and sheet base, a kind of rough surface agent is contained on said upper strata, the particle mean size of this roughening agent is not more than 2 microns, generally in the 0.1-2 micrometer range, be preferably between the 0.2-2 micron, this one deck has the outside surface of superfine microroughness, so consequently every square millimeter should contain 200000 particles in the surface at least, these particles are given prominence on this surperficial average level and are at least 30% of its single diameter, or 0.2 micron, no matter with any calculating, outstanding all less, said outermost backing layer contains a kind of rough surface agent, the particle mean size of this roughening agent is not more than 2 microns, usually in the 0.1-2 micrometer range, be preferably between the 0.2-2 micron, this one deck has the surface of superfine microroughness, so consequently every square millimeter should contain 200000 particles in the surface at least, these particles are given prominence on this surperficial average level, be at least 30% of its single diameter, or 0.2 micron, no matter with any calculating, outstanding all less, the coating of said one deck between backing layer and sheet base contains a kind of anti-halo dye, and this dyestuff is for more than 750 nanometers, and the light that is preferably in the 750-1500 nanometer wavelength range provides the peak transmission optical density (OD) to be at least 0.2.
(8) one deck contains a kind of backing layer and/or upper strata of bonding agent, the particle refractive index that this bonding agent contains is basically greater than the refractive index of bonding agent (for example non-sensitizing silver halide particle), said average particle size is lower than 5 microns, is preferably the 0.2-3 micron, and this layer is removed when taking pictures flushing.
Find that when with the imaging of one scan laser instrument, the superfine microroughness of the material of taking pictures influences the tendency that this material forms contactless interference fringe significantly.Particularly found to provide one deck outer backing layer, this layer provides the superfine microroughness of every square millimeter of at least 250000 protrusions on this surperficial average level, supposes that radiation when taking place on the material another side, will prevent the formation of striped.Similarly, suppose photographic material from the same one side of this one deck during by radiation, the formation of interference fringe can prevent that this upper strata has imperceptible surfaceness by one deck upper strata is provided, this roughness provides every square millimeter 250000 at least, is preferably 450000 protrusions.This imperceptible surfaceness and prior art contain found in the material of taking pictures of matting agent layer greatly different; Usually, delustring layer of the prior art often provides and has the surperficial protrusion that also often contains less than 1/10th quantity on surface used herein that lacks half quantity than protrusion of the presently claimed invention.
By using one deck backing layer or bottom, mix a kind of anti-halo dye so that at least 0.75 peak transmission optical density (OD) to be provided in the 750-1500 nanometer range, the formation that suppresses interference fringe basically is possible.
As mentioned above, can utilize the combination of matte layer and antihalation layer, in this case, reduce desired the comparing of the only resource that interference fringe forms with using this binding layer, the surfaceness of each individual layer and optical density parameter may reduce, because binding layer has additive effect.Found and another interference fringe to suppress the layer used outer field suitable superfine little surfaceness that combines be every square millimeter of 200,000 protrusions.The optical density (OD) that the antihalation layer that is used in combination with matte layer requires is at least 0.3.
The aforesaid superficial layer that contains particle preferably is used in the back of the body surface of material, or two outmost surface, rather than the upper strata on the photosensitive material emulsion side only, because, be unexpectedly, suppress contactless laser scanning interference fringe (when supposition exposes from emulsion side) with shaggy backing layer, be better than being used in the similar upper strata on the emulsion side.
The favourable rough surface agent that is used for these layers is the particle of organic polymer, polymethylmethacrylate or dissolve in the polymkeric substance of developer solution particularly, as the particle of methacrylic acid-methacrylate copolymer (for example US Patent specification № 2,992,101 in disclosed).That in this granularity scope, use and need to load with other suitable organic polymers that obtain eliminate optical property described above be for example british patent specification № 2078992 and 2033596 and US Patent specification № 4287299 and 3079257 in the multipolymer of disclosed other polyvinyls or vinyl compound.
Other suitable materials comprise for example US Patent specification № 4235959,3920456, the composition of disclosed silicon dioxide or silicon dioxide and polymkeric substance and as the gelatin of disclosed post bake among the british patent specification № 2077935 in 3591379 and 3222037, the water-soluble inorganic salt, or starch, glucosan and these mixture of polymers.
One type of matting agent well known in the prior art is superfine silica dioxide granule, and diameter often is 0.1 micron or littler.When disperse this binders for coatings as aqueous gelatin in the time, these granules form the aggregation of combining closely, general diameter is 1 micron or bigger, the surface goes out to seem that they are single particles.Both can be by having used the single particle of the magnitude range that requires, or similarly also can obtain being eliminate optical property of the presently claimed invention by using the aggregation of its total size in claimed range equally.
Suitable high-index material comprises non-Photoactive silver-halide crystal, and these crystal are easy to make uniform size and the stop bath of being taken pictures is eliminated.Usually in the 2.0-2.2 scope, other suitable high-index materials comprise zinc paste and lime carbonate to the refractive index of silver halide.
Gelatin is to the suitable bonding of all these coatings and has about 1.5 refractive index.
When little polymkeric substance or other particles, when particularly mean diameter those particles below 1 micron or 1 micron are used for delustring to the adhesive layer surface that applies, height at the above protrusion of average surface level, and outstanding granule number, not only depend on particles contained weight, also depend on used coating and drying condition, select to apply and dry condition, these conditions produce the degree of particle protrusion of the presently claimed invention, and these parameters will to be understood by those of ordinary skill be important.Verified, a kind of technology that satisfied surfaceness is provided when using together with suitable prescription be after coating immediately wet stock send into 13 ℃ of relative humidity 30% the cooling zone so that gel solidify, then in 30 ℃ and 30% time drying of relative humidity.Find that thin layer was at 30 seconds to 1 minute inner dryings.
According to the present invention, except that add above-mentioned delustring particle for surface roughening, the material of taking pictures can contain in a small amount (less than 0.1 gram/rice
2) bigger polymkeric substance, silicon dioxide or have other matting agents of 5 microns of mean diameters or larger particle is to improve mechanical property, as adhesion and wearing quality.
Be used for the take pictures silver emulsion of material of the present invention and can comprise silver bromide, silver chloride, chlorine silver bromide, bromo-iodide and silver chloroiodobromide, and it is available any known, for example, at Research Disclosure 17643, in Dec, 1978, disclosed method preparation in II section and the III section.The emulsion granularity is not more than 0.4 micron, usually at the 0.05-0.4 micrometer range.
Disclosed dyestuff or use any other spectral sensitizing dyes known in the prior art among the open № 0088595 of available european patent application for example at Mees and James, The Theory of The Photographic Process, the third edition, disclosed in the 198-199 page or leaf to wavelength 750-1500 nanometer, the dyestuff of (being preferably the 750-900 nanometer) radiation sensitization can make this emulsion sense near infrared ray.
The silver emulsion that exists in the present invention takes pictures material can prevent to produce photographic fog and during preservation stable, prevents that sensitivity from reducing.Suitable antifoggant and stabilizing agent are for example in Research Disclosure in Dec, 17643,1978, and be disclosed in the VI section.
The take pictures silver emulsion that exists in the material of the present invention for example can use in the Dec, 17643,1978 at Research Disclosure, disclosed optical whitening agent in the V section.
The silver emulsion of the spectrum sensitive that the present invention is used for example can contain in the Dec, 17643,1978 at Research Disclosure, disclosed those speedup compounds in the X XI section.
Originally the coating of material of taking pictures for example can contain in the Dec, 17643,1978 at Research Disclosure, and disclosed those various colloids are as carrier or bonding agent in the IX section.Such colloid can be with for example in Research Disclosure in Dec, 17643,1978, disclosed those various organic and inorganic hardener post bakes in the X section.
The material of taking pictures of the present invention for example can contain in the Dec, 17643,1978 at Research Disclosure, XI, disclosed antistatic or conductive layer in XII and the X III section, plastifier, and lubricant, surfactant.
The material of taking pictures that the present invention is used for example is applied in the Dec, 17643,1978 at Research Disclosure, in the X VIII section on the disclosed various filmbases.
In Research Disclosure in Dec, 17643,1978, disclosed those known the whole bag of tricks penetrate into photosensitizing dye and other emulsion condiment in the coating of the material of taking pictures in the XI X section by for example.Similarly, also available various methods of operating will be taken pictures coated materials on the sheet base of taking pictures.Sheet base and to apply operation be for example, Research Disclosure in Dec, 17643,1978, disclosed in X V and the X VII section.
Can pass through for example at Research Disclosure 17643, in Dec, 1978, disclosed in the XI X section, when having developer to exist, silver halide is combined with a kind of aqueous alkaline medium, the used sensitizing silver emulsion of the present invention is developed to generate visible silver and/or dye image.
Though of the present invention detailed openly be to containing the silver halide particle material that diameter is lower than 0.4 micron, but the inhibition method of interference fringe is equally applicable to the material that contains other Photoactive silver-halide crystal, and these materials are because low turbidity can limit the formation of scanning striped.Particularly the present invention surpasses 0.4 micron and the silver halide flaky grain of big length-diameter ratio is arranged applicable to containing diameter, if particularly these particles in material with low silver halide mark (all the other are made up of fine grained) when existing.
The material of taking pictures of the present invention can be used, for example, in Research Disclosure 17643, in Dec, 1978, X XII, X XII I, X XI V, the XX V, disclosed physical development system in XX VI and the XX VII section, image transferring system, the dry process development system, the diffusion transfer system, impression and lithography duplicate and direct print system.To the present invention be described by following examples now.
The evaluation of carrying out sample as described below in an embodiment:
By the scanning of contactless laser diode to the evaluation of sample measurement to striped
In a scanner device, to the sample evaluation, the radiant rays by 815 nanometers of Hitachi HLP1400 laser diode emission is focused into 50 microns little round dots on sample surfaces therein by uniform exposure.With a kind of vibration galvanometer catoptron of infrared beam stroke on sample with 200 row/centimetre the point that focuses on of raft formula (rafter) raster scanning.Progressively improve exposure intensity, so that after developing, on sample, obtain from minimum to the most highdensity scale.Utilize an automatic roll-type developing machine of 3M type XP507 then, use Eastman Kodak RPX-Omat processing solution that sample is developed.Stripe is carried out visual examination, uses following ordering that it is estimated:
1. there is not visual striation
2. almost can not find striped
3. very faint, only under examining, see
4. diffusion pattern
5. faint, but obvious striped clearly
6. be easy to the striped observed
7. obvious stripe clearly
By a Joyce-Loebl MDM6 microdensitometer, use a little slit fenestra (2.0 * 0.25 millimeters) to follow the tracks of, estimated stripe quantitatively.Provided the max transmissive optical density (OD) that between bright and dark striped, measures poor (O.D.) in an embodiment with this method.Measured O.D. in the sweep limit of the average optical density between to 1.0 and 2.0 in this scope, emulsion has from 2.5 to 3.5 contrast value.
Carry out the measurement of sample surfaces reflectivity is following in an embodiment:
The measurement of direct (minute surface) surface reflectivity on the back of the body surface of delustring
Before test, remove sensitive emulsion layer, and a kind ofly absorb ultrared non-reflector layer densely and make sample by on its position, using by physics.Use then a branch of by a laser diode 5 millimeters of the diameters of 815 nanometers radiation, the collimated light beam of known energy is with 10 ° of untreated faces to method angle these samples of irradiation.Use a radiation detector to monitor at 20 ° of reflected energies (optronics type 730A) to incident beam total angle place.
This detector device is arranged on the 30 cm distance places on separating test surface, and allows that light passes through the circular hole of one 1 cm diameter.
When using same detector with evaluation incident and reflected energy, a kind of simple calculating enables to determine the percentage reflectivity.Careful select laser diode/sample film/detector be configured to eliminate external energy in guaranteeing to measure.
Check to the frosting of sample among the embodiment is carried out as follows:
Scanning electron microscope (S.E.M.) check frosting
A film sample (about 1 centimetre) is adhered on the syringe needle measured surface in the superiors, and the PS-2 coating unit that uses international scientific Instr Ltd. (ISI) was coated with last layer gold plating, about 25 nanometer thickness of this layer in 1.2 kilovolts and 10 milliamperes through 2 minutes.Check these samples with ISI Super III A sweep electron microscope (10 kilovolts of operating voltages).These samples are placed+20 ° of angles.In all cases, amplification is taken the photograph for 5000 times and is used the internal labeling thing mutually.In a grid of representing 10 microns * 10 microns zones, carry out grain count.Appear to as fruit granule that to exceed the average surface level be 30% of its diameter at least, or 0.2 micron, outstanding all less no matter with that a kind of calculating, then particle is counted.As only being big in sample, uncommon particle exists, and then takes the photograph phase with 2000 times or lower enlargement factor, and in the scope inside counting of bigger area.
The result who is reported is a mean value that is verified the photograph gained counting of two surperficial different pieces from each.
Embodiment 1
The preparation of sense near infrared ray silver emulsion and test application in the used photographic material at the laser diode scanner
Arrogating all powers to oneself with Europe, the embodiment 17B of the open № 0088595 of application is described twoly to be annotated the precipitation method to prepare a kind of particle mean size that contains is 0.28 micron the 64%(mole with cubic granules and a narrow distribution curve) silver chloride and 36%(mole) emulsion of silver bromide.
Use continuously lower precipitation temperature, prepare average particle size equally and be 0.23 micron, 0.20 micron, 0.16 micron with 0.13 micron similar emulsion.All these emulsions all are gold and sulphur sensitizing and stable traditionally.And press the basic recipe described in the embodiment 18 of the open № 0088595 of european patent application and add near infrared spectrum sensitizing dye, triphen phosphorus hypersensitizer, wetting agent and hardener.Coat emulsion on the polyester base plate seriatim transparent 0.18 millimeter be coated with, to obtain 2.7 to 3.0 gram/rice
2Heavy silver coating.Apply the protective seam of 200 milliliter 5% the aqueous gelatin that contains 100 milligrams of Superamide L9C and 0.15 milliliter of Teepol610 wetting agent and 45 milliliter 2% formaldehyde hardener solution during the ridge, but do not apply matting agent or filter dye, to obtain 1.33 gram/rice
2The upper strata of gelatin.The back of the body surface of film base plate stays and is not coated with.Superamide L9C is the commercial a kind of high activity lauric acid-diethanolamine condensation product that can buy from Britain Millmaster-Onyx.Teepol610 is a kind of secondary alkyl sulphate sodium salt that can buy from Britain Shell Chemicals company limited.
Ping Ding sample the results are shown in table 1 as stated above.
Table 1
Emulsion granularity is to the influence of scanner striped
Silver halide granularity visual appearance stripe optics
(micron) density difference
0.28 2 0.02
0.23 4 0.03
0.20 6 0.04
0.16 7 0.07
0.13 7 0.06
This embodiment proof is along with the silver halide granularity reduces, and the scanner striped increases.
Embodiment 2
Photographic material and anti-scanner striped with the back layer that contains polymethylmethacrylate (PMMA) particle of the present invention
Performance
Prepare emulsion, near infrared sensitizing and apply emulsion as embodiment 1, different is to use 0.18 millimeter to be coated with the polyester base plate, and this base plate provides one deck at gelatin adhesive (1.3 gram/rice
2) in contain 0.3 gram/rice
2The backing layer of poly-(methyl methacrylate) particle of 0.5 micron of mean diameter.This backing layer is applied by the aqueous solution and the formaldehyde hardener that also contain as the Superamide L9CT Teepol610 wetting agent among the embodiment 1.After being coated onto on the film base plate, just make wet backing layer at once,,, and within one minute, finish then by temperature about 30 ℃ and relative humidity 30% drying so that colloid solidifies momently by the chill zone of 13 ℃ of temperature and relative humidity 30%.As mentioned above, sample is tested in the laser diode scanner system, the results are shown in table 2.
The coating of same granularity emulsion standard in contrast in embodiment 1.
Embodiment 3
Photographic material with the backing layer that contains the non-photosensitivity silver halide particle of the present invention
As applying 0.16 micron chlorobromide of one deck among the embodiment 1, different be to use 0.18 millimeter polyester base plate, this base plate is provided at (1.3 gram/rice in the gelatin adhesive
2) contain silver halide particle, the different grain size and the heap(ed) capacity of the photostable backing layer particle of near infrared light are listed in table 3 to the influence of scanner striped.
Embodiment 4
Photographic material with the backing layer that contains other rough surface agent
As applying 0.16 micron chlorine bromine of one deck emulsion in embodiment 1, different is, and this emulsion is coated in 0.18 millimeter is coated with on the polyester base plate, and this base plate has one deck (1.3 gram/rice in gelatin adhesive
2) contain the backing layer of the particle (particle mean size is 0.5 to 2.0 micron) of alkali-solubility methacrylic acid-ethyl methacrylate copolymers, apply this backing layer by containing as the aqueous solution of Superamide L9C in embodiment 1 and Teepol610 wetting agent with as the formaldehyde hardener in embodiment 1.Prepare a same sample in addition, wherein polymer beads is replaced by the silica dioxide granule of 5 microns of the mean diameters of low heap(ed) capacity.The sample of testing the same no backing layer of these samples compares, and the results are shown in table 4.
Conventional silicon dioxide delustring is fallen and can not be prevented outside the grain coating scope of the present invention that striped from forming.
Embodiment 5
The antihalation backing layer is to the influence (0.16 micron chlorobromide) of scanning striped
As apply 0.16 micron chlorobromide of one deck in embodiment 1, different is that this emulsion is coated on 0.18 millimeter polyester base plate, and this base plate has by 5 gram/rice
2One deck backing layer that gelatin is formed, this backing layer contains a kind of at the strong anti-halo dye that absorbs between 750 and 900 nanometers (dyestuff 29 in the open № 101646 of european patent application), this dyestuff is 0.40 in 820 nanometers optical density (OD)s, in the laser diode scanner system,, the results are shown in table 5 with this coating of sample comparison test of a no backing layer.
Embodiment 6
The application of bromine iodine emulsion
Produce according to the method for embodiment 17A among the open № 008595 of european patent application that to have average grain volume be 0.21 micron chemically 3% responsive stable sulphur bromide on the spectrum, and be coated on the clear polymer base plate of 0.18mm, be coated with last layer 1.3g/m simultaneously
2The gelatin top layer.
Same coating also is coated on the polyester base plate of 0.18mm, and this base plate has continuous three layers and is (5g/m
2) the antihalation backing layer of gelatin, this backing layer contains the dyestuff of (dyestuff 29 among the open № 0101646 of european patent application), can powerful be absorbed in the wavelength between 750 to 900 nanometers, and this dyestuff is 0.45,0.8 and 1.2 in the total optical density (OD) of 820 nanometers.These coatings test findings in the laser diode scanner system arrives in table 5.
Embodiment 7
The relation of formation of scanner striped and surface reflectivity and surfaceness
If apply 0.16 micron chlorobromide of one deck among the embodiment 1 like that, the different polyester base plates that are to use 0.18 micron, this base plate provides the backing layer of polymethylmethacrylate (PMMA) particle that contains 0.5 micron of a series of dense mean diameter, and this backing layer is with a kind of gelatin adhesive as embodiment 2 (1.3 gram/rice
2) apply.These samples are tested in the laser diode scanner system, and table 6 is listed in the influence that striped forms.
Embodiment 8
The coating that anti-halo dye and polymethylmethacrylate (PMMA) particle all applies
(a) anti-halo dye and conventional matting agent are only arranged
The chlorobromide for preparing 0.26 micron of a kind of granularity, and use the method for embodiment 1 to make sensitizing.This emulsion is coated on 0.18 millimeter polyester base plate, at 2.4 gram/rice
2The silver coating rate applies one deck simultaneously and contains 0.036 gram/rice
2Dawn glue (1.3 gram/the rice of the particle that polymethylmethacrylate (PMMA) mean diameter is 2.5 microns
2) upper strata.Reverse side coating one deck of base plate contains the gelatin layer (5 gram/rice that absorb infrared ray dyestuff (dyestuff 17 among the open № 0101646 of european patent application)
2), this dyestuff has the infrared ray absorbing of from 750 to 900 nanometers, is 0.6 in the optical density (OD) of 815 nanometers, and the base plate reverse side also has one deck and contains 0.065 gram/rice
2Gelatin upper strata (1.3 gram/the rice of the polymethyl methacrylate that mean diameter is 6 microns (PMMA) particle
2) (backing layer).Test this coating with the laser diode scanner, the results are shown in table 7.
(b) halation dye and rough surface agent of the present invention
Apply by method in (a) and add 0.18 gram/rice
20.5 micron polymethyl methacrylate (PMMA) rounded grain to the top coat of pros and cons, test this sample with laser scanner, the results are shown in table 7.
Table 7
Sample laser scanning every at backing layer
Influence (10 microns)
2
Visual appearance is given prominence to granule number
a 5 2
b 1 35
Find that sample (a) has clearly visible contactless scanning striped, and sample (b) under the strictest laser diode scanner test condition without any contactless scanning striped.
Embodiment 9
Photographic material with outer delustring layer of the particle that contains alkali-soluble copolymer
As applying 0.16 micron chlorobromide of one deck among the embodiment 1, different is with a kind of gelatin adhesive (1.3 gram/rice
2) this emulsion is coated on 0.18 millimeter polyester base plate, this negative has a backing layer, this backing layer contains alkali solubility methacrylic acid-ethyl methacrylate copolymers, as being applied by a kind of aqueous solution and formaldehyde hardening agent that contains Superamide L9C and Teepol610 wetting agent among the embodiment 1.0.75 micron of this copolymer pellet mean diameter, but comprise that diameter is up to 2 microns big scope.The sample that contains this matting agent of different densities is relatively done striped formation test with no backing layer sample, the results are shown in table 8.
The degree that striped is eliminated depends on structure type, and depends on the superficial density of the outstanding particle that is produced by matting agent.Other coating makes with a kind of similar methods, use the suspending liquid of same 0.16 micron oxygen bromide and multipolymer matting agent, different is to use 0.18 millimeter polyester base plate as embodiment 5, and this base plate has in one side and applies one deck and absorb ultrared antihalation layer.The delustring layer directly is coated onto above the antihalation layer, and photosensitive emulsion is coated onto the reverse side of sheet base.
Made by the same chlorobromide on a kind of 0.18 millimeter polyester base plate that does not have a backing layer as 1, the three group of coating of embodiment, different is that common emulsion protective seam is replaced by the delustring suspending liquid of copolymer pellet recited above.
On antihalation layer, apply the coating of delustring layer and those coatings that the delustring protective seam is coated on the emulsion are also used the test of laser diode scanner, the results are shown in table 8.
Table 2
0.5 the effect of micron polymethylmethacrylate (PMMA) particle backing layer
0.5 micron PMMA visual appearance of silver emulsion stripe optics every (10 microns)
2
Granularity (micron) backing layer gram/rice
2Density difference is given prominence to granule number
0.20 0.3 1 0.015 153
0.16 0.3 1 0.015 154
0.13 0.3 1 0.015 154
Table 3
The silver halide backing layer of non-photosensitivity
Grain type granularity coating visual appearance striped
(micron) gram/rice
2O.D.D. '
Do not have--7 0.06
(contrast)
AgIBr 0.6 0.4 2 0.02
AgIBr 0.6 0.8 2 0.02
AgIBr 1.0 0.5 2 0.02
AgIBr 1.0 1.0 1 0.015
' O.D.D.=optical density (OD) is poor
Table 4
Backing layer is formed heap(ed) capacity visual appearance striped every (10 microns)
2
Gram/rice
2O.D.D. ' outstanding granule number
Nothing-7 0.06-
Alkali-soluble copolymer
Particle mean size 0.5 to 0.32 2 0.02 46
20 microns
Silicon dioxide
5 micron 0.1 7 0.06 7 of granularity
' O.D.D.=optical density (OD) is poor
Table 5
The effect of antihalation coating (A II)
Embodiment emulsion is at 820 nanometers visual appearance stripeds
Antihalation O.D. O.D.D. '
5 oxygen bromides 07 0.07
5 oxygen bromides 0.40 5 0.035
6 iodine bromides 07 0.06
6 iodine bromides 0.45 6 0.04
6 iodine bromides 0.80 3 0.025
6 iodine bromides 1.20 2 0.02
' O.D.D.=optical density (OD) is poor
One deck antihalation coating halation coating helps to suppress striped significantly
Table 6
0.5 the interference fringe that micron PMMA produces reduce with the relation (surface reflectivity determination method) of surface dulling effect with and the surface outstanding
0.5 the backside reflection rate that influences every (10 microns) of micron PMMA laser scanning
2
Backing layer gram/rice
2Visual appearance striped O.D.D. ' gives prominence to granule number
Do not have 7 0.07 46 2
0.04 6 0.05 44 27
0.07 4 0.04 3.1 51
0.13 2 0.025 1.49 83
0.20 1 0.02 0.76 126
0.27 1 0.02 0.46 157
' O.D.=optical density (OD)
Table 8
Be coated with of the influence of the delustring layer of alkali-soluble copolymer at backing layer or upper strata to striped formation
Multipolymer delustring ball every (10 microns)
2After the scanning of dyestuff bottom
The outstanding granule number outermost emulsion of particle loaded amount is at 820 millimeters visual appearances
Gram/rice
2Backing layer upper strata O.D.=0.4
Do not have 7
0.06 26 + 5
+ + 4
+ 6
0.10 42 + 3
+ + 3
+ 4
0.14 58 + 2-3
+ + 2-3
+ 3
0.20 70 + 1-2
+ + 1-2
+ 2
The O.D.=optical density (OD)
Claims (17)
1, a kind of photographic material, this material comprises the sheet base of the saturating near-infrared radiation of one deck, one or more layers average diameter of particles is not more than 0.4 micron, to the silver emulsion of near-infrared radiation sensitization, it is characterized in that this photographic material comprises one or more layers following coating:
(1) one deck upper strata, this upper strata be the sheet base with the one side on outermost layer as silver halide emulsion layer, this upper strata is the diffuse transmission layer to infrared radiation,
(2) one deck backing layer, this backing layer are the outermost layers at the another side that photosensitive emulsion synusia base is arranged, and this backing layer is to the diffuse reflector of near-infrared radiation or absorption layer,
(3) one deck bottom, this bottom are between sheet base and sensitive emulsion layer, and this bottom is the diffuse transmission layer or the absorption layer of a pair of near-infrared radiation,
Wherein said diffuse transmission layer or diffuse reflector contain bonding agent, have particle mean size to be not more than 2 microns particle in the bonding agent; Said absorption layer contains the bonding agent that the dyestuff that absorbs infrared radiation is wherein arranged, so this photographic material can be by the laser scanning system imaging of emission near-infrared radiation, and does not form contactless interference fringe basically.
2, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises one deck backing layer, this backing layer contains bonding agent commonly used in the photosensitive material, bonding agent contains the rough surface agent that a kind of particle mean size is not more than 2 microns, this backing layer has imperceptible outer surface roughness, so that every square millimeter this surface contains 250 at least, 000 particle, particle is with at least 30% single diameter, or 0.2 micron long given prominence to more than surperficial average level, no matter, outstanding all less with that a kind of calculating.
3, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises one deck upper strata, bonding agent commonly used in the photosensitive material is contained on this upper strata, bonding agent contains the rough surface agent that particle mean size is not more than 2 microns, this upper strata has imperceptible outer surface roughness, so that every square millimeter this surface contains 250 at least, 000 particle, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than average level of surface, no matter, outstanding all less with that a kind of calculating.
4, as desired a kind of photographic material in the claim 1, it is characterized in that this atomic thin surfaceness is, this surface contains 450 for every square millimeter at least, 000 particle, these particles are given prominence to be at least single diameter more than surperficial average level 30% or 0.2 micron, no matter, outstanding all less with that a kind of calculating.
5,, it is characterized in that this photographic material comprises that one deck contains and absorbs near infrared light and have close backing layer or the bottom that is at least 0.75 anti-halo dye of peak transmission optics in this scope as desired a kind of photographic material in the claim 1.
6, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises one deck backing layer, this backing layer contains to be had the peak transmission optical density (OD) to be at least 0.3 anti-halo dye and contains the rough surface agent that particle mean size is not more than 2 microns near infrared light, this one deck has the outside surface of superfine microroughness, so that this surface of every square millimeter contains at least 200,000 particle, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than surperficial average level, no matter that a kind of calculating, outstanding all less.
7, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises that one deck has and near infrared light peak transmission optical density (OD) is at least backing layer and one deck of 0.3 contains the upper strata that particle mean size is not more than 2 microns rough surface agent, this upper strata has imperceptible outer surface roughness, so that this surface of every square millimeter contains 200 at least, 000 particle, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than surperficial average level, no matter, outstanding all less with that a kind of calculating.
8, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises that one deck has peak transmission optical density (OD) near infrared light and is at least antihalation undercoat and one deck of 0.3 and contains backing layer or the upper strata that particle mean size is not more than 2 microns rough surface agent, this layer has imperceptible outer surface roughness, so that this surface of every square millimeter contains 200 at least, 000 particle, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than surperficial average level, no matter that a kind of calculating, outstanding all less.
9, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises that one deck contains the upper strata that particle mean size is not more than 2 microns rough surface agent, this layer has imperceptible outer surface roughness, so that every square millimeter should contain 200 in the surface at least, 00 particle, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than surperficial average level, no matter that a kind of calculating, outstanding all less, and comprise that one deck contains the backing layer that particle mean size is not more than 2 microns rough surface agent, this backing layer has imperceptible outer surface roughness, so that this surface of every square millimeter contains 200,000 particles at least, particle is with at least 30% single diameter, or 0.2 micron given prominence at this more than surperficial average level, no matter, outstanding all less with that a kind of calculating, and comprise selectively that one deck contains and provide the peak transmission optical density (OD) to be at least the bottom of 0.3 anti-halo dye near infrared light.
10, as desired a kind of photographic material in the claim 1, it is characterized in that this photographic material comprises one deck backing layer and/or upper strata, they comprise bonding agent commonly used in a kind of photosensitive material, this bonding agent contains refractive index is lower than 5 microns bonding agent basically greater than particle mean size the particle of refractive index, and these layers are removable in photographic process.
11,, it is characterized in that this photographic material is to the radiation sensitization of wavelength coverage 750 to 900 nanometers as desired a kind of photographic material in the claim 10.
12, as each desired a kind of photographic material in claim 1 to 3 and 5 to 9, the particle mean size that it is characterized in that the roughening agent particle is within 0.2 to 2 micrometer range.
13, as claim 1 to 3,5 to 9 each desired a kind of photographic materials is characterized in that roughening agent is selected from the multipolymer of polymethylmethacrylate and metering system and methyl methacrylate or Jia Jibingxisuanyizhi.
14,, it is characterized in that roughening agent is selected from the multipolymer of polymethylmethacrylate and methacrylic acid and methyl methacrylate (or ethyl ester) as desired a kind of photographic material in the claim 12.
15, as desired a kind of photographic material in the claim 10, the particle mean size of material that it is characterized in that high index of refraction is in 0.2 to 3 micrometer range.
16,, it is characterized in that the material of high index of refraction is selected from silver halide, zinc paste and lime carbonate as desired a kind of photographic material in the claim 15.
17, the photographic material in above-mentioned each claim of use is in the video record that does not have contactless interference fringe basically, it is characterized in that under the situation that does not contact other surface, exposing, wash above-mentioned material then its video is developed with said photographic material with the near-infrared radiation that produces by the laser diode scanning system on the emulsion side that is positioned at photographic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85106475 CN1011833B (en) | 1984-08-31 | 1985-08-29 | Photographic elements sensitive to near infrared |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848422069A GB8422069D0 (en) | 1984-08-31 | 1984-08-31 | Photographic elements |
| CN 85106475 CN1011833B (en) | 1984-08-31 | 1985-08-29 | Photographic elements sensitive to near infrared |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106475A CN85106475A (en) | 1987-03-11 |
| CN1011833B true CN1011833B (en) | 1991-02-27 |
Family
ID=25741996
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85106475 Expired CN1011833B (en) | 1984-08-31 | 1985-08-29 | Photographic elements sensitive to near infrared |
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| Country | Link |
|---|---|
| CN (1) | CN1011833B (en) |
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| US9696139B2 (en) * | 2012-06-25 | 2017-07-04 | The Boeing Company | System and method for improved visual detection of protective coatings |
| CN103008201A (en) * | 2012-12-26 | 2013-04-03 | 海南赛诺实业有限公司 | Post-curing method for double-faced crylic acid coating film |
| CN114683675B (en) * | 2020-12-28 | 2023-11-14 | 乐凯华光印刷科技有限公司 | Flexible resin plate with surface provided with textured flat top dots and plate making method thereof |
| CN114015181A (en) * | 2021-12-02 | 2022-02-08 | 海越红外光学研究院(广东)有限公司 | High-heat-resistance anti-red-exposure infrared-transmitting optical composite material composition and preparation method thereof |
-
1985
- 1985-08-29 CN CN 85106475 patent/CN1011833B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85106475A (en) | 1987-03-11 |
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