JPS584337B2 - Kogakurokuontaino Keiseihouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recording a sound image in a color photographic material, and more particularly to a method for forming an optical recording band in a multilayer color photographic material.

Methods for recording sound images on color photosensitive materials generally used in movies or television include optical recording methods and magnetic recording methods.

The present invention relates to a method of forming a recording band suitable for optical recording.

The reproduction of sound by optical recording on color print film, color reversal film, color reversal print film, etc. used in the fields of movies and television is as follows:
The sound signal recorded as density or area on the film is converted into an optical signal, which is converted into an electrical signal by a photoreceiver, and which is further converted into a sound signal.

In this regeneration process, phototubes with various spectroscopic customizations are used as photodetectors.

The most commonly used type is called the S-1 type, which has a maximum spectral sensitivity at about 800 mμ in the infrared region (for example, AdrinOornwellQl).
[See Color Oinematograph, p. 593 (1951)].

On the other hand, in conventional subtractive color photographic light-sensitive materials, the main absorption of dyes produced by the oxidation products of developing agents such as paraphenylene diamines and color couplers are all in the visible range. This does not match the spectroscopic customization of the phototube mentioned above.

Therefore, the sound output of these colored pigment images alone is extremely weak and is of no practical use.

However, in order to reproduce sound in color photographic light-sensitive materials, a process is usually performed in which a silver image or silver sulfide image is formed on the recording band, and this silver image or silver sulfide image is The concentration in the infrared region of the light is used for sound reproduction.

In this case, the infrared density (transmission density) is usually 1.0 to 1.
．． It is about 6.

The production of recording bands for color print films is described, for example, in the Journal of the Society of Motion Picture and Television Engineers.
of Motion Picture and Tele
vision Engineers) J vol. 77, 11
54 (1968).

According to this method, the color image in the image area and the sound image in the recording band are simultaneously color-developed in the color developing bath.

The first fixing bath removes unexposed silver halide, and the bleaching bath rehalogenates the developed silver produced during the development step.

In the sound development process, the silver halide in only the recording band is converted into a silver image by selectively applying a viscous sound developer to the recording band.In the second fixing bath, the silver halide in the image area is converted into a silver image. is fixed and removed, and the stabilization bath stabilizes the image dye.

The infrared density of the silver image of the recording band thus formed is primarily used for sound reproduction.

In this way, in the production of color film recording bands,
As mentioned above, processing steps are required to produce a silver or silver sulfide image.

The reason for providing such a recording band made of silver or silver sulfide is, as already mentioned, that the spectral sensitivity of the phototube used for sound reproduction has a maximum sensitivity in the infrared region, and that the maximum sensitivity is produced by the color development process. This is because coloring dyes do not have sufficient density in this wavelength range.

The process of forming a silver image or silver sulfide image on the recording band is as follows:
This is necessary in addition to the step of forming a dye image on the image area, and there has been a desire for a method of forming a sound image without requiring such a special processing step.

As one means of solving this problem, recently, color processing bleaching techniques have been developed for the silver halide emulsion layer of color photographic light-sensitive materials.
Compounds that have the property of significantly reducing the desilvering rate or substantially eliminating the -L desilvering effect during the desilvering process, or compounds that cause the desilvering effect only at the initial stage of the desilvering process to reach a certain degree of desilvering. In the above methods, a method has been proposed in which a compound having a property of substantially preventing desilvering is contained.

A compound that inhibits or interrupts such desilvering action is hereinafter referred to as a "desilvering inhibitor." Generally, color photographic materials are produced by layering silver halide emulsion layers with different photosensitive regions on a support. I will do it.

After imagewise exposure of such a photographic material, color development is performed to form a dye image and a silver image.

The silver image is then oxidized by a bleaching process and removed from the photographic material by a fixing process.

A color photograph consisting of a dye image is thus obtained.

The above color photographic light-sensitive material has a layer forming a silver image that is not removed by such a desilvering process,
By carrying out conventional color processing, a color photograph having a silver image as well as a color image can be provided.

This silver image is advantageously used as a recording band.

- A layer containing a desilvering inhibitor as described in L and forming a silver image that is not removed in the desilvering process (hereinafter referred to as "recording band forming layer")
For example, as a color photographic light-sensitive material having an image-forming layer and a diffusion-resistant material that does not form an image upon image-forming exposure, as described in U.S. Pat. No. 3,715,208, Examples include color photographic materials having a silver halide emulsion layer containing a desilvering inhibitor (for example, a diffusion-resistant thiol compound).

In addition, an image forming layer such as that described in U.S. Pat. Examples include color photographic materials having a silver halide emulsion layer containing a compound that releases an inhibitor.

Also, U.S. Patent Application No. 360,507 (filed date 1973)
A color photographic light-sensitive material having an image-forming layer and a silver halide emulsion layer containing a compound having at least two oxyethylene groups as a desilvering inhibitor as described in May 15, 2007). I can do it.

Also, U.S. Patent Application No. 439,675 (filing date 1974)
A color photographic light-sensitive material having an image forming layer and a silver-genide emulsion layer containing a nitrogen-containing heterocyclic compound having a thioether bond as a desilvering inhibitor as described in I can give it to you.

Also, U.S. Patent Application No. 451,658 (filing date 1974)
Nitrogen-containing heterocyclic ring having a nitrogen atom that forms a quaternary salt by bonding with a group having 11 or more carbon atoms, as described in the following: Examples include color photographic materials having a silver halide emulsion containing the compound.

In any of the above-mentioned photosensitive materials having a recording band forming layer, the recording band forming layer should not have a silver density that is unfavorable for color reproduction after normal image forming exposure and normal processing. .

That is, if a large amount of silver overlaps the color image after normal image forming exposure and normal processing, the color becomes cloudy, which is extremely inconvenient in terms of color reproduction.

In order to avoid the formation of such a silver image which is undesirable in terms of color reproduction, for example, US Patent Application No. 451,658 (filed on March 15, 1974) discloses that the spectral sensitivity of the recording band forming layer is adjusted to form an image. If the spectral sensitivity of the recording band forming layer overlaps with the spectral sensitivity of the layer, it is described that the sensitivity of the recording band forming layer is set to one fourth or less, preferably one sixth or less, of the sensitivity of the image forming layer.

In this way, after image-forming exposure, the silver image formed in the recording band forming layer by normal processing is limited to the very high density part of the color image, and this silver image covers the black part of the color image. This results in a stronger effect, which can bring about a rather preferable result in terms of color reproduction.

On the other hand, sound exposure from a sound original film to create an optical recording band needs to be carried out at high illuminance because the sensitivity of the recording band forming layer is low as mentioned above. Because the more sensitive imaging layer is overexposed, a color image is formed along with the silver image in the recording band area.

This color image tends to become blurred due to excessive exposure, resulting in unfavorable sound reproduction.

In order to avoid such inconveniences, it is desirable to separate the spectral sensitivity of the recording band forming layer from the spectral sensitivity of the image forming layer.

That is, ideally, the recording band forming layer would not be exposed by normal imaging exposure, while the image forming layer would not be exposed by sound imaging exposure from the sound original film.

Tsuki's subtractive multilayer color photographic light-sensitive material has a first light-sensitive silver halide emulsion layer that is sensitive to the blue region of the spectrum and contains a coupler that reacts with an oxidized form of a developing agent to form a yellow dye. a second light-sensitive silver halide emulsion layer, sensitive to the red region of the spectrum and containing a coupler that reacts with the oxidized form of the developing agent to form a cyan dye, sensitive to the green region of the spectrum; The third photosensitive silver halide emulsion layer reacts with the oxidized form of a developing agent to form a magenta dye.

Color image formation is performed using the blue, red, and green photosensitive components of this spectrum, but the spectral sensitivity of the optical recording band forming layer mentioned above is separated from the spectral sensitivity of these color image forming layers. By exposing them to light of different wavelengths, it is possible to prevent undesirable overlapping of the silver image on the color image and undesirable overlapping of the undesirable color image on the official image.

In one such attempt, U.S. Patent No. 3,737
, No. 312 proposes a color photographic material having a silver halide emulsion layer (optical recording band forming layer) having a photosensitive area in the region where the spectral sensitivity of the color image forming layer is the lowest.

In this case, the region where the spectral sensitivity of the color image forming layer is the lowest is 470 nm to 4 nm between the blue region and the green region of the spectrum in the case of ordinary color photographic materials.
around 80 nm, and around 580 nm to 600 nm between the green and red regions of the spectrum.

Therefore, by setting the spectral sensitivity of the recording band forming layer in the vicinity of 470 nm to 480 nm or in the vicinity of 580 nm to 680 nm, and performing sound image forming exposure with light of these wavelengths, it is possible to avoid undesirable overlapping of silver images in the color image. It should be possible.

However, since light with a wavelength of 580 nm to 600 nm is normally used as safe light for color print films, if the spectral sensitivity of the recording band forming layer is set within this range, the safe light will cause the recording band forming layer to Therefore, it is not preferable to set the spectral sensitivity of the recording band forming layer in the vicinity of 580 nm to 600 nm.

The aforementioned U.S. Pat. No. 3,737,312 includes
It is stated that the spectral sensitivity of the recording band forming layer should be set from 470nm to 480nm.
The area where the spectral sensitivity of the image forming layer is lowest near m is actually the area where the image forming layer has overcome its relatively high sensitivity, so the spectral sensitivity of the recording band forming layer is set around this area. In this case, it is difficult to avoid undesirable overlapping of the silver image on the color image and undesirable overlapping of the undesirable color image on the sound image.

Therefore, a second method to avoid the undesirable overlap of the silver image into the color image and the undesirable overlap of the color image into the sound image is to set the spectral sensitivity of the recording band forming layer to the infrared region. In order to achieve the above object, the maximum spectral sensitivity of the recording band forming layer must be at a wavelength longer than 750 nm.

However, such spectral sensitizing dyes that provide spectral sensitivity in the infrared region are generally unstable, and sensitive materials that have been spectral sensitized using such spectral sensitizing dyes are also unstable. , poor practicality.

Furthermore, the wavelength of the exposure light applied to the recording band forming layer must naturally be infrared light, and the selection of filters for filtering such light is generally quite limited.

Next, as a third method for avoiding the undesirable overlap of the silver image on the color image and the undesirable overlap of the color image on the sound image, it is possible to set the spectral sensitivity of the recording band forming layer to the ultraviolet region.

Generally, the photosensitive region of a photosensitive silver halide emulsion itself extends from the ultraviolet region to the visible region of around 500 nm, but the binder for the silver halide grains, generally gelatin, absorbs light on the short wavelength side of the ultraviolet region. for,
It is rare to have sensitivity on the wavelength side shorter than 300 nm.

The spectral sensitivity of the recording band forming layer is set to the spectral sensitivity possessed by this silver halide emulsion itself, and the wavelength of the exposure light given to the recording band forming layer is set to light of a wavelength shorter than about 400 nm, and the exposure light applied to the color image forming layer is adjusted to the wavelength of light shorter than about 400 nm. By setting the wavelength to so-called visible light having a wavelength longer than about 400 nm, it is possible to prevent undesirable superimposition of the silver image on the color image.

Additionally, filters for filtering light of these wavelengths are easily available.

That is, first, the image forming layer is exposed to light using an ultraviolet absorption filter that absorbs light on the shorter wavelength side of about 400 nm, and then a visible light absorption filter that absorbs light on the longer wavelength side of about 400 nm from the sound original is used. The recording band cambium is exposed to light.

However, in this case, when the recording band forming layer is exposed to light, since the image forming layer is also sensitive to wavelengths shorter than about 400 nm, it is exposed at the same time, resulting in undesirable color image overlap on the sound silver image. occurs.

In general, on the shorter wavelength side of about 400 nm, among the color image forming layers, the light-sensitive silver halide emulsion layer containing a blue-sensitive yellow dye-forming coupler has the highest sensitivity, so undesirable color image overlap with the sound image occurs. has the largest yellow image.

Avoiding such an undesirable superimposition of the color image on the sound image has been achieved by providing a layer containing an ultraviolet absorbing substance between the support and the recording band forming layer.

That is, when the recording band forming layer is exposed to light having a wavelength shorter than about 400 nm, a latent image is naturally formed on the silver halide grains of the recording band forming layer.

Further, due to the action of the ultraviolet absorbing substance, no latent image is formed on the silver halide grains in the image forming layer, and therefore, a sound silver image obtained by processing a multilayer color photographic material having this recording band forming layer. Undesirable color image overlap can be avoided.

On the other hand, the exposure for forming a color image is 400 nm as mentioned above.
By using so-called visible light with a wavelength longer than m, the developable latent image formed in the silver halide emulsion of the recording band-forming layer is reduced, thus reducing the superimposition of the silver image on the color image areas. It is possible to reduce the

Accordingly, one object of the present invention is to provide a new method by which color photographs with optical recording bands can be scanned without sound development.

Another object of the present invention is to provide a new color photographic material that allows color photographs having an optical recording band to be obtained without sound development.

Another object of the present invention is to provide a color photographic material that has improved color reproducibility and does not require sound development.

Another object of the present invention is to provide a color photographic material that has improved sound quality characteristics and does not require sound development.

Other objects of the invention will become apparent from the following description of the specification.

The above and other objects of the present invention comprise a support and at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler and at least one red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler. at least one green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler and at least one ultraviolet-sensitive silver halide emulsion layer containing a diffusion-resistant desilvering inhibitor; A multilayer color photographic light-sensitive material consisting of layers, characterized in that at least one layer between the ultraviolet-sensitive silver halide emulsion layer and the support contains a diffusion-resistant ultraviolet absorbing substance. Achieved by exposing the optical recording band portion of the color photographic material to ultraviolet light and exposing the color image forming portion to visible light, and then photoprocessing the multilayer color photographic material without a sound development process. It was done.

According to one embodiment of the present invention, the photosensitive material contains on a support a coupler that reacts with the oxidized form of a color developing agent to form a yellow dye, and is sensitive to the blue region of visible light. a second silver halide emulsion layer containing a coupler that reacts with an oxidized form of a color developing agent to form a cyan dye, and having a photosensitive property in the red region of visible light;
A third silver halide emulsion layer containing a coupler that reacts with an oxidized form of a color developing agent to form a magenta dye and is sensitive to the green region of visible light, and a desilvering inhibitor, and is sensitive to ultraviolet light. (The above layer structure is not particularly limited.) At least one layer between the support and the fourth silver halide emulsion layer contains an ultraviolet absorbing substance. It contains.

This layer containing the ultraviolet absorbing substance is
, a third emulsion layer, or an intermediate layer provided elsewhere that does not have photosensitivity.

Further, this ultraviolet absorbing substance may be contained in one layer, or may be contained in two or more layers.

When such a multilayer color photographic light-sensitive material is subjected to image-forming exposure using visible light and sound image-forming exposure using ultraviolet light from a suitable original material, color development is performed to form the first image.
The second silver halide emulsion layer contains a yellow dye image and a silver image, the second silver halide emulsion layer contains a cyan dye image and a silver image, and the third silver halide emulsion layer contains a magenta dye image and a silver image. A silver image is formed in the silver halide emulsion layer No. 4.

Next, when unexposed silver halide is removed by fixing treatment and then bleached, the silver images formed in the first, second and third silver halide emulsion layers are bleached, but the silver images formed in the fourth silver halide emulsion layer are bleached. The silver image in the silver emulsion layer remains unbleached by the action of the desilvering inhibitor.

A color photograph with a dye image and a silver tone image is thus obtained.

A preferred embodiment of the light-sensitive material of the present invention includes a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler on a support, and a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and an ultraviolet absorber. A green-sensitive silver halide emulsion layer containing a macenta dye-forming coupler and an ultraviolet-sensitive silver halide emulsion layer containing a desilvering inhibitor are coated in this order.

In this case, the ultraviolet-sensitive silver halide emulsion layer containing the desilvering inhibitor is comprised of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler. Alternatively, an intermediate layer may be provided between each photosensitive silver halide emulsion layer.

The ultraviolet absorber may be contained in any layer between the silver halide emulsion layer containing the desilvering inhibitor and the support; for example, in a blue-sensitive silver halide emulsion containing a yellow dye-forming coupler. It may be contained in a layer or the above-mentioned intermediate layer, or it may be contained in two or more layers at the same time.

Another preferred embodiment of the light-sensitive material of the present invention is a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a yellow-sensitive silver halide emulsion layer containing a yellow dye-forming coupler on a support. A yellow filter layer containing colloidal silver or yellow dye, a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler and an ultraviolet absorber, and an ultraviolet-sensitive silver halide emulsion layer containing a desilvering inhibitor. It is applied in sequence.

In this case, an intermediate layer may be provided between each light-sensitive silver halide emulsion layer or between the light-sensitive silver halide emulsion layer and the yellow filter layer.

Further, the ultraviolet absorber may be contained in two or more layers at the same time.

Figures 1a, 1b and 2 show the photosensitive material of the present invention and the method of making a color photograph with an optical recording band using the same, and the conventional photosensitive material and the method of making a color photograph using the same.
a, 2b, 3a, 3b, 4a, 4b, 5a, 5b, 6a
, 6b.

In the figure, 1 represents ultraviolet light exposure, and 2 represents visible light exposure.

3 represents a recording band, and 4 represents a color image forming section. Z is a support, BL is a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, ML is a gelatin intermediate layer, RL is a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, and GL is a magenta dye-forming coupler-containing layer. UL represents a green-sensitive silver halide emulsion layer, UL represents an ultraviolet-sensitive silver halide emulsion layer containing a desilvering inhibitor, PL represents a gelatin protective layer, and U represents an ultraviolet absorber.

Further, the hatched area represents the dye image formed in each layer, and the cross-hatched (#) area represents the silver tone image.

Figure 1-a shows a conventional multilayer color photographic material before processing.
FIG.

A schematic diagram of a film obtained by exposing the recording band of this multilayer color photographic material to ultraviolet light and exposing the image area to visible light, followed by photographic processing. is shown in Figure 1-b.

In this case, since no sound development is performed, no silver image is formed on the recording band portion after processing.

Further, since all three color image forming silver halide emulsion layers are sensitive to visible light and ultraviolet light, dye images are formed in both the recording band and the image area.

The blue-sensitive silver halide emulsion layer has a high sensitivity to ultraviolet light, and the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer have a high sensitivity to ultraviolet light. It has lower photosensitivity compared to other species.

Therefore, in the recording band exposed to ultraviolet light, most yellow dye images are formed, and some cyan and magenta dye images are formed, but these dye images are As a sound image, it has little utility value.

Here, the term "recording band" refers to a part of a motion picture film, and its position and size are, for example,
For 35mm, US standard PH22.40-19
67.16 is described in PH22, 41-1969.

FIG. 2-a is a sectional view of a multilayer color photographic material containing a desilvering inhibitor before processing.

When this multilayer color photographic material is exposed and processed in the same manner as shown in FIG. 1-a, a film as shown in the schematic diagram of FIG. 2-b is obtained.

In this photosensitive material, a silver sound image is formed on the recording band portion even without sound development due to the action of the desilvering inhibitor in the recording band forming layer.

However, for the same reason as described in FIG. 1, a color image is formed overlapping the silver image on the recording band.
5-a, FIG. 5-a, and FIG. 6-a specifically illustrate cross sections of the multilayer color photographic light-sensitive material of the present invention before processing. The silver halide emulsion layer, the intermediate layer in contact with the green-sensitive silver halide emulsion layer, and both the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer contain an ultraviolet absorber.

The examples shown here are merely illustrative to help understand the gist of the present invention, and the invention is not limited to the examples shown here.

Schematic diagrams of films obtained by processing these photosensitive materials are shown in 3-b, 4b, 5-b and 6-b, respectively.

In these light-sensitive materials, due to the action of the ultraviolet absorber, the overlap of the dye image on the silver image on the recording band is greatly reduced, and therefore, as mentioned earlier, favorable results are obtained in terms of acoustic reproduction. I can do it.

In addition, there is less overlap of the silver image with the dye image in the image area, which results in favorable color reproduction.

The ultraviolet absorbing substance used in the photographic material of the present invention is diffusion-resistant, and if it has the effect of absorbing substantially most of the ultraviolet rays in the layer of the photographic material, what kind of compound (which has an adverse effect on the photographic image) may be used? UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers) or ultraviolet-absorbing polymers.

Examples of ultraviolet absorption include benzene in which an aryl group is replaced with the nitrogen atom at the 2-position, and more specifically, U.S. Patent No. 3,253,92, which is represented by the following general formula 1 and 3,5 3 3
, 7 9 4 (where R, R, , R2 are hydrogen, halogen, nitro group,
Indicates an alkyl group, an alkoxy group, an aryl group, and an aryloxy group.

); or U.S. Patent No. 3,3 1 4,7 9 4
No. 3,507,858, U.S. Patent No. 3,352,681 and British Patent No. 1,
Examples include 4-thiazolidone compounds as described in No. 054,120, penzophenone compounds, cinnamic acid ester compounds, and penzoxazole compounds.

Examples of desilvering inhibitors that can be used in the present invention include compounds (such as thiol compounds) described in U.S. Pat. No. 3,715,208, U.S. Pat.
A compound which reacts with an oxide of a developing agent to release a diffusion-resistant desilvering inhibitor as described in No. 5,801;
U.S. Patent Application No. 360,507 (filed on May 1973)
Compounds having at least two oxyethylene groups, such as those described in U.S. Patent Application No. 439,67
No. 5 (filing date: February 14, 1974), nitrogen-containing heterocyclic compounds having a thioether bond as described in U.S. Patent Application No. 451,658 (filing date: March 1, 1974).
Examples include nitrogen-containing heterocyclic compounds having a nitrogen atom that forms a quaternary salt by bonding with a group having 11 or more carbon atoms, such as those described in Section 5).

The ultraviolet absorbing filter used for color image forming exposure of the light-sensitive material of the present invention may be any filter that absorbs light on the shorter wavelength side of about 400 nm, and is easily available commercially.

For this purpose, for example, Fuji filter SO
-39, Fuji filter SO-40, Fuji filter SC3-41, Kodatsu Kuratuten filter -
2A, Kodak Ratten Filter 2B, Kodak Ratten Filter 2C, etc. are suitable.

As color separation filters for color image-forming exposure, conventional subtractive color separation filters are advantageously used.

Additive color printers using dichroic mirrors are also advantageously used for color image-forming exposure.

The above-mentioned ultraviolet absorption filter is advantageously used as a pre-filter in both subtractive color baking and additive color baking.

The visible light absorption filter used for the sound image forming exposure of the photosensitive material of the present invention may be of any kind as long as it absorbs light with wavelengths longer than about 400 nm and transmits light with wavelengths shorter than about 400 nm. Commercially available products are easily available.

In this case, infrared light with a wavelength longer than about 700 nm and ultraviolet light with a wavelength shorter than about 300 nm may be transmitted, since the photosensitive material has substantially no photosensitivity in that region.

Filters such as Wratten 18A, Toshiba Glass Filter UV-DIO, UV-D2, UV-D25 are suitable for this purpose.

The hydrophilic colloids used in the present invention include proteins such as gelatin, albumin, and casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate, and starch derivatives, and synthetic hydrophilic colloids, such as: Examples include polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, and derivatives thereof.

Mixtures of two or more of these colloids may be used if desired.

The most commonly used of these is gelatin, but some or all of the gelatin can be replaced by synthetic polymeric substances.

That is, an amine group as a functional group contained in the molecule,
Imino groups, hydroxyl groups, and carboxyl groups may be treated with a reagent having one group capable of reacting with them, or a graft polymer in which molecular chains of polymeric substances are bonded may be used instead.

The photosensitive silver halide emulsion of the present invention can be prepared by combining silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or mixtures thereof as described above. It is suspended in hydrophilic colloids, such as hydrophilic colloids, and is made according to known methods.

For example, it is also useful to use a single jet method, a double jet method, a controlled jet method, etc. according to various methods such as the ammonia method, the Nakaso method, and the acid method.

Furthermore, two or more types of silver halide emulsions formed separately may be mixed.

For the emulsion manufacturing method, see, for example, rThe Theory.
of Photo-graphic Process
J.C. E. K. Maci l l by Mees
Published by ansha, *Photographic (3hem
i-strynP. Fount by Grafkides
Published by Ain Press, etc.

It is well known that the photosensitivity of a silver halide emulsion itself varies depending on the halogen composition of the emulsion.

In other words, the long wave end of the spectral sensitivity of the silver chloride emulsion is approximately 410 nm.
m, the long wave end of the spectral sensitivity of the silver bromide emulsion is about 470 nm, and the long wave end of the spectral sensitivity of the silver iodobromide emulsion is about 530 nm, although it varies depending on its iodide content.

The Theory of the Photog
r-apic Process O. E. K. Mee
s, published by Macmi-11an, p. 199).

When the long wave end of the spectral sensitivity of the photosensitive silver halide emulsion used in the recording band forming layer of the light-sensitive material of the present invention exceeds 480 nm, the photosensitive halogen in the recording band forming layer may be removed by image-forming exposure with visible light. The silver oxide emulsion is exposed, thus resulting in increased overlap of the silver image into the final color image area.

Therefore, it is desirable that the number of developable latent images formed when the photosensitive silver halide emulsion in the recording band forming layer is exposed to visible light is as small as possible.

For this reason, it is desirable that the photosensitive emulsion used in the recording band forming layer has a halogen composition which has a lower photosensitivity to visible light among the above-mentioned photosensitive emulsions.

For example, for this purpose, the composition of the photosensitive silver halide of the recording band forming layer should not exceed 60 mol% bromide (preferably less than 40 mol%) and iodide should not exceed 1 mol%. (preferably 0.5 mol% or less) is desirable.

By using such a halogen composition, it is possible to obtain a photosensitive silver halide emulsion for forming a recording band that has low sensitivity to visible light and high sensitivity to ultraviolet light.

Regarding the halogen composition of the photosensitive silver halide emulsion used in the image forming layer, there is no particular preferable range, and as mentioned above, silver chloride, silver bromide, silver iodide, silver chlorobromide,
Silver iodobromide, silver chlorobromide, silver chloroiodobromide or a mixture thereof is preferably used.

The light-sensitive 19E silver halide emulsion of the present invention can be prepared using active gelatin or U.S. Pat.
It may be chemically sensitized according to the method described in No. 0,689.

The photosensitive L silver halide emulsion of the present invention is disclosed in U.S. Pat.
4 4 8,0 6 0, 2,3 9 9,0 8
No. 3, No. 2,642,361 may be used for sensitization using noble metal salts such as palladium salts or gold salts.

The photosensitive silver halide emulsion of the present invention is disclosed in U.S. Pat.
1 9,0 0 1, 2,6 6 6,7 6
No. 1, No. 2,7 3 4,9 0 0, No. 2,7
3 9, 9 6 4, 3, 4 8 1, 7 4
It may be spectrally sensitized using cyanine or merocyanine dyes such as those described in No. 2.

The photosensitive silver halide emulsion of the present invention is disclosed in U.S. Pat.
stannous salts such as those described in U.S. Pat. No. 8,7,850, or polyamines such as those described in U.S. Pat. It may be reduced sensitized by reducing agents such as the following.

The light-sensitive silver halide emulsion of the present invention may be stabilized using an anticapri agent or a stabilizer.

Examples of compounds for this purpose include azaindenes, mercaptotetrazoles, noble metal salts such as palladium and platinum, oximes, imidazolium salts, and tetrazolium salts.

These include, for example, U.S. Pat.
No. 5, No. 2, 8 8 6, 4. 3 No. 7, No. 2
, 4 0 3, 9 2 7, 3, 2 6 6, 8
9 7, same No. 3, 3 9 9, 9 8 7, same No. 2, 5 9 7, 9 1 5, same No. 3, 5 6 6,
No. 265, No. 2,694,716, and No. 994,869.

The photosensitive material of the present invention includes a plasticizer such as glycerin, sabonin, or U.S. Pat. No. 3,415,649,
Same No. 3,4 4 1,4 1 3, Same No. 3,50
2,4 7 3, 3,5 1 4, 2 9 3, 3,5 0 6,4 4 9, 3,5 3
9,3 5 2, 3,5 4 5,9 7 4
No. 3,507,660, No. 3,442,
6 5 4, same No. 3, 4 7 5, 1 7 4, same No. 3.4. 6 2, 5 2 0, 3, 4 9
3,3 7 9, 3,5 1 6,8 3 3, 3,5 1 6,8 3 5, 3,5 8
No. 9,906, No.3,617,292, No.3,619,199, No.3,663,
It may also contain a coating aid as described in No. 2 2 9 and the like.

The photosensitive material of the present invention has an antistatic agent, for example, U.S. Pat. No. 3,428,456, U.S. Pat.
No. 484, No. 3, 4 5 7, 0 7 6, No. 3
, 5 4 9, 3 7 5, same No. 3, 5 4 9, 3
6 No. 9, No. 3,551,152, No. 3, 5
5 2,9 7 2, 3,547,643, 3,5 6 4,0 4 3, 3,6 1 5
, 5 3 1, 3, 6 2 5, 6 9 5,
Same No. 2,1 3 1,0 3 8, Same No. 2,5 1
8.6 9 8-, same No. 3,369,904, same No. 2,4 1 9, 9 7 4, same No. 2,4 1 9,
No. 975, British Patent No. 623,448.

The hydrophilic colloids used in the photosensitive material of the present invention include aldehyde hardeners, methylol hardeners, 1,4-dioxane hardeners, aziridine hardeners, inoxazole hardeners, and carbodiimide hardeners. It may be hardened with hardeners such as hardeners, activated vinegar halogen hardeners, activated vinyl hardeners, etc.

Typical examples of these hardening agents are, for example, U.S. Pat.
, 2 3 2, 7 6 4, 3, 2 8 8, 7
7 5, same No. 2, 7 3 2, 3 0 3, same No. 3, 6 3 5, 7 1 8, same No. 3, 2 3 2,
7 6 3, same No. 2, 7 3 2, 3 1 6, same No. 2, 5 8 6, 1 6 8, same No. 3, 4 0 3
, 4 3 7, 3, 0 1 7, 2 8 0,
Same No. 2,9 8 3,6 1 1, Same No. 2,7 2
5,294, same No.2,725,295, same No.3,100,704, same No.3,09
1,5 3 7, 3,3 2 1,3 1 3
British Patent No. 3,543,292, British Patent No. 974,723, British Patent No. 1,167,207, British Patent No. 3,655,387, British Patent No. 3, 6 5 3
, No. 906, No. 3,655,386,
Same No. 3,6 8 6,3 6 8, Same No. 3,7 5
6,828, 3,754, 924, etc. may be included.

The photosensitive material of the present invention is used as a filter dye or an irradiation prevention dye, and is disclosed in U.S. Patent No. 2,274,
7 8 No. 2, No. 2,527,583, No. 2, 9
5 6, 8 7 9, same No. 3,177,078,
It may contain compounds described in Synchronization No. 3,25, 2.9, 21, and Japanese Patent No. 39-22,069.

These dyes may be used as required in U.S. Pat. No. 3,282.
, No. 6,999.

The light-sensitive material of the present invention uses a fluorescent whitening agent as described in U.S. Patent No. 3,
6 3 0, 7 3 8, 3, 6 1 5, 5
．． 4. No. 4, No. 3, 5 8 6, 6 7 3, No. 3, 4 3 4. , 8 3 7 and British Patent No. L
3 3 2,4. 7 No. 5, same No. 1, 3 1 9, 7
6 3, No. 1, 3 3 3, 5 8 6 may be included.

The photosensitive material of the present invention uses U.S. Pat. No. 2,360,290 and U.S. Pat.
No. 27, No. 2, 3 8 4, 6 5 8, No. 2,
4 0 3, 7 2 1, 2.4. 1 8,6
1 3, same No. 2, 6 7 5, 3 1 4, same No. 2, 7 0 1, 1 9 7, same No. 2, 7 0 4,
7 1 3, same No. 2, 7 2 8, 6 5 9, same No. 2, 7 3 2, 3 0 0, same No. 2, 7 3 5
, 7 6 5, may be contained.

In the photographic material of the invention, all open-chain ketomethylene yellow dye-forming couplers are advantageously used.

Typical examples include penzoylacetanilide-based couplers, hivarilacetanilide-based couplers, and the like.

Also, all magenta dye-forming couplers such as pyrazolone and intazolon series are advantageously used.

All cyan dye-forming couplers, such as phenolics and naphthols, are also advantageously used.

These color couplers may have a campling-off group on the active carbon atom at the coupling site.

It is preferable that the color coupler has a ballast group in its molecule to provide diffusion resistance.

The terms "coupling-off group,""ballastgroup," and "diffusion resistance" are commonly used in connection with color couplers, and their meanings are readily understood by those skilled in the art.

In order to impart diffusion resistance to the coupler, a hydrophobic group having at least 8 carbon atoms, such as an alkyl group or an alkylaryl group, can be introduced into the coupler molecule by a cavity method.

Many such hydrophobic groups are known and can be used in the present invention.

The ballast group is bonded to the coupler skeleton directly or via an amine bond, ether bond, thioether bond, carboxamide bond, sulfoamide bond, urea bond, ester bond, imide bond, carbonyl bond, sulfonyl bond, or the like.

Typical diffusion-resistant materials used in the present invention are described below.

Generally, open-chain diketomethylene compounds are widely used as yellow couplers.

Examples thereof include, for example, U.S. Pat.
3 1, German Patent Publication No. 2,87 5,0 5 7, German Patent Publication No. 3,5 5 1,1 5 5, German Patent Publication No. 1,
5 4 7,8 6 8, U.S. Patent No. 3,265,5
No. 06, No. 3, 5 8 2, 3 2 2, No. 3,
7 2 5,0 7 2, German Patent Publication No. 2,1
6 2,8 9 9, U.S. Patent No. 3,3 6 9,8
9 5, German Patent Publication No. 3,4 08,1 94, German Patent Publication No. 2,057,941, German Patent Publication No. 2,221
3,4 6 1, 2,2 1 9,9 1 7, 2,2 6 1,3 6 1, 2.2 6
3, 8, 7, 5, etc.

As the magenta coupler, 5-pyrazolone compounds are mainly used, but indadurone compounds and cyanoacetyl compounds are also used.

An example of this is U.S. Patent No. 2.439.09.
No. 8, No. 2, 6 0 0, 7 8 8, No. 3, 0
6 2, 6 5 3, 3, 5 5 8, 3 1
No. 9, British Patent Publication No. 956,261, U.S. Patent No. 3,582,322, U.S. Patent No. 3,615,
5 0 6, same No. 3, 5 1 9, 4 2 9, same No. 3, 3 1 1, 4 7 6, same No. 3, 4 1 9
, 391, Patent Application No. 48-21, 454, 48
-56,050, German Patent Publication No. 1,810,
4 6 No. 4, Special Publication No. 1974-2016, Special Application No. 1972-
45971, U.S. Patent No. 2,983,608
There is a description in the issue etc.

Cyan couplers mainly include phenol or naph1
- Derivatives of - are used.

Examples include, for example, U.S. Patent No. 2,369,92
9, 2.4 7 4, 2 9 3, 2.
6 9 8, 7 9 4, 2, 8 9 5, 8
2 6, same No. 3, 3 1 1, 4 7 6, same No. 3
, 4 5 8, 3 1 5, 3, 5 6 0, 2
1 2, same No. 3,5 8 2.3 2 2, same No. 3,5 9 1,3 8 3, same No. 3,3 8 6,
301, same No.2,434,272, same No.2.706,684, same No.3,034
, 8 9 2, 3, 5 8 3, 9 7 1,
German Patent Publication No. 2,16 3,811, Special Publication No. 1973
-28,836, Japanese Patent Application No. 1988-33, 238, etc.

In addition, a coupler that releases a development-inhibiting compound (so-called DIR coupler) or a compound that releases a development-inhibiting compound during the color-forming reaction may be added.

Examples of these are U.S. Pat.
No. 3,227,554, No. 3,253,
9 2 4, 3,617,291, 3,6
No. 22,328, No. 3,705,201,
British Patent Publication No. 1,20 1,1 10, U.S. Patent No. 3,297,445, U.S. Patent No. 3,379,
No. 529, No. 3,639,417, Japanese Patent Application No. 48-33,238, No. 48-41,870, etc.

Two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers.

Couplers and the like are introduced into the hydrophilic colloid of the photographic material by known methods.

This method is described, for example, in U.S. Pat.
2 No. 7, etc., but generally the boiling point is about 180
High boiling point organic solvents above °C, such as methyl phthalate,
Alkyl esters of phthalic acid such as ethyl phthalate, probyl phthalate, n-butyl phthalate, di-n-butyl phthalate, n-amyl phthalate, in-amyl phthalate, and dioctyl phthalate, N,N
Alkylamides such as diethyl laurylamide, trimellitate esters such as tri-tert-1r'7 thylmelitate, polyphenyl phosphates, phosphoric acid esters such as tricresyl phosphate, dioctyl butyl phosphate, and acetyl tributyl citrate. citric acid esters, or low-boiling organic solvents with boiling points of about 30°C to 150°C, such as ethyl acetate,
After dissolving in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobunal ketone, β-ethoxyethyl acetate, methyl seron rub acetate, etc., it is dissolved in any known photographic hydrophilic colloid. distributed.

These high boiling point organic solvents and low boiling point organic solvents are used in combination, if necessary.

Further, when the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an aqueous alkali IJI4 solution.

These couplers generally contain 2
x10-3 moles to 5X10' moles, preferably IXIO-2 moles to 5X10-1 moles.

The photographic support to which the coating material for forming the hydrophilic colloid photographic layer according to the present invention is coated may be cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose ordinarily used in photographic light-sensitive materials. Examples include acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, and laminates thereof.

When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties for both is provided as an undercoat layer.

Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

In order to obtain a dye image of the color photographic light-sensitive material of the present invention, it is necessary to process it according to the usual color processing steps after exposure.

The main processing steps basically include color development; bleaching; and fixing steps.

In this case, each process may be independent, or two or more of the processes may be performed in a single process using processing liquids that have these functions.

An example is a one-bath bleach-fix solution.

In addition, each step can be carried out in two or more parts if necessary, or a combination of processes such as color development, first fixing, and bleach-fixing is also possible.

In addition to the above, the development process may include a pre-hardening bath,
Various steps such as a neutralization bath, first development (black and white development), image stabilization bath, and water washing are combined.

The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription, and may be lower than 18°C, but is often 18°C or higher.

The most commonly used range is 20°C to 60°C, and recently the range is particularly 30°C to 60°C.

Note that it is not necessary that the set temperature for each step in the series of treatments be the same.

The color developing solution is an alkaline aqueous solution having a pH of 8 or more, preferably 9 to 12, and containing a compound whose oxidation product reacts with a color former called a coupler to form a color product, that is, a developing agent.

The above-mentioned developing agent refers to a compound having a primary amine group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound.

For example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethyl Aniline, 4-amino-3-methyl-N-ethyl-N-
β-methanesulfamide ethylaniline, 4-amino-N,N-dimethylaniline, 4-amino-3-methoxy-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, 4-
Amino-3-methoxy-N-ethyl-N-β-methoxychetylaniline, 4-amine-3-β-methanesulfamidoethyl-N,N-diethylaniline and salts thereof (
For example, sulfate, hydrochloride, sulfite, P-1-luenesulfonate, etc.) are mentioned as preferred representative examples.

Others, U.S. Patent No. 2,193,015, No. 2
, 5 9 2, 3 6 4, JP 48-64933
No. or L. F. A. Written by Mason, Photog
rapicProcessing Chemistry
y ゜ (Focal Press-London edition, 1
(published in 1966), pages 226-229.

Moreover, the above-mentioned compounds can also be used in combination with 3-virazolidones.

Various additives are added to the color developing solution as necessary.

Typical examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates and phosphates), pH adjusting or buffering agents (e.g. weak acids and bases such as acetic acid and boric acid, and their salts); Development accelerators (e.g., U.S. Pat. No. 2,648,604, U.S. Pat. No. 3,671,
Various pyridinium compounds and cationic compounds, potassium nitrate and sodium nitrate, as described in U.S. Patent No. 2.533.990, U.S. Pat.
577,127, 2,950,970, etc., polyethylene glycol condensates and derivatives thereof, British Patent No. 1,020,033
and nonionic compounds such as polythioethers as typified by the compounds described in U.S. Patent No. 3,068,097. Polymer compounds with sulfite esters as typified by the compounds listed above, other organic amines such as viridine and ethanolamine, benzyl alcohol, hydrazines, etc.) Antifoggants (for example, alkali bromides, alkali iodides, and 2,4 9 6,9 4 0, same No. 2,
6 5 6, 2 7 Including the nitropenzimidazoles described in No. 1, mercaptobenzimidazole, 5
Methylbensotriazole, 1-phenyl-5-mercabutotetrazole, U.S. Pat. No. 3,113,864, U.S. Patent No. 3,34 2,59
No. 6, No. 3, 2 9 5, 9 7 6, No. 3, 6
Compounds for rapid processing liquids described in No. 15,522, No. 3,597,199, etc., British Patent No. 97
2.2 Thiosulfonyl compounds described in No. 1 1, or phenazine N oxides as described in Patent Publication No. 46-41675, and others as described in Scientific Photography Handbook, Vol. 2, pages 29 to 47. fog suppressant, etc.), and other U.S. Patent Nos. 3,1 6 1,5 1 3
No. 3,16 1,5 14, British Patent No. 1
, 0 3 0, 4 4 2, same No. 1, 1 4 4, 4
8 1, the stain or sludge inhibitor described in U.S. Patent No. 1,2 5 1,5 5 8;
There are interlayer effect accelerators and preservatives (for example, sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite additives, etc.) known as No. 3, 6, 4, 8, 7, etc.

All bleaching solutions containing known bleaching agents such as blush salt, dichromate, iron(III), etc. are used.

Also, any of the silver oxidizing agents used in bleaching solutions can be used in the bleaching bath of the present invention.

For example, water-soluble ferricyanides (sodium ferricyanide, potassium ferricyanide, ammonium ferricyanide, etc.), water-soluble quinones (quinone, chloroquinone,
methylquinone, etc.), water-soluble ferric salts (ferric chloride, ferric sulfate, ferric thiocyanide, ferric oxalate, etc.), water-soluble cupric salts (cupric chloride, cupric nitrate, etc.) etc.), water-soluble cobalt salts (cohalt chloride, cobalt ammonium nitrate, etc.) are used.

Polyvalent cations and alkali metal complex salts of water-soluble organic acids are also preferably used.

Representative examples of organic acids include malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, amino l-I
Examples include J acetic acid, ethylene dithioglycolic acid, dithioglycolic acid, and the like.

Polyvalent cations are ferric ions, ferric ions, and cupric ions.

The iron-sodium complex salt of ethylenediaminetetraacetic acid is particularly useful as a bleaching agent.

Specific examples of bleaching solutions include, for example, Journal of
e Society of Motion Picur
e andTelevision Engineers
Magazine, vol. 61, p. 667'701 (1953), U.S. Patent No. 3,189,452, German Patent No. 866,605
No. 966,410, U.S. Patent No. 3,5 8 2,3
2 No. 2, and British Journal
of Photography magazine, vol. 107, 122-1
23 and 126 (1966).

Fixers are used to remove soluble silver salts from photographic materials.

Any fixing solution containing a compound commonly used as a solvent for silver halide can be used.

For example, water-soluble thiosulfates (sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.), water-soluble thiocyanides (sodium thiocyanide, potassium thiocyanide, ammonium thiocyanide, etc.), water-soluble thiocyanides containing oxygen or sulfur atoms, etc. organic diol fixing agent (3-thia 1,5-pencune diol, 3,6-dithia 1,
8-octanediol, 9-oxer 3,6,12,l
5-tetrathia-1,17-heptadecanediol, etc.)
, water-soluble sulfur-containing organic dibasic acids, and their water-soluble salts (ethylenebisthioglycolic acid, its sodium salt, etc.), imidazolidinethione (methylimidazolidinethione, etc.)
, etc. are advantageously used.

Also, L. F. A. Written by Mason, Photograp
hicProcessing Chemistry,
187-188, Focalpress (
(1966).

Fixing agents are also advantageously used.

The bleaching and fixing steps can be carried out in one bath if necessary.

The bleaching agents and fixing agents mentioned above may be used in appropriate combinations.

Specific examples of bleach-fixing baths include, for example, German Patent No. 866,
No. 605, US Pat. No. 3,582,322, Nade.

Each treatment bath is advantageously used for cyclic regeneration.

Such methods are described, for example, in “Journal of
theSociety of Motion Pict
ure andTelevision Engineering
rsJ magazine, volume 81, pages 293-295 (1972),
It is stated in.

Silver is advantageously recovered from the fixer.

For example, methods of silver recovery are described in [Journal of th
e Society of Motion Pict
ure and Televis-ion Engine
It is described in eersJ magazine, volume 81, pages 603-608.

Example 1 A cellulose triacetate film support having an antihalation layer containing black and white carbon black on one side, a subbing layer on the other side, and a silver halide multilayer coated on -L in the following order: Created color photographic material.

1st layer Blue sensitive layer 2nd layer Intermediate layer (1) 3rd layer Red sensitive layer 4th layer Intermediate layer (2) 5th layer Green sensitive layer 6th layer Protective layer Blue sensitive layer, red sensitive layer, green sensitive layer The couplers in each layer had the following structure, and each coupler was dissolved in a mixed solvent of dibutyl phthalate and ethyl acetate, emulsified and dispersed in gelatin, and then added to each emulsion layer.

Yellow dye-forming coupler Magenta dye-forming coupler The structures of the spectral sensitizing dyes used in the red-sensitive layer and the spectral sensitizing dyes used in the green-sensitive layer, and the amounts added per mole of silver, were as follows.

Spectral sensitizing dye for the red-sensitive layer Spectral sensitizing dye for the green-sensitive layer The coating amounts of silver, coupler, and gelatin in each layer were as follows.

A coating liquid in which liquid paraffin was dispersed in an aqueous gelatin solution was applied as the sixth protective layer.

Sample (1) prepared in this way was used as a control, and a gelatin intermediate layer (gelatin coating amount 0.8. yen/m2) was added between the 5th green-sensitive layer and the 6th protective layer. An ultraviolet-sensitive silver halide emulsion layer containing desilvering inhibitors A and B (
Recording band forming layer: A sample (sample 2) coated in this order with silver coated amount of 1.5 g/m2 (silver chlorobromide emulsion containing 10 moles of bromide), and sample (2) further coated with ultraviolet absorbers A and B. A sample (sample 3) was prepared in which the green-sensitive layer of the fifth layer contained the following.

The structures of the desilvering inhibitor used in the ultraviolet-sensitive silver halide emulsion layer of Sample 2 and the ultraviolet absorber used in the green-sensitive silver halide emulsion layer of Sample 3 are shown below.

Desilvering inhibitor UV absorber The above desilvering inhibitors A and B and UV absorbers A and B
The coating amounts are shown in Table 2.

Samples (1) to (3) were exposed stepwise (sound image (This exposure is hereinafter referred to as "exposure 1").

) Separately, samples (1) to (3) were exposed to stepwise exposure (equivalent to image-forming exposure) using tungsten light as a light source through a silver wedge and an ultraviolet absorbing film Fuji filter SC-41. ) was given.

(This exposure will be referred to as "Exposure 2" hereinafter.) The sample exposed in this way was processed according to the following processing (■) and (■), and the infrared density of each film obtained was determined by Macbeth TD.
Measurements were made using a Status S-58 filter with a -206A densitometer, and the results are shown in Table 3.

Treatment I Treatment process Temperature Time Before Bath 27°G 10 seconds water washing tt l 5 seconds color development
〃 5 minutes 20 seconds washing with water 〃 15 seconds first fixing
〃 Wash with water for 1 minute, bleach for 40 seconds
〃 Wash with water for 3 minutes 〃
1 minute sound development Room temperature 15 seconds water wash 27°C 15 seconds second fixing 〃 2 minutes water wash 〃 5 minutes stable
〃 10 seconds The composition of each treatment bath is as follows.

Prebath liquid water 800WLl carbonate'noda (monohydrate) io. og sodium sulfate (anhydrous) 50.0. ! Add T' water and 1
．． Set it to 0l.

Color developer water 800ml Sodium hexametaphosphate 2.0g Anhydrous sodium sulfite 4.0g 2-amino-5-diethyl 3.0g Amine toluene hydrochloride Sodium carbonate (monohydrate) 25.0g Potassium bromide 2.0g Add water The volume is 1.0l.

First fixer and second fixer water 600ml Sodium thiosulfate (pentahydrate) 240g Anhydrous sodium sulfite 15.0g Glacial acetic acid
12.0g Boric acid 6.0g Potassium alum 15.0g Add water to make 1.0L.

Bleach solution water 800ml Potassium bromide 20.0g Potassium dichromate 5.0g Potassium alum
40.0g Sodium acetate (trihydrate)
3.0g glacial acetic acid
Add 10.0g water to make 1.0L.

Sound developer (solution A) Water 600ml Anhydrous sodium sulfite 40.0g N-methyl-
p-Amino 40.0g Phenol sulfate Caustic soda 40.0g Hydroquinone 40.0g (Liquid B) Water 300TLl
Tragacanth rubber 5.0! j Denatured alcohol 10ml (C liquid) Ethylene diamino (70%) 20ml Mix liquids A and B and add liquid C and water just before use.1. Let's be Ol.

Stable bath water 800ml/
l/? Phosphorus (37%) 10ml polyethylene 17 glycol (molecular weight 400) Add 5ml of 40% aqueous solution water.1. Let's be Ol.

Treatment ■ Treatment process Temperature Time Before bath
27°c io second water wash
〃 15 seconds color development
5 minutes 20 seconds water washing 15 seconds first fixing 1 minute water washing
Bleach for 40 seconds
Wash with water for 3 minutes
1 minute second fixing 〃 2 minutes water washing 〃 5 minutes stabilizing bath
10 seconds〃 Each treatment liquid is the same as described in @treatment A.

As shown in Table 3, conventional photosensitive material 1 that does not contain a desilvering inhibitor did not show sufficient infrared density without sound development, but the photosensitive material that contains a desilvering inhibitor Samples Nos. 2 and 3 showed sufficient infrared density without sound development.

In addition, in comparison with sample (3), the overlap of the color image on the silver image portion was extremely small when the sound image forming exposure was applied and the processing (2) was performed.

Furthermore, when sample (3) was subjected to processing (1) with dye image forming exposure, the overlap of the silver image on the color image area was extremely small compared to sample (2).

Example 2 A sample (4) was prepared in which the ultraviolet absorber was added to the red-sensitive silver halide emulsion layer of the third layer instead of adding the ultraviolet absorber to the green-sensitive silver halide emulsion layer in Example 1.

Sample (4) was subjected to Exposure 1 and Exposure 2 in the same manner as in Example 1, and subjected to treatment (2).

There is little overlap of the dye image on the silver image obtained when sample (4) is processed with exposure 1, and there is little overlap of the silver image with the dye image obtained when processed with exposure 2. There were few.

Preferred embodiments of the present invention are listed below.

1. a support, at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, at least one red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, a magenta dye-forming coupler; In a light-sensitive material comprising at least one green-sensitive silver halide emulsion layer containing a green-sensitive silver halide emulsion layer and at least one ultraviolet-sensitive silver halide emulsion layer containing a diffusion-resistant desilvering inhibitor, the ultraviolet-sensitive The optical recording band portion of a multilayer color photographic material containing a diffusion-resistant ultraviolet absorbing substance in at least one layer between the silver halide emulsion layer and the support is exposed to ultraviolet light, and the image portion is visible. A method of forming a recorded image on an optical recording band by exposing it to light and then performing a photographic process that does not include a sound development process.

2. The method for forming an optical recording band according to item 1, wherein the wavelength of the ultraviolet light applied to the recording band portion is shorter than about 400 nm.

3. The method for forming a color image according to item 1 above, wherein the visible light applied to the image portion has a wavelength longer than about 400 nm.

4. A multilayer color photographic material comprising an edge-sensitive silver halide emulsion layer containing the ultraviolet absorbing substance according to item 1 above.

5. A multilayer color photographic material, wherein the ultraviolet absorbing substance according to item 1 is contained in an intermediate layer in contact with a green-sensitive silver halide emulsion layer.

6. A multilayer color photographic material, wherein the ultraviolet absorbing substance according to item 1 is contained in a red-sensitive silver halide emulsion layer.

7. A multilayer color photographic material, wherein the ultraviolet absorbing substance according to item 1 is contained in an intermediate layer in contact with a red-sensitive silver halide emulsion layer.

8. A multilayer color photographic material in which the ultraviolet absorbing substance according to item 1 is contained in a blue-sensitive silver halide emulsion layer.

9. 2. The multilayer color photographic material according to item 1, wherein the light-sensitive silver halide emulsion layer of the green band forming layer is a silver chlorobromide emulsion containing no more than 60 moles of bromide.

10. A multilayer color photographic material, wherein the ultraviolet absorbing substance according to item 1 above is a penzotriazole compound.

11. 11. The multilayer color photographic material according to item 10, wherein the penzotriazole compound is a benzoIJ azole compound having an aryl group at the nitrogen atom at the 2-position.

12. A multilayer color photosensitive material, wherein the benzoto IJ azole compound described in item 8 above is a compound represented by the following general formula.

(In the formula, R, R1, and R2 represent hydrogen, halogen, nitro group, alkyl group, alkoxy group, aryl group, and aryloxy group.

)13. A multilayer according to the claims, wherein a blue-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a recording band forming layer are coated in this order on a support. Color photographic material.

14. A patent in which a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a yellow filter layer, a blue-sensitive silver halide emulsion layer, and a recording band forming layer are coated on Support L in this order. A multilayer color photographic material as claimed.

[Brief explanation of drawings]

Figure 1-a shows "Processing 11" of a conventional multilayer color photographic material.
1" is a cross-sectional view of FIG. Figure 1-b shows the recording band of this sensitive material exposed to ultraviolet light, the image area exposed to visible light, and then photographically processed. It is a schematic diagram of a film. FIG. 2-a is a cross-sectional view of a multilayer color photographic material containing a desilvering inhibitor before processing, and FIG. 2-b is a cross-sectional view of a multilayer color photographic material containing a desilvering inhibitor, and FIG. 2-b shows a method similar to that shown in FIG. 1 is a schematic diagram of a film obtained by exposure and photographic processing. 3-a, 4-a, 5a and 6-a are all cross-sectional views of the multilayer color photographic material of the present invention before processing. Moreover, FIGS. 3b, 4b, sb and 6-b are respectively shown in FIG.
FIG. 2 is a schematic diagram of a film obtained by exposure and photographic processing in the same manner as in case -a. In the figure, 1 represents ultraviolet light exposure and 2 represents visible light exposure. 3 represents a recording band section, and 4 represents a color image forming section. In addition, S is a support, BL is a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, ML is a gelatin intermediate layer, and R
L is a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, GL is a green-sensitive silver halide emulsion layer containing a Mazenk dye-forming coupler, UL is an ultraviolet-sensitive silver halide emulsion layer containing a desilvering inhibitor, and PL is gelatin. The protective layer, U, represents an ultraviolet absorber. Further, the hatched areas represent the dye images formed in each layer, and the cross-hatched areas (■■) represent the silver/sound images.

Claims (1)

[Claims] 1 a support; at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler; at least one red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler; and a magenta dye-forming layer. Color image-forming layers of at least one green-sensitive silver halide emulsion layer containing a coupler and at least one ultraviolet-sensitive silver halide emulsion layer containing a diffusion-resistant desilvering inhibitor ( A multilayer color photographic light-sensitive material comprising a band-forming layer), characterized in that at least one layer between the ultraviolet-sensitive silver halide emulsion layer and the support contains a diffusion-resistant ultraviolet absorbing substance. A method for forming an optical recording band, which comprises exposing the optical recording band portion of a multilayer color photographic light-sensitive material to ultraviolet light.