JPS61137149A - Color photographic element - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Description of Related Applications This is filed on November 26, 1984.
'[This is a continuation-in-part of Application No. 674583.

FIELD OF THE INVENTION This invention relates to color photographic elements, particularly at least 52 to 15
The present invention relates to a color photographic element capable of providing a full color image by exposing a single silver halide emulsion layer to light outside the visible region of the electromagnetic spectrum. In particular, the present invention provides at least three emulsion layers, each emulsion layer being sensitized to a different region of the electromagnetic spectrum, and one or more of which is sensitized to light in the infrared region of the electronic spectrum. in combination with a color image-providing material.

Dyes capable of sensitizing frontal technology silver halide agents to the infrared region of the electromagnetic spectrum have been known for some time. Merocyanine dyes and cyanine dyes, especially those with long bridging groups between ring moieties, have been used for many years to sensitize silver halides to infrared radiation. U.S. Patent No. 3.619.15/l; No. 3, 682;
No. 630; No. 2,895.955; No. 3,482.978: No. 3,758.461; No. 2.731'1.900: and British Patent No. 1,19
No. 2.234; No. 1.188.784 discloses a well-known class of dyes that sensitize silver halides to the infrared region of the electromagnetic spectrum. U.S. Patent No. 4,362,8
No. 00 discloses dyes used to sensitize inorganic photoconductors to infrared radiation, and these dyes are also effective sensitizers to silver halides.

Lasers, especially in the infrared region of the electromagnetic spectrum (e.g. 78
With the advent of solid state laser diodes that emit in the range 0 to 1500 nm+, interest in infrared sensitization has greatly increased. A number of different methods and products useful with laser diodes have been proposed. For example, U.S. Patent No. 4.
No. 416,522 proposes a daylight photoplotting device for film infrared exposure. This patent also generally proposes a film consisting of three emulsion layers sensitized to different parts of the non-visible electromagnetic spectrum, including the infrared. However, this description of the film is quite comprehensive, and the density of the imagewise exposure on each layer appears to depend on the filtering of the light beam from the device before it hits the film surface.

Part 1 of the Invention A photographic element is described that is capable of providing a full color image without exposure to visible light. The element consists of at least three silver halide emulsion layers on a substrate. Each of this at least three layer emulsion diagram contains various photographic color imaging materials, such as color couplers, diffusible dyes, and bleaching dyes that can form different color dyes upon reaction with oxidized color photographic developers. , and in combination with oxidative leuco dyes. The three emulsion layers are sensitized to three different parts of the electromagnetic spectrum;
The at least two layers are sensitized to different regions of the infrared region of the spectrum. These layers must be constructed to prevent or reduce exposure by radiation intended to expose only other layers. This is done by making a difference.

18 Details of one drawing The 1st Δ diagram shows Example 1 when exposed to a 780 nm light beam.
represents the D-log 2 curve for a photographic element of . The curve (c) shows the density of the yellow forming layer sensitized to 780 nm. The curve (c) shows the density of the magenta forming layer sensitized to 830n111.
f) shows the density of the cyan forming layer sensitized to 880 mm.

Secondary absorption is cyan and magenta color D-log 2
Observed in the low concentration region (0.1-0.5) of the curve. These unwanted low density bumps are due to residual green absorption properties of the yellow dye or residual red absorption properties of the magenta dye and can be read by the green or red filter of the densitometer. The same second-order absorption is observed in the cyan curve of FIG. 1B. Appropriate separation should be made by subtracting these unwanted, associated color absorptions from the actual exposure curve.

FIG. 1B shows the D-1o (IE concave curve not shown) for the photographic element of Example 1 when exposed to 830 nm light. Show layers.

FIG. 1C shows the D-IQ! for the photographic element of Example 1 when exposed to 39 Q nm light! Represents an IIE curve. The curve (to) indicates the cyan cambial layer.

Figure 2 shows Example 2 when exposed to 780 nm light.
represents the D-+00E curve for the photographic element. Curve A shows the yellow forming layer. Curve B shows the magenta forming layer in the element without the filter layer. Curve B' shows the magenta forming layer when a filter dye is present between layers 3 and 5. Curve C shows the cyan forming layer. The shift of the F curve is 0.38100 E units.

DETAILS OF THE INVENTION Wood K describes a photographic element in which at least two silver halide emulsion layers can be exposed to light outside the visible region of the electromagnetic spectrum to provide a full color or three color image. a) a substrate; and 1) at least three silver halide emulsion layers on one side of the substrate, each layer of the silver halide emulsion layers forming a monochromatic image of a different color dye. a first emulsion sensitized to a first part of the infrared region of the electromagnetic spectrum, the first emulsion being sensitized to a first part of the infrared region of the electromagnetic spectrum, in any order; a second silver halide emulsion sensitized to a second portion of the outer region, the wavelength of maximum spectral sensitivity of the second emulsion differing by at least 15 nIll from the wavelength of maximum spectral sensitivity to which the first emulsion was sensitized; , OJ: a third silver halide agent sensitized to a third portion of the electromagnetic spectrum, the wavelength of maximum spectral sensitivity of the third portion being the maximum spectral sensitivity wavelength at which the first and second emulsions were sensitized. differing by at least 15 nm from each of the wavelengths, and the sensitivity of each of the three emulsion layers differs by at least 15 nm from each of the wavelengths of The emulsion on the back of the two infrared-sensitive layers having a shorter wavelength of maximum spectral sensitivity is at least 0.2 logE lower than the other of the two infrared-sensitive layers at the wavelength of its maximum spectral sensitivity.
It is like having a unit fast sensitivity. at least 1
It has been found that a wavelength difference of 5 nm allows color separation of the final image using only the sensitivity difference at the wavelength of maximum spectral sensitivity of each layer. This is particularly surprising given that infrared sensitizing dyes (even those that are J-bandable) tend to have absorbance and therefore photosensitivity over a long range.

For example, if a dye is selected that sensitizes the emulsion to 850n+, the dye should be at least 800 to 850r+n+
There is also a tendency to sensitize with essentially equal effectiveness over the entire range of . Therefore, if two identical emulsions in the same photographic element each have a wavelength of maximum spectral sensitivity of 800 nm,
and 850 nm when sensitized with a dye, 800 nm
Exposure to nm light tends to expose both emulsions equally, so there is essentially no color separation.

Often large (e.g. 50 nm) towards shorter wavelengths within the region of the electromagnetic spectrum where infrared sensitizing dyes effectively sensitize
Since the decrease in photosensitivity caused by fluctuations is small, a wavelength difference of maximum spectral sensitivity of at least 15 nm is required. The difference between any two infrared sensitive layers is at least 2 Qnm
, more preferably the difference is at least 35 nm, and most preferably the difference in wavelength of maximum spectral sensitivity is at least 50 nm between any two infrared sensitized layers. The closer the wavelengths of maximum spectral sensitivity between the layers are, the greater the sensitivity difference should be and the higher the contrast should be. The use of filter layers between emulsion layers can help reduce the required level of sensitivity difference between layers. By using filter dyes between the layers that absorb strongly at the wavelength of maximum spectral sensitivity of the top emulsion layer (as viewed from the direction of exposure), the required sensitivity differences of the layers below can be reduced somewhat.

A preferred arrangement of the layers is such that the wavelength of maximum spectral sensitivity of each layer becomes longer as it is farther from the exposure direction (or surface). That is, for example, when using color paper or print 1- as a reference, the infrared-sensitive layer furthest from the paper base has a wavelength of maximum spectral sensitivity that is shorter than the wavelength of maximum spectral sensitivity of all other emulsion layers closer to the base. has. This arrangement was selected because the sensitizing peak of the dye tends to decline more rapidly as the wavelength becomes longer, making sensitivity separation easier and filter dye selection easier.

As mentioned earlier, if all three emulsion layers are in the infrared region of the electromagnetic spectrum, then any two layers have at least 15
nm different maximum spectral sensitivity wavelength and at least 0.2t
It must have a sensitivity difference in units of oqF. two layers are sensitive to wavelengths in the infrared range, and a third layer is sensitive to wavelengths in the infrared range;
If the layer is sensitized to wavelengths in the visible range,
Such differential sensitivity considerations should be made unnecessary by reasonable selection of the maximum sensitization wavelength. Spectral sensitizing dyes are available throughout the visible spectral region and even in the ultraviolet region. Therefore, one skilled in the art could readily sensitize the third emulsion layer to wavelengths other than the infrared that do not overlap in practice with the spectral sensitization achieved by the various sensitizing dyes. For example, the third emulsion layer may contain blue, green, or
Or it can be sensitized to the yellow region. If for any reason it is desired to sensitize the third emulsion layer to a spectral region less than 1100 nm shorter than the shortest wavelength in the infrared range to which the emulsion is sensitized, visible light may be used. It may be desirable to take care to adjust the sensitivity of emulsions sensitized to light in a manner similar to that done for shorter wavelengths within the infrared. Emulsion layers that are sensitized to the visible part of the electromagnetic spectrum are close to the infrared (e.g., 50nm from the shortest wavelength in the infrared range for which the element's emulsion is spectrally sensitized).
m range), the sensitivity of an emulsion sensitized to the visible region is also less than the sensitivity of an emulsion sensitized to wavelengths in the infrared range closest to the visible region of the spectrum. It should be at least 0.2 or at least 0.5 logE units faster. The use of J-band forming spectral sensitizing dyes in the visible region of the electromagnetic spectrum would effectively reduce this consideration. The wavelength of maximum spectral sensitivity of each layer, whether within or outside the infrared range, has at least 1
There should still be a difference of 5 nm.

The sensitivity of an emulsion layer is always to be measured at the wavelength of maximum spectral sensitivity of the emulsion layer. The term wavelength of maximum sensitivity is to be referred to in the practice of this invention as the wavelength of maximum spectral sensitivity, ie, the wavelength of maximum sensitivity brought about by the addition of a spectral sensitizing dye.

Contrast I used in the construction of emulsions within the scope of the invention
The widest range of ~ is about 0.5-12.

The lower limit is essentially a function of the power available from the imaging device's laser. The upper limit tends to be a function of the type of application for which the film or paper is to be used. Contrast is preferably in the range of 1 to 10; contrast of 2 to 8 is more preferred.

The present application further includes a) a substrate, and b) at least three silver halide emulsion layers on one side of the substrate, the combination of the silver halide emulsion layers for forming a monochromatic color image of different color dyes. A photographic element comprising: wherein at least two silver halide emulsion layers can be exposed to radiation outside the visible region of the electromagnetic spectrum to provide a full color image, in combination with means of:
The three silver halide emulsion layers include a first emulsion sensitized to a part of the infrared region of the electromagnetic spectrum; a part J to which the first emulsion is sensitized; A second emulsion sensitized to a portion of the infrared region of and the three silver halide emulsion layers are: i) each of the three layers has a molecular weight of 0.5 to 12, preferably 1 to 11;
most preferably has a contrast of 2 to 8, and
Regarding photographic sensitivity, the third emulsion (
The sensitivity of the first emulsion layer (J) which is sensitized to the infrared is at least 0.21 ooE units faster than the second emulsion layer and the second emulsion is at least 0.210 (l
ii) between the first emulsion layer and the second emulsion layer, the first emulsion layer is sensitized without absorbing more than 40% of the infrared radiation; When there is a filter layer that absorbs infrared radiation in a range that overlaps the maximum sensitivity region of the second emulsion layer, and the third layer is also sensitized to the infrared region of the spectrum, the second emulsion layer and the third emulsion layer, the second layer is sensitized to absorb a range of infrared rays that overlaps the maximum sensitivity region of the third emulsion layer without absorbing more than 1.0% of the infrared rays. an absorbing filter layer is present, and iii) the first and second emulsion layers or the second and third emulsion layers (when the third layer is also sensitized to the infrared region of the spectrum); ) absorbs light in a range that overlaps the maximum sensitivity region of the layer farther from the substrate, but the use of the two layers is sensitized. and another pair of emulsion layers consisting of said second and third emulsion layers or said first and second emulsion layers, respectively. is 0.5 to 12, preferably 1 to 1
1, most preferably with a contrast of 2 to 8; and for photographic speed, the sensitivity of the emulsion layer furthest from the substrate of the other pair of emulsion layers at an optical density of 1.3 a photographic element having a configuration selected from the group consisting of: differing from each other by at least 0.21 ooE units faster than the sensitivity of the emulsion layer closest to the substrate of the pair of emulsion layers. Are listed.

In the practice of this invention, the higher the contrast of the emulsion layer, the more
The requirement for sensitivity difference becomes smaller. For example, if an emulsion layer has a contrast of 8, at the wavelength of its maximum sensitivity it will have a contrast of 0.2
The logE small unit sensitivity difference would be 4-minutes. For contrasts below about 4.5, the sensitivity difference should typically be at least 0.410+IF units, and for contrasts between about 2 and 4, the sensitivity difference should typically be at least 0.5 logE units.

The relative order of the emulsion layers of this invention is important in obtaining benefits from this technique. As noted above, the first layer must be the emulsion layer furthest from the imaging radiation. Thus, when exposure is through a transparent base, the first layer is the emulsion layer furthest from the base, ie, the top emulsion layer in a normal perspective view. The first layer is usually the infrared sensitized emulsion layer closest to the base, since photographic elements are not normally exposed through the base.

As mentioned above, it is preferred that all of the silver halide emulsion layers are sensitized to different infrared portions of the electromagnetic spectrum. It is essential that at least two layers are sensitized to different infrared regions of electromagnetic spectrum. The order of the at least two layers should still be such that the longer wavelength sensitized emulsion image is closest to the side of the photographic element first struck by the exposure light. There is considerable flexibility as to the placement of other silver halide emulsion layers sensitized to the visible part of the electromagnetic spectrum. For example, for 800nm, 880nm, and 580nm (yellow), 3
When a system consisting of emulsion layers of layers is created, it is not essential to reduce the sensitivity of the filter layer as well as the emulsion layer between the yellow-sensitive layer and either of the infrared-sensitive layers. However, the sensitivity difference and/or
Also, a filter layer must be present between the two infrared sensitive layers. elements (when counted in the base direction)
1) 58Qnm, 2) 800nm, and 3)
When composed of emulsion layers sensitized to 880 nm, a filter layer (if present) must be placed between layers 2) and 3) or the emulsion sensitivity is must be different between layers 2) and 3) as required. Layer 1) is simply a conventional yellow-forming silver halide emulsion layer (or negative dye-forming layer).
Constructed as. 1) 800nm.

When a single yellow layer is placed between two infrared sensitizing layers, such as 2) 580 nm1 and 3) 880 nm, a filter layer must be present between layers 1) and 3). Instead, it is placed between layers 1) and 2) or between layers 2) and 3). A difference in emulsion sensitivity, if used, exists between layers 1) and 3) according to the practice of the invention. The sensitivity of layer 2) is selected solely based on the activity required to produce an effective yellow color.

No significant consideration is given to preventing layer 2) from being exposed by the light rays used to expose layer 1) or 3). A filter may be used if the dye in layer 2) leaves a long tail on its absorption curve, but this will only occur with unskillful selection of the yellow sensitizing dye.

Similar considerations must be made when a visible light sensitive emulsion layer is used as the emulsion layer furthest from the base. If a filter layer is used, it must also be present between the two infrared-sensitive layers. A difference in emulsion sensitivity must still exist between the two infrared sensitized layers when the method is used in accordance with the teachings of the present invention.

The infrared portion of the electromagnetic spectrum is given a diverse range, but generally falls within the visible region of the electromagnetic spectrum (e.g., from about 750 to
750-1500n with a slight partial type at 780nm)
It is considered that m. A number of dyes are known for sensitizing silver halide emulsions to various parts of the infrared region of the spectrum. In particular, cyanines and merocyanines have been widely documented as infrared sensitizers for various types of imaging systems, including silver halide emulsions.

For example, U.S. Patent No. 2,104. ,．． No. 064: No. 2,
No. 734.900: No. 2.895,955; No. 3,1
No. 28,179; No. 3,619.154; No. 3.682.630; and No. 4,362.800 disclose a number of dyes that are infrared sensitizers. Photographic Chemistry Volume 2 (P., Graff Kais, 1960, Fountain Press), Chapter XL, pages 882-901 describes infrared spectral sensitization of silver halide emulsions, and more generally. The Theory of the Photographic Process, 3rd Edition (Meig and James, 1966)
2007) Chapter Ⅰ, especially pages 199 and 205.

The formula below represents an example of a known infrared sensitizing dye. These dyes are described in Mieg and James, supra; Grafkeis, supra; and US Pat. No. 2,895,955.

The sensitizing dye selected is critical to the construction of the color multilayer material in order to sensitize each emulsion to a specific region of the infrared spectrum. As shown in the formula below, the structure of these dyes is usually a symmetrically or asymmetrically substituted dicarbocyanine 1 and tricarbocyanine 2, with a compound in the median chain to increase the auxochrome rigidity and stability of the dye. A betero ring may be introduced into.

Some representative IR sensitizing dyes 7-9 are shown in the formulas below. Each of these dyes is added to a silver chlorobromide emulsion, coated, and then exposed to light from a tungsten light source in a wedge spectrophotographic weapon for various times. The characteristic shape of these isocurves is that they have a long tail extending from the maximum sensitization peak to the short wavelength side of the spectrum by 150 to 300 nm, but a short tail of approximately 50 to 7 Onm width to the long wavelength side.

10 Other cyan-type dyes with various auxochrome end groups
20 also showed a similar sensitization curve on the emulsion. The wavelength (peak) of the maximum sensitization peak and the wavelength (minimum) at the point where the minimum sensitization occurs on the longer wavelength side are also shown. Although any known useful anions may be combined with these compounds, 1-1Br-11 to cyley-1 and para-toluenesulfonate are preferred.

These infrared sensitizing dyes, like most other sensitizing dyes, do not follow a monochromatic absorption curve, but they absorb light within a range of wavelengths and are therefore sensitizing. They absorb over a range of the electromagnetic spectrum, even comprising J-banding dyes, which tend to have a narrow range of absorption for each dye. This range can extend from a few nm to several hundred nm. Even though the exposure light source from a laser is essentially monochromatic light and has a wavelength of 1 q, the spectral sensitivity of a single layer emulsion has a maximum sensitivity at the wavelength of the exposure light, but still has a sensitive range that includes that wavelength.

The state of art infrared laser diode is wavelength 750~9
It tends to emit light between 50 nm.

This tends to be too narrow a range to allow for multilayer photographic emulsions with a diverse range of sensitivities. On the other hand, sensitizing dyes selected to sensitize, for example at about 780,830, and 880, have sensitizing effects that may overlap at each other's wavelengths. Particularly for photographic elements intended to provide full color images, overlapping sensitization ranges result in poor color rendering fidelity due to false imaging of multiple layers with light of the same wavelength. The structure of the present invention makes it possible to form high quality color photographic images even when several emulsion layers are sensitized to have maximum sensitivity with peaks within 50 nm of each other.

Any of a variety of types of photographic silver halide emulsions can be used in the practice of this invention. For example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobromoiodide, and mixtures thereof can be used. Any morphology of the particles can be used, cubic, orthorhombic, hexagonal, epitaxial, or platelet (high aspect ratio).

The coupler may be present either directly bound by the hydrocolloid or supported in a high boiling organic solvent and then dispersed in the hydrocolloid. The colloid may be partially or fully cured in any of a variety of known photographic hardeners. Such hardeners include free aldehydes (U.S. Pat. No. 3,232,764), aldehyde-releasing compounds (
U.S. Patent Nos. 2,870,013 and 3.819,
608), S-triazines and diazines (U.S. Pat. Nos. 3.325.287 and 3,992.366), aziridine (U.S. Pat. No. 3.271.175),
Nilsulfone (U.S. Patent No. 3.490.911),
carbodiimide, etc.

In this application, the silver halide photographic emulsion is selected from the dyestuff 37
= Can be used to form dye images via selective formation. The photographic element described above for forming a silver image is disclosed in British Patent No. 4.
No. 78,984, U.S. Patent No. 3,113 to Earl Jaeger.
．． No. 864, U.S. Pat. No. 3.002.8 to Veetam et al.
No. 36, No. 2.271,238, and No. 2.362.598, US Pat.
No. 950.970, Carroll U.S. Patent No. 2.592,
No. 243, U.S. Pat. No. 2,343,703 to Porter et al.
No. 2.376.380 and No. 2.369.48
No. 9, Spas UK Patent No. 886,723 and US Patent No. 2.899,306, Teuto US Patent No. 3.15
No. 2.896, and U.S. Pat. No. 2.115 to Manis et al.
．． No. 394, 2.252,718 and 2.108,602, and Pilate U.S. Pat.
It can be used to form dye images by using developers containing dye image forming agents such as color couplers as described in No. 547.650. In this form, the developer contains a color developing agent, such as a primary aromatic amine which is capable of reacting (coupling) with a coupler in oxidized form to form an image dye.

heat-developable photographic color film or paper using silver halide and leuco dye in catalytic proximity to a reducible silver source;
Instant self-developing diffusion transfer films can also be used.

The dye-forming coupler is 9K Hemi written by Schneiko et al.
(Die Chemie) Volume 57, 19471I)
113, U.S. Patent No. 2.304 to Manis et al. ．． No. 940, Marginis U.S. Patent No. 2.
No. 269,158, U.S. Patent No. 2.322 to Gierley et al.
．． No. 027, U.S. Pat. No. 2,376.6 to Floridge et al.
No. 79, U.S. Pat. No. 2,801.171 to Feilke et al.
No., Smith U.S. Pat. No. 3,748.141, Tong U.S. Pat. No. 2,772.163, Zartl et al.
No. 533.514, Beaterson U.S. Pat. No. 2,353
．． No. 754, Seidel U.S. Pat. No. 3,409.435, and Ken Research Disclosure No. 159.
Vol. (July 1977) No. 15930. Dye-forming couplers can be introduced at different m to achieve different photographic effects.

For example, British Patent No. 923.045 and U.S. Pat. No. 3,843.369 to Kumai et al. It teaches what to do.

Dye-forming couplers are typically selected to form image dyes of the subtractive primaries (i.e., yellow, magenta, and cyan) and provide hydrophobic ballast groups for incorporation into high-boiling organic (coupler) solvents. The open-chain ketomethylene, pyrazolone, pyrazolo-1-lyazole, pyrazolobenzimidazole, phenol, and naphthol type 2- and 4-equivalent couplers are non-diffusible, colorless couplers. Such couplers (Masalminen et al., U.S. Pat. No. 2.4.23.730, 2.
No. 772.162, No. 2.895,826, No. 2.7
No. 10,803, No. 2.407.207, No. 3.737.316, and No. 2.367.531, U.S. Pat. No. 2,772,161 to Lauria et al., No. 2,600,788 , No. 3.006,759, No. 3,214.437 and No. 3.253.924, U.S. Pat. No. 2,875.057 to McCrossen et al., U.S. Pat.
No. 08.573, U.S. Pat. No. 3,034 to Gledhill et al.
, No. 892, U.S. Patent No. 2.4.7 to Peisberger Re.
No. 4,293, No. 2.407.210, No. 3.062
．． No. 653, No. 3.265,506 and No. 3.384,657, U.S. Pat.
No. 343.703, U.S. Patent No. 3 to Greenhalsch et al.
．． No. 127.269, U.S. Patent No. 2.8 to Feniak.
No. 65.748, No. 2.933,391 and No. 2.865.751, U.S. 14th Edition 3 of Bailey et al.
．． No. 725.067, Peever et al.
No. 8.308, Lau U.S. Patent No. 3.779,763;
Fernandez U.S. Patent No. 3.785.829, U.K.-'[No. Patent No. 3,762.921, Viva U.S. Patent No. 2,983.608, Loria U.S. Patent No. 3,311.
476, 3.408.194, 3,458,315, 3.4.47,928, 3,476.563, Cressman et al.
No. 3,419.390, Young U.S. Time W [No. 3.419
．． No. 391, Restina U.S. Patent No. 3.51'9.429
No. 975.928, 'UK Patent No. 1.111.554, Jieken U.S. Patent No. 3.2
No. 22.176, and Canadian Patent No. 726,651, British Patent No. 1.248.924 to Schulte et al.
: U.S. Patent No. 3,227.550 by Whitmore Sen.
It is explained in the issue. Dye-forming couplers of different reaction rates can be used in a single layer or in separate layers to achieve the effects required for specific photographic applications.

Dye-forming couplers are used during coupling as development inhibitors or accelerators, bleach accelerators, carriers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, competitive couplers, chemical or spectral sensitization. photographically effective fragments such as agents, desensitizers, and desensitizers. Development inhibitor releasing (DIR) couplers are disclosed in U.S. Pat. No. 3,148,062 to Whitmore et al. and U.S. Pat.
No. 7,554, Barr U.S. Pat. No. 3.733.201;
Sodi Yoneda Patent No. 3,617,291, Glue 1~
U.S. Pat. No. 3,703,375, Abbott et al. U.S. Pat. No. 5, U.S. Patent No. 3 to Marks et al.
No. 632,345, U.S. Pat. No. 3,869 to McCu et al.
No. 291, British Patent No. 1.201110, U.S. Patent No. 3,6 to Oishi et al.
No. 42.4.85, Vabru Hemlock British Patent No. 1.236
．． No. 767, U.S. Pat. No. 3,770,43 to Fujiwara et al.
No. 6, and Matsuo et al. U.S. Pat. No. 3,808,94.
It is explained in No. 5.

Dye-forming couplers and non-dye-forming compounds that release a variety of photographically effective groups upon coupling are described in Lau U.S. Pat.
No. 248.962.

A DIR compound that does not form a dye upon reaction with an oxidized color developing agent is described by Fujiwara et al. in West Germany 018 No. 2.529.
No. 350 and U.S. Pat. No. 3.928.041, No. 3
．． No. 958.993 and No. 3,961.959, West German OL S No. 2,448.0 of Oudein Valkou et al.
No. 63, West German OLS No. 2,610.546 to Tanaka et al., U.S. Pat. No. 4,049,455 to Kikuchi et al., and U.S. Pat. ．． No. 052,213. DIR compounds that undergo oxidative cleavage are described by Porter et al. in U.S. Pat. No. 3,379,529, Green et al. in U.S. Pat.
No. 22, Duerenbeer et al.'s American W [No. 3,297
, 445 and Riessen U.S. Pat. No. 3,287.1.
It can be used as described by No. 29. Relatively light-insensitive silver halide emulsions, such as the Lippmann emulsions, are disclosed in Shiva et al., US Pat. No. 3,892. ．． It has been utilized as interlayers and overcoat layers to prevent or control migration of development inhibitor fragments as described in US Pat.

Photographic elements include Hanson Yoneda Patent No. 2.4.49,966, Glass et al. U.S. Pat.
No. 521,908, U.S. Patent No. 3,03 to Gledhill Sen.
4. ．． No. 892, Lauria U.S. Patent No. 3.476.56
No. 3, Lestina U.S. Patent No. 3,519,429, Friedman U.S. Patent No. 2,543,691, Pütschiel Sen U.S. Patent No. 3,028,238, Mentzel et al. U.S. Patent No. 3,061,432 dye-forming colored couplers such as those used to form integral masks for negative color images as described in No. 1 and Greenhalsch British Patent No. 1,035,959;
and/or U.S. Patent No. 3.876.42 to Mullin et al.
No. 8, Leekamoto et al. U.S. Pat. No. 3,580,722, Pütschiel U.S. Pat. Competitive couplers may be involved as described in other US Pat. No. 2,689,793.

Particularly effective color couplers include those shown in the list of compounds as Nos. 21 to 24.

As previously mentioned, the color imparted to the image formed by exposure of each of the differently sensitized silver halide emulsion layers is due to the reaction of the oxidized color developing agent with the color coupler. It doesn't have to be. A number of well-known color imaging mechanisms may also be used. Among the commercially available color imaging mechanisms are dye diffusion transfer, dye bleaching, and leuco dye oxidation. Each of these procedures is used commercially, is well understood by those of ordinary skill in the photographic art, and is used with silver halide emulsions. This is a multi-layered element that uses sophisticated technology and is commercially available by hand. Copying existing commercially available systems to the embodiments of the present invention is to mechanically re-RQ the system's sensitometrics 1 to 1 and 2.
training and/or intermediate filter layer (=J
This can be done by adding For example, in conventional instant color dye transfer diffusion elements, room speed differences and/or placement of filter layers between silver halide emulsion layers are introduced according to the teachings of the present invention, while otherwise remaining the same. This can be done with either negative-acting or positive-acting halogenated emulsion elements. The only major obvious consideration that must be taken for such construction is to ensure that the placement of the filter layer does not impair the transfer of the diffuse dye to the receiving layer within the element. Using a non-burr filter between the receiver layer and the dye-containing layer is the simplest way to address that consideration.

These types of imaging systems are well known. A detailed discussion of various/r dye transfer diffusion processes can be found, for example, in ``A Fundamental Nikko Imaging Technology for Instances 1-.
Harrison) Journal of Fuo Volume 1 ~ Graphic Science and Engineering Vol. 20 No. 4 July/August 1976 Reply [
1 Graphie Materials and Systems No. 7
Edition (John M. Stang, Phono Nostrand Reinhold, NY, 1977) No. 324-330
Found on page 126 and negative.

A detailed discussion of dye-bleached color imaging systems can be found, for example, in The Reproduction of Color, 3rd Edition (R.

W.G. Han] ~, Fountain Press, London, UK, 1975) pp. 325-330; (Author, Macmillan Publishing, N.Y., 1977), pages 363-366. No. 366 of the above-mentioned book by Mead James
Dye transfer methods are also discussed in great detail on page 372. Oxidation of leuco dyes in silver halide systems is described in U.S. Pat. ? It is disclosed in No. IO.

As previously mentioned, these existing color forming systems can be modified by those skilled in the art in accordance with the teachings of the present invention. for example,
In the heat-developable multilayer color photographic article of Example 1 of U.S. Pat. No. 4,460.681, the following steps are employed to convert the element into an embodiment of the present invention. The sensitizing dye used to spectral sensitize the first silver halide thermally developable photographic emulsion is the sensitizing dye used to sensitize the first emulsion 49 of Example 1 of the present application. Replace with

The filter layer described in Actual Example 2 of the present application is added to the series of first and adhesion layers of Example 1 of Yoneda Toku No. 4,460,681. Place it on top. Each filter layer can also function as a barrier layer as required in the practice of the invention. Then rice 11. [Patent No. 4. A series of second layers essential for the formation of the following colors are deposited according to '160.681 (=J) and the spectral sensitizing dye of that example is replaced by the spectral sensitizing dye of Example 1 of the present application. The remaining layers in the type photographic element can be the same as those described in that patent if the photosensitivity of the element (depending on the photosensitivity of the third color-forming layer) is acceptable. If so, place the second filter layer of Example 2 of the present application on the second color-forming layer of the heat-developable photographic element.
A third set of color-forming layers of Example 1 of U.S. Pat. Totsu 50 - Change the spectral sensitizing dye in the emulsion layer. Similar substitutions of sensitizing dyes in any of the other known color imaging methods, addition of filter layers, and/or changes in the relative sensitivity of silver halide layers are also readily available in accordance with the teachings of the present invention. British Patent No. 3,100,
Diffusion phos I such as those disclosed in No. 4.58A
- Thermographic color imaging systems are also useful in practicing the present invention.

Photographic elements can contain image dye stabilizers. Such image dye stabilizers are described in British Patent No. 1.326.889, US Pat. [No. 3,432,300 and 3,698,909S”!, Stern et al., U.S. Pat. No. 3,574..627, Plannock et al., U.S. Pat. Patent No. 3.76
No. 4,337 and U.S. Pat. No. 4,042 to Smith et al.
No. 394.

Filter dyes are materials well known to photographic chemists. The dye, if used, must be selected based on its optical filter properties to ensure that it filters the appropriate wavelengths. Filter dyes and methods of incorporating them into photographic elements are described in U.S. Patent No. 4. /1
10.8ri No. 2; No. 3,671.648; No. 3.42
3.207; and 2,895.955; British Patent No. 485.624, and Research Disclosure Vol. 176 (December 1978) No. 17643. . Filter dyes can be used in the present invention to impart room light handling properties to the element. A dye that does not allow the transmission of light having a wavelength shorter than the shortest wavelength of the sensitized layer at the back of the emulsion layer is added in a layer above one or more (preferably all) of the emulsion layers. Can be used. The cutoff filter dye is preferably about 5Qn shorter than the shortest wavelength to which any of the emulsion layers is sensitized.
Does not transmit light over m. The filter dye should also be rendered non-fugitive (i.e., non-migratory) and decolorizable (e.g. by bleaching in a developer or with heat).
It should be extractable (e.g. removed by the action of some bath solvent).

Sen's usual photographic additives such as coating aids, antistatic agents,
acutance dyes, antihalation dyes and layers,
J: Yes, even if antifoggants, latent image stabilizers, anti-kink agents, etc. are present.

Although not essential to the practice of the present invention, one particularly important additive that has been found to be particularly useful in the application of the present invention is a high intensity failure failure (HIRF) reducer. Among the numerous types of stabilizers for this purpose are chloroparadites and chloroplatinates (U.S. Pat. No. 2,566.
263), iridium and/or rhodium salts (U.S. Pat. No. 2,566.263: 3.901.713)
(Beck et al., Journal 1976.4.131).

Example 1 A multilayer IR-sensitive photographic color material was prepared by coating the following layers in sequence on a resin-filled paper base: 1st layer: antifogging agent, speed agent, and cyan color-forming coupler 23 and 2=1. (U.S. Patent No. 4..36
No. 3.873, a gelatin chemically sensitized (sulfur) silver chlorobromide emulsion containing (88 mole % 3r) (prepared by the standard method described in No. 3.873).

4.2% Ag, and approximately 0.6μ particle size) at 880r+m with dye 9 in an amount of 4,0X10'moles per mole of silver.
It is sensitized to the spectrum in the region of , and the silver and cyan coupler coatings M are each 346 m! j/m2 and 51
7 mg/TrL2 was coated with Ruyouni.

The gelatin intermediate layer containing the second layer Nigel hardener, U, V, absorbent, and antioxidant has a gelatin coverage of 823
It was coated to give a concentration of mg/TrL2.

Third layer: The same silver chlorobromide emulsion as the first layer containing magenta color-forming coupler U is sensitized to a spectrum in the 830 nm region with an amount of dyestuff in an amount of 1.6 x 10-4 moles per mole of silver. The silver and magenta power blur were coated at a coverage of 402 my/m' and 915 mg/7rL2, respectively.

4th layer: gelatin intermediate layer containing hardener, U, V, absorbent, and antioxidant with gelatin coverage of 1.19y
/m2.

Fifth layer: The same gelatin silver chlorobromide emulsion as in the first layer containing the yellow coloring coupler λY was added at 5.9×10 per mole of silver.
The dye was dye sensitized to the 780 nm range of the spectrum with a molar amount of J and coated with In of silver and yellow couplers of 346 mg/TrL2 and 474 mg/TrL2, respectively.

6th layer: gelatin intermediate layer containing hardener, U, V, absorbent, and antioxidant; gelatin coverage is 873L
It was coated so as to have an area of 100 m2.

7th layer: Protective gelatin top layer containing hardener and surfactant with gelatin coverage of 1.039/
The above structure was first exposed to 2400 mC on the filter surface using a tungsten lamp at 2950 m2, and 20 cm continuous type M
Carbon wedge (gradient 20.2011i1 degree/cm>
, Latten red-selective interference filter, and 780 nm
Exposure was performed for 0.1 seconds through a near-infrared glass bandpass filter. Then separate samples in the same manner as 83
Exposure was performed using a 0 nm or 890 n1ll infrared filter. After exposure, these samples were transferred to a standard Kodak I
E I-)-2 Professional Dressing Color Chemistry 1-Lee Rice 11.1 Special W [4th. ．． The conditions were as described in No. 363.873.

After treatment, perform status D moisture measurement and use the results as the first
Shown in the table. The corresponding DlooE curve, excluding the effects of secondary exposure, is shown in FIG. At 780r+m exposure, color separation is excellent and the sensitivity jfi difference between layers is 0.71ooE
That was it. With 830 nm exposure, no yellow color was observed, and the 830 nm layer (main color) and 8
The separation between 90nmlffi (cyan color) was 0.65logE in terms of sensitivity. Upon exposure to 890 nm, only a cyan coloring layer was observed.

The results of a set of exposures on this color multilayer construction suggest that the introduction of filter dyes in the interlayer is unnecessary.

A three-color infrared-sensitive material was prepared for coating on a resin-coated paper substrate as follows: 1) containing an antifoggant, a speed enhancer, and a cyan color-forming coupler; Consisting of a silver chlorobromide emulsion (4.2% Aq) sensitized to the 880 nm range of the spectrum with a concentration of approximately 3.0 to 6.0 x 10-4 moles of dyestuff per mole, each approximately 450 to 550~/m” and 250~450mg/
First layer of m coupler and silver coating B1.

2) Approximately 0.8 to 1.2 g/m2F (m):
: Gelatin, U, V, absorbent, antioxidant, gel hardener, and filter dye of type 25, λ1.27 or H (this means that the absorbance of the coated dye is 0.830r+n+).
1 to 0.6, with a minimum absorption at 880 nm. a second layer containing 100% acetate (dispersed in oil, such as in the dispersion process described in '873).

3) A spectrum in the 83' Onm region with a concentration of approximately 0.8 to 2.4 x 10-4 moles of dye per mole of silver =
59 Silver chlorobromide emulsion similar to the first layer sensitized and coated with a silver coverage of 300-500 m9/m2, various sensitivity enhancers, antifoggants, and 850-950 mg/TrL
A third layer containing a magenta color-forming coupler coated in an amount of 2.

4) Type 2 dispersed in oil and coated in gelatin such that the absorbance at 780r+n+ is 0.1-0.6 and the minimum absorbance is observed at 830 and 880 nm, and or 28 A fourth layer similar to the gelatin interlayer of the second layer containing pigments.

5) 780r containing the yellow coloring coupler λ and in an amount of 3.0 to 7.0X10' moles of L per mole of silver.
Dye sensitized to the +IIl range of the spectrum and with silver and yellow coupler coverages of 250 to 450, respectively.
A fifth layer of silver chlorobromide emulsion similar to the first layer coated with mg/TrL2 and varying from 425 to 525 IRg/m2.

6) A first 60-6 layer containing gelatin as an intermediate layer, U, V, absorbent and antioxidant, with gelatin coverage varying from 0.8 to 1.2 g/m2.

7) Protective gelatin top containing a gel hardener and a surfactant and coated with a gelatin coverage of 0.9 to 1.1 g'/m2]-1.

The above structure is a tungsten lamp sensitometer that provides 2400 mC illuminance at the filter surface, and a 20 cm continuous wedge (
Slope: 0.20 degrees/cm), shown in Figure 2 when exposed for 0.1 seconds through a Latin red selective filter, and a 7-8.0 nm near-infrared glass bandpass filter. It has a -10(] E curve. If no filter dye is present in layer 4, the D-100E curve (shown as a solid line) for M5 and layer 3 is partially applicable, so the Pure color separations are not allowed.

However, if the filter dye in layer 4 is 780 nm
After introduction at an absorbance of 0.4, the D-
10 (the effect on the IE convex curve is shown by the dotted line), where full density of the color was achieved in the dew of layer 3 and the head of the layer 5.

The same effect is observed for exposure of the material with a tungsten sensitometer as described above but using an 830 nm narrow bandpass filter. If no filter dye is present in layer 2, an overlap of the D-10gE curves is observed. However, 8 filter dyes in layer 2
The effect on layer 1 after introduction at 0.4 absorbance at 30 r+n+ is shown by the dotted D-10 (IE convex curve, so that the full density of color in layer 3 before exposure of layer 1 is achieved.

Example 3 As an alternative to the color multilayer construction described above, if the sensitivity of emulsion layers 1 and 3 is appropriately manipulated as follows,
n1ll absorbing filter dye becomes unnecessary: 1) Contains a silver chlorobromide emulsion sensitized to 880 nm and cyan color forming coupler 23 with an amount of 4.0 x 10-4 moles of dye per mole of silver. However, the coating amount of silver and coupler is 346mg/m2 and 517I respectively! g/TrL2
The first layer as described in Example 1 was coated to give a.

2) Second layer contains Nigel hardener, U, V, absorbent, and antioxidant, and gelatin coverage is 823 mg/TrL
Gelatin middle layer coated as 2.

3) All of the third to seventh layers have the same structure as described in Example 2.

This multilayer color material, when exposed using the 780 and 830 n1ll filters of a tungsten sensitometer as described in Example 2, produced a D-1 image similar to that shown in FIG.
0 (12 curves to the right. D-10 for layer 5 and layer 3 at 780 nm exposure (12 curve overlap is layer 4)
Occurs when there is no filter dye in the filter (solid line),
Then, by introducing dye into layer 4, the pure color separation by 780 rv exposure is determined by the D-10gF curve for layer 3 (
is achieved, as shown by the dotted line). However, in the case of an 830 r+m filter exposure, full density of color in layer 3 is achieved before exposure of layer 4, which negates the need for filter dye in layer 2. In this case, good color separation was achieved by precise electrocution of both layers.

2H5 Example 4 To demonstrate the usefulness of the present invention, two types of diffusion transfer constructions in two different colors were prepared as follows.

Photographic elements were prepared by sequentially coating the following three layers onto a coated polyester film support.

a) A first layer consisting of a yellow dye developer of Structure A dispersed in gelatin. The amount of pigment coverage is 5mg/dn+2
and that of gelatin was 7.2 my/dn+2.

b) Addition of a dye of structure B (3x10-4 mol dye 1 mol silver) with J: 0, sensitized to 780 nm light;
Silver chlorobromide emulsion (36/64:
A second layer consisting of Br/C1). The amount of silver coating is 5 m! J
/ m2.

C) Saleta 1 dispersed in gelatin (145 mg/dm2)
-Phenyl-5~pyrazolidinone (2, 2111!?/dm2) Kara 1 Nyl'M3Fm
.

Coating 2 Coating 2 is based on the fact that a magenta dye developer of Structure C was used in place of the yellow dye developer in No. 1M, and that the silver halide emulsion contained a sensitizing dye with an IR structure at 780 nm. (5x10-5 mol dye 1 mol silver) by addition of 8
Coating 1 except that it was sensitized to 30 nm light.
It was the same.

Five lean pulls taken from Sosada Covering 1 were separately subtracted in a sensitometer with 0 to 4 consecutive neutral density wedges and 73
0nm, 760nm, 790nm, 820nm, 850
A 500 watt tungden filament was exposed to light from a 1~lamp filtered with a 880 nm or 880 nm narrow bandpass interference filter.

The sample was prepared using an Agfa Gouvell l-r Cl) 380J color diffusion transfer processing machine with a 2% potassium hydroxide aqueous solution as a processing solution.
Gewert [copy color CCF J laminated to dye-receiving sheet. The receptor sheet was separated after 1 minute.

Coating 1 had maximum sensitivity at 760 nm and produced a positive yellow image on the receiving sheet. Coating 1 is 820 nm
It showed no measurable sensitivity at longer wavelengths.

This test procedure was repeated with coating 2. In this case 8
Maximum sensitivity was observed at 20 r+m, producing a positive magenta image. Coating 2 exhibited 0.57 +00 E units less sensitivity at 760 nm than at 820 nm. The sensitivity was 1.70 inverse log E units lower at 880 nm than at 820 nm.

These layers should function properly in accordance with the teachings of the present invention when used in currently commercially available diffusion transfer elements.

Example 5 A monochromatic infrared-sensitive photographic material was prepared by sequentially coating a Ted paper base with the following layers.
: 1) Chemically sensitized silver chlorobromide emulsion (6
, 8%Act> to l'J.

The emulsions are 1.12g/m" and 503mg/m" respectively.
With a coupler of 2 and a coating amount of silver, 1. l
It was sensitized to the spectrum in the 830 nm region with a dye sample having a dye concentration of 10' mol %.

2) 1.20g/m2F coating filter: Ceftin, U, V, absorbent, antioxidant, gel hardener, and filter dye λtan (which was dissolved in methanol and added to the geladine mixture) and coated to give a filter dye coverage of 15.1 Ig/m, 2).

3) Contains a gel hardener and a surfactant and is coated with gelatin.
The third layer coated so that m is 1.04 g/m2 (
Protective gelatin knob]

Example 6 A ψ-color infrared-sensitive fiber was prepared as described in Example 5, except that Shidan was added as the filter dye and the filter dye coverage in the second layer was 15.
It was coated at a concentration of 11 ng/TrL2.

Example 7 A monochromatic infrared sensitive membrane was prepared as described in Example 5, except that no filter dye was introduced in the second layer (control). In all samples, the material was irradiated with a 20 cm continuous wedge (slope: 0
．． 20i [t/cm), a Latin red selective interference filter, and an 830 nm near-infrared glass bandpass filter for 0.1 seconds. After exposure, the samples were processed in a standard Kodak E-2 Processing Color Chemistry under conditions as described in U.S. Pat. No. 4,363,873.

After the treatment, status Dllf was measured once, and the results are shown in Table 1. Gel interlayers containing the filter dyes of Examples 5 and 6 were manually applied onto polyethylene terephthalate, dried, and the absorption properties determined by Perkin-
Measured using an Elmer absorption spectrophotometer. These results show that dye 29 of Example 5 has a maximum sensitization peak at 810 nm, a secondary peak at 705 nm, and a peak of maximum sensitization at 705 nm.
It was shown to have residual absorption at 900 nm. The filter dye used in Example 6 had a maximum sensitization peak at 780 r+m and a secondary absorption at 700 nm, with a broad residual absorption from 520 nm to 880 nm.

These results suggest that the photographic sensitivity of the emulsion layer can be manipulated by introducing an infrared absorbing dye into the gel layer on the infrared sensitized emulsion. These filter dyes are from Example 5.
Although not completely processable as reflected by a high D□in of 6 and 6, the photographic sensitivity of the emulsion was reduced by about 0.510 gE compared to Control Example 7).

Table 2 Example 5 0.33 1.92 3,45
1.82 Example 6 0,30 1.85 3,55
1.56 Example 70.18 2.23 3,
97 2.27 (Control) 1) Relative sensitivity measured at absolute density 0.75 2) Slope of the line connecting density points 0.50 and 1.30 from base + fog.

Example 8 A full color infrared sensitive material was prepared by sequentially coating the following layers onto a resin coated paper base: Multilayer IR sensitive photographic color discrimination by sequentially coating the following layers onto a resin coated paper base: Prepared: 1st layer: Cyanide chemically sensitized silver chlorobromide emulsion (6.7% Δg) containing antifogging agent, speed enhancer, and cyan color-forming coupler z1 at 1.6X10' per silver mole. It was sensitized to the B 80 nm region of the spectrum with a molar amount of dyestuff and coated with silver and cyan coupler coverages of 412 and 634 mg/m2, respectively.

2nd layer; gelatin intermediate layer containing gel hardener, U, V, absorbent, and antioxidant with gelatin coverage of 828
It was coated in a ratio of m1/m2.

3rd m: Antifogging agent, speed increasing agent, J5 J:
gelatin chemically sensitized silver chlorobromide emulsion (6.6% to 8) containing magenta color-forming coupler 22 per mole of silver.
sensitized to the 830 nm region of the spectrum with an amount of x10' mole of dyestuff, and the silver and magenta coupler coverages were 492 μ/m and 1.12 g/TrL2, respectively.
It was coated so that

4th layer: gelatin intermediate layer containing hardener, LJ, V, absorber, antioxidant and filter dye λD (which was dissolved in methanol and added to the gelatin mixture) with filter dye and gelatin. The coverage amount of each is 8.
It was coated at 31Q/m2 and 0.65g/TrL2.

5th layer: U cyanide chemically sensitized silver chlorobromide emulsion (6.7%Ag) containing antifogging agent, speed enhancer, and yellow coloring coupler 21-3.4X10 per silver mole.
Dye sensitization to the spectrum in the 780nlIl range with a molar amount of dye 7, resulting in silver and yellow coupler coverages of 679mg/I97Ing/TrL2, respectively.
It was coated to a thickness of m2.

6th layer: Gelatin intermediate layer containing hardener, U, ■, absorbent, and antioxidant with gelatin coverage of 876Rg
/m2.

7th layer: Protective gelatin top coat containing hardener and surfactant with gelatin coverage of 1.04g/T.
rL2 niru J: -) ni receive I L, ta.

Example 9 A multicolor infrared-sensitive material was prepared as described in Example 8: however, dyestuff was added as the filter dye and the filter dye coverage in the i4 layer was 8. It was coated on a sea urchin at a rate of 31n9/m2.

Example 10 A multicolor infrared-sensitive material was prepared as described in Example 8: however, no filter dye was introduced in the fourth layer (control) and the gel coverage was 1.20 g. /
It was m2.

In Examples 8 to 10, all materials were those of Examples 5 to 7.
Exposure to tungsten sensitizer as described in:
However, other samples were similarly exposed using 780 nm or 890 nm infrared filters.

The sensitometric results are shown in Table 1. Filter dye gel interlayer (layer 4) from Examples 8 and 9
) was manually applied onto polyethylene terephthalate as described above. The absorption curves show that the absorption of 780n1ll light and 83Or+m light are similar for the dye interlayer of Example 8 and 780 nm for the dye interlayer of Example 9.
This suggests that a lower absorption of 830 nm light is observed than that of 830 nm light. Sensitometric results for the multilayer materials of these examples also support this observation. 7801
111 exposure, the sensitivity loss of layer 3 (magenta color) when compared to the unfiltered layer 3 of example 10 (control) was approximately 25,100 for examples 9 and 8, respectively.
F and 361ogE. For 830 nm exposure, the layer-by-layer sensitivity loss compared to the control (Example 10) was smaller in Example 9 (lower filtering effect of the dye interlayer) than in Example 8. (Q, 91oΩF for 27100E).

In addition, the loss of photographic sensitivity was as follows in Example 10 at 780 nm exposure.
Also observed in layer 5 (780 nm sensitized yellow color of Examples 8 and 9) compared to the (control) interlayer without filter dye. 780 in layer 4 after the first unfiltered 80 nm exposure of layer 5 is made.
Although absorption of nm light occurs, a sensitivity loss is observed in the layer 5. These results show that for the unfiltered material of Example 10, each layer of the photographic material is exposed twice because the 780 nm light passes through all the layers, reaches the base, and then flows back through all the layers. It suggests. When filter dye is introduced into layer 4,
The first pass of 780 nm light through the multilayer materials of Examples 8 and 9 is unfiltered for layer 5 (780 nm sensitized) so that the first exposure occurs and the remaining 780 nm light passes from each
When nm light passes through layer 4, a portion of the light is absorbed.

After this filtration, the remaining 780nm light continues to pass through the layer, reaches the base, is then reflected back through the layer, and finally, as it passes through layer/I (filter layer), much of this light is Reabsorbed or filtered (effectively double filtered) to 780n
The ll1 layer (layer 5) is re-exposed. Therefore, valid 7
Since the total amount of 80 r+m exposure is lower in the multilayer material supporting the filter dye interlayer than in the interlayer construction without filter dye, the observation sensitivity of the 780 nm sensitized layer 5 is lower than this low 1-tal exposure maximum. Therefore it is low.

The results obtained from a series of exposures on the color multilayer constructions of Examples 8-10 suggest that the photographic speed of the emulsion layer can be effectively manipulated through the introduction of filter dyes.

Table 3 780nm exposure D,
Dmin - Ri V Knee Example 8 Yellow, 20
2.28 magenta, 19 1.8
5 Example 9 Yellow, 19
2.25 magenta, 18 1.
99 Example 10 Yellow, 13
2.25 magenta, 14 2
．． 16830nm exposure D
II11oDllIax Example 8 Magenta
, 20 2.13 cyan
, 31 ★Example 9 Magenta
, 18 2.23 cyan ,
25 ★Example 10 Magenta
, 13 2.22 cyan , 1
5 ★Example 9 Cyan
0.24. 713 Example 10 Yellow, 15. 803SPD2
Ac1 5.68 2.70 4.89. 1.93 5.79 2.80 5.00 2.00 6.03 2.78 5.25 2.17 3.22 2.27 ★ ★ 3.4.0 2.27 ★ ★ 3.49 2. 27 ★ ★ ★ ★ 2.54 ★ 2.58 ★ Example 11 A multilayer IR-sensitive photographic color material was prepared by sequentially coating the following layers on a resin-coated paper base: 1st layer: antifoggant A gelatin/chemically sensitized silver chlorobromide emulsion (88 mole % [3r, 16.7% Ao, and about 1.0 micron grain size) containing cyan color-forming coupler 23 per mole of silver. 1.6X10'
sensitized to a region of the spectrum of 880 nl with a molar amount of dyestuff, and a coverage of silver and coupler of 4
It was coated at a concentration of 17η/77L2 and 636 mg/m 2 .

The gelatin intermediate layer containing the second layer Nigel hardener, U, V, absorbent, and antioxidant has a gelatin coverage of 828.
It was coated so that it was my/m2.

Layer 3: Gelatin/chemically sensitized silver chlorobromide emulsion containing antifoggant, speed enhancer, and magenta color forming coupler 22 (88 mol% Br, 6.7% ACI and approx.
．． 5μ grain size) was sensitized to the 830 nm region of the spectrum with an amount of 8.8 x 10 moles of dyestuff per mole of silver, and this was combined with silver and coupler coverages of 4
It was coated so that it was 92 my/m2 and 1.12 g/m2.

4th layer: gelatin intermediate layer containing hardener, U, V, absorbent, and antioxidant, with a gelatin coverage of 1.20
The coating was carried out to give a coating weight of g/m2.

5th layer: Contains yellow coloring coupler 21 and contains the same gelatin silver chlorobromide emulsion as the overlying first layer at 3.4X10 per mole of silver.
' molar amount of dye 7r780r+n+ spectrum was dye sensitized. This was coated so that the coating amounts of silver and coupler were 54.2 m9/m2 and 748 mg/TrL2, respectively.

6th layer: Gelatin intermediate layer containing hardener, U, V, absorbent, and antioxidant with gelatin coverage of 876 m'
It was coated so as to have an area of 100 m2.

7th layer: Protective gelatin containing hardening agent and surfactant Tobuko 1 ~ gelatin coverage 1.04 g/m
It was coated so that it became 2.

Example 12 A multilayer IR-sensitive photographic material was prepared as described in Example 11, except that a 780 nm sensitized layer (fifth layer)
was coated as the third layer and the 830 nm sensitized layer (third layer) was coated as the fifth layer.

Example 13 A multilayer IR-sensitive photographic material was prepared as described in Example 11, except that the 780r+n+ sensitized layer (5th layer) was coated as the first layer and the 880 nm sensitized layer (5th layer) 1 layer) was coated as the 5th layer.

The construction was first exposed to light from a 780 nm 2m laser diode sensitometer. The sensitometer is capable of writing laser raster exposures onto a film strip through a circular wedge, neutral 11 FI filter (metallic vacuum deposition, 0-4 neutral density). Then, another sample was exposed in the same manner by the 820 nm or 880 nm laser diode light source of the sensitometer. After exposure, the samples were processed with standard Kodak EP-2 processing color chemistry.

After treatment, a status DFiJ degree measurement was performed and a corresponding D-1ogE curve was generated. The results show that the slower (faster) 830 nBnIIl sensitive emulsion layer has a full yellow color density of Example 11 before imaging by exposure.
This shows that it can be achieved for a 780 n1ll sensitized layer of ~13. The results also show the arrangement within the multilayer structure (layer 1 in Example 13, layer 3 in Example 12, layer 3 in Example 12,
1 layer 5). Unparalleled color separation was achieved between the 780 nn+ and 830 nm sensitized layers. In Examples 11 and 12, a magenta color density of 2.0 is achieved by 820 r+m laser exposure prior to imaging by exposure to the slower (>880 nm sensitive) sensitized emulsion layer. This unique color separation It is also achieved when the sensitivity of the 88Onllll sensitizing layer (layer 5) of Example 13 is further slowed down.Surprisingly,
Color separation was achieved independent of the placement of the 830 nlR and 880 nm sensitizing layers within the construct. The 880nl exposure exposes only the 880nm sensitized layers of Examples 11-13, regardless of their placement within the structure.

Results from these examples indicate that if sufficient sensitivity separation is maintained between the emulsion layers (780Bm layer is faster than 830nm layer, which is faster than 880r+n+ layer), unique color It shows that decomposition is achieved.

[Brief explanation of drawings]

1A, 1B, and 1C show the photographic elements of Example 1 at 780 Bm, 830 Bm, and 89 Bm, respectively.
D-1Cg when exposed to light with a wavelength of 0 nm [
It represents the g curve. FIG. 2 shows the photographic element of Example 2 exposed to light at a wavelength of 780 nm at 1)'-10! It represents the lE curve.

Claims (37)

[Claims] (1) a) a substrate; and b) at least three silver halide emulsion layers on one side of the substrate, each of the silver halide emulsion layers being associated with a different color photographic coupler; each can form a different color dye upon reaction with an oxidized color photographic developer, and can provide a full color image without exposure to light in the visible region of the electromagnetic spectrum. In a photographic element, the three silver halide emulsion layers are arranged in order from the substrate toward the surface of the element: a first emulsion sensitized to a portion of the infrared region of the electromagnetic spectrum; a second emulsion sensitized to a portion of the infrared region of the electromagnetic spectrum having a shorter wavelength than the portion to which the emulsion is sensitized; comprising a third emulsion sensitized to the infrared portion of the spectrum, and the three silver halide emulsion layers have: i) each of the three layers has a contrast of 0.5 to 12;
In addition, regarding photographic sensitivity, the sensitivity of the third emulsion is at least 0.2 log higher than that of the second emulsion layer at an optical density of 1.3.
E units faster and different from each other such that the second emulsion layer is at least 0.2 log E units faster than the first emulsion layer;
ii) between said first emulsion layer and said second emulsion layer, in the maximum sensitivity region of said second emulsion layer without absorbing more than 40% of the infrared radiation to which said first emulsion layer is sensitized; There is a filter layer that absorbs infrared radiation in an overlapping range, and between said second emulsion layer and said third emulsion layer, said second layer absorbs more than 40% of the infrared radiation to which it is sensitized. iii) from either the first and second emulsion layers or the second and third emulsion layers; The layer between the two layers absorbs the infrared rays in a range that overlaps the maximum sensitivity region of the layer farther from the substrate, but absorbs the infrared rays in the range where the other of the two layers is sensitized. There is immediately a filter layer which does not absorb more than 0.5 to 12%, and the second and third emulsion layers or the other pair of emulsion layers comprising the first and second emulsion layers respectively , and with respect to photographic sensitivity, at an optical density of 1.3, the sensitivity of the emulsion layer furthest from the substrate among the other pair of emulsion layers is A photographic element having configurations selected from the group consisting of: differing from each other by at least 0.2 logE units faster than the sensitivity of the nearest emulsion layer. (2) The photographic element of claim 1, wherein each of the at least three silver halide emulsion layers has a contrast of 2 to 8. (3) The structure is between a pair of adjacent emulsion layers, where the layer farther from the substrate is sensitized and absorbs 10 to 80% of the infrared rays, while the layer closer to the substrate is sensitized. at least one filter layer that absorbs less than 40% of infrared rays of
3. The photographic element of claim 2, having a layer. (4) there are two filter layers, one between the first and second emulsion layers and one between the second and third emulsion layers;
Each of the filter layers absorbs at least 10% and less than 80% of the infrared radiation to which the adjacent layer farther from the substrate is sensitized, but absorbs at least 10% but less than 80% of the infrared radiation to which the adjacent layer closer to the substrate is sensitized. A photographic element according to claim 2, having an absorption of less than 25%. (5) At least two adjacent emulsion layers have a difference in photographic speed and a contrast of 2 to 5, and the sensitivity difference between the two adjacent layers is at an optical density of 1.3. 3. The photographic element of claim 2, wherein the sensitivity of the nearest adjacent emulsion layer is such that the sensitivity of the adjacent emulsion layer furthest from the substrate is at least 0.5 logE units slower. (6) both pairs of adjacent emulsion layers in the three-layer emulsion layer system have a difference in photographic speed and a contrast of 2 to 5;
The sensitivity difference between adjacent layers is such that at an optical density of 1.3, the sensitivity of the adjacent emulsion layer closest to the substrate of each pair is at least 0.5 logE units slower than the sensitivity of the adjacent emulsion layer farther from the substrate. The photographic element of claim 2, which is a photographic element. (7) a) a substrate; and b) at least three silver halide emulsion layers on one side of the substrate, each of the silver halide emulsion layers being associated with a means for providing a different color dye image; A photosensitive element comprising: at least two silver halide emulsion layers capable of being exposed to light in the infrared region of the electromagnetic spectrum to provide a full color image, the three layers comprising: The silver halide emulsion layers are arranged in order toward the unexposed surface of the photographic element: a first emulsion sensitized to a portion of the infrared region of the electromagnetic spectrum; a second emulsion sensitized to a portion of the infrared region of the electromagnetic spectrum having shorter wavelengths; and a second emulsion sensitized to a portion of the electromagnetic spectrum having shorter wavelengths than the portion to which it was sensitized. and the three silver halide emulsion layers have: i) each of the three layers has a contrast of 0.5 to 12;
In addition, the first two layers have an optical density of 1.3 for photographic speed.
the sensitivity of the second emulsion layer and the second emulsion are different from each other such that the second emulsion is at least 0.2 logE units faster than the first emulsion layer; and ii) between the first emulsion layer and the second emulsion layer. , there is a filter layer that absorbs infrared rays in a range that overlaps the maximum sensitivity region of said second emulsion layer without absorbing more than 40% of the infrared rays to which said first emulsion layer is sensitized. A photosensitive element having a composition selected from: (8) The photographic element of claim 7, wherein each of the at least three silver halide emulsion layers has contrast tabs 2 to 8. (9) The structure is between a pair of adjacent emulsion layers, where the layer farther from the substrate is sensitized and absorbs 10 to 80% of the infrared rays, while the layer closer to the substrate is sensitized. at least one filter layer that absorbs less than 40% of infrared rays of
8. The photosensitive element of claim 7, comprising a layer. (10) There are two filter layers, one between the first and second emulsion layers and one between the second and third emulsion layers, each of the filter layers being adjacent to the one distal to the substrate. Claims in which the layer absorbs at least 10% but less than 80% of the infrared radiation where it is sensitized, but the adjacent layer closer to the substrate absorbs less than 25% of the infrared radiation where it is sensitized. Section 7 Photosensitive Elements. (11) At least two adjacent emulsion layers have a difference in photographic sensitivity and a contrast of 2 to 5, and the sensitivity difference between the two adjacent layers is at an optical density of 1.3 on the substrate. 8. The photosensitive element of claim 7, wherein the sensitivity of the nearest adjacent emulsion layer is such that the sensitivity of the adjacent emulsion layer farther from the substrate is at least 0.5 logE units slower. (12) Both pairs of adjacent emulsion layers in a three-layer emulsion layer system have a difference in photographic speed and a contrast of 2 to 5, and the sensitivity difference between adjacent layers is The sensitivity of the adjacent emulsion layer closest to the substrate of the pair is at least 0.51 ogE greater than the sensitivity of the adjacent emulsion layer furthest from the substrate.
8. The photosensitive element of claim 7, which is such that the unit slow. 13. The photosensitive element of claim 7, wherein said means for providing different colors comprises a dye diffusion system. 14. The photosensitive element of claim 7, wherein said means for providing different colors comprises a dye bleaching system. 15. The photosensitive element of claim 7, wherein said means for providing different colors comprises a leuco dye oxidation system. 16. The photosensitive element of claim 7, wherein said means for providing different colors consists of reaction of a photographic color coupler in each emulsion layer with an oxidized color photographic developer. (17) a) a substrate; and b) at least three silver halide emulsion layers on one side of the substrate, each of the silver halide emulsion layers being associated with a means for providing a different color dye image. A photosensitive element comprising: at least two silver halide emulsion layers capable of being exposed to light in the infrared region of the electromagnetic spectrum to provide a full color image, the three layers comprising: The silver halide emulsion layer includes a first emulsion sensitized to a portion of the infrared region of the electromagnetic spectrum; a second emulsion sensitized to a portion of the electromagnetic spectrum and a third emulsion sensitized to a portion of the electromagnetic spectrum having a shorter wavelength than the portion to which the second emulsion was sensitized;
and the three silver halide emulsion layers have: i) each of the three layers has a contrast of 0.5 to 12;
In addition, the first two layers have an optical density of 1.3 for photographic speed.
the second emulsion layer differs from each other such that the sensitivity of the second emulsion layer is at least 0.2 logE units faster than the first emulsion layer, and ii) between the first emulsion layer and the second emulsion layer, selected from the group consisting of: a filter layer that absorbs infrared radiation in a range that overlaps the maximum sensitivity region of the second emulsion layer without absorbing more than 40% of the infrared radiation to which the emulsion layer is sensitized; A photosensitive element comprising: (18) Claim 17, wherein each of the at least three silver halide emulsion layers has a contrast of 2 to 8.
Section photo element. (19) The first and second emulsion layers have a difference in photographic sensitivity and a contrast of 2 to 5, and the sensitivity difference between the two adjacent layers is at an optical density of 1.3. 19. The photosensitive element of claim 18, wherein the sensitivity of the adjacent emulsion layer closest to the substrate is at least 0.5 logE units slower than the sensitivity of the adjacent emulsion layer farther from the substrate. (20) Both pairs of adjacent emulsion layers in a three-layer emulsion layer system have a difference in photographic speed and a contrast of 2 to 5, and the sensitivity difference between adjacent layers is The sensitivity of the adjacent emulsion layer closest to the substrate of the pair is at least 0.5 logE greater than the sensitivity of the adjacent emulsion layer furthest from the substrate.
19. The photosensitive element of claim 18, wherein the photosensitive element is such that the unit is slow. (21) the third emulsion layer is spectrally sensitized to wavelengths within the visible portion of the electromagnetic spectrum, and the third emulsion layer is further from the substrate than the first and second emulsion layers; 19. The photosensitive element of claim 18. (22) the third emulsion layer is spectrally sensitized to wavelengths within the visible portion of the electromagnetic spectrum, and the third emulsion layer is disposed between the first and second emulsion layers; 19. The photosensitive element of claim 18. (23) the third emulsion layer is spectrally sensitized to wavelengths in the visible part of the electromagnetic spectrum, and the third emulsion layer is closer to the substrate than the first and second emulsion layers; The photosensitive element of claim 18. (24) A color photographic element comprising at least three silver halide emulsion layers on a substrate, each of the three silver halide emulsion layers being capable of forming a monochromatic image of a different color dye; The three silver halide emulsion layers include, in either order, a first silver halide emulsion layer sensitized to one part of the infrared region of the electromagnetic spectrum, and a first silver halide emulsion layer sensitized to another part of the infrared region of the electromagnetic spectrum. a second silver halide emulsion layer sensitized to a third portion of the electromagnetic spectrum, the wavelengths of maximum spectral sensitivity of the first and second emulsion layers differing by at least 15 nm; and a third halogen sensitized to a third portion of the electromagnetic spectrum. a silver halide emulsion layer, wherein the wavelength of maximum spectral sensitivity of the third layer differs by at least 15 nm from the wavelength of maximum spectral sensitivity of the first and second layers; The sensitivity is such that, between any two layers having maximum sensitivity in the infrared region, the emulsion layer with a shorter wavelength maximum spectral sensitivity has a sensitivity that is at least 0.2 logE units faster than the other of the two layers. A color photographic element characterized by being something. (25) The photographic element of claim 24, wherein each of the at least three silver halide emulsion layers has a contrast of 0.5 to 12. 26. The photographic element of claim 24, wherein each of the at least three silver halide emulsion layers has a contrast of 2 to 8. (27) The wavelength of maximum sensitivity for each of the at least three emulsion layers differs from each other by at least 35 nm, and the contrast of each of the three emulsion layers is from 1 to 11. Color photo elements. (28) The wavelengths of maximum sensitivity for each of the at least three emulsion layers differ from each other by at least 50 nm, and the contrast of each of the three emulsion layers is from 2 to 8. Color photo elements. (29) Claim 24, wherein among the two layers, the emulsion layer with a shorter maximum sensitivity wavelength has a sensitivity that is at least 0.5 logE units faster than the other of the two layers; Color photographic elements of paragraph 27 or paragraph 28. (30) The emulsion layer of claim 27, wherein among the two layers, the emulsion layer having a shorter wavelength of maximum sensitivity has a sensitivity that is at least 0.5 logE unit faster than the other of the two layers. Color photo elements. (31) Among the two layers, the emulsion layer having a shorter maximum sensitivity wavelength has a sensitivity that is at least 0.5 logE unit faster than the other of the two layers. Color photo elements. 32. The color photographic element of claim 24, 25, or 26, wherein the means for providing different color dye images is a photographic color coupler. 33. The color photographic element of claim 28, wherein said means for providing different color dye images is a photographic color coupler. 34. The color photographic element of claim 30, wherein said means for providing different color dye images is a photographic color coupler. 35. The color photographic element of claim 24, wherein said means for providing different color dye images is diffusion transfer. 36. The color photographic element of claim 26, wherein said means for providing different color dye images is diffusion transfer. 37. The color photographic element of claim 30, wherein said means for providing different color dye images is diffusion transfer.