JPS5852212B2 - Kakusantenshi Palm Yorinyori Pojitoumeigaokaiseisuru Tameno Kankoyouso Oyobi Kakusantenshahou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to diffusion transfer photography, and more particularly to diffusion transfer photography suitable for providing a positive silver transfer image that can be viewed as a positive transparency without separation from a developed negative silver image. Regarding diffusion transfer films and diffusion transfer methods.

The diffusion transfer film and diffusion transfer process provided by the present invention are particularly suited for use in forming additive color projection positive images.

It is, of course, well known to form positive images in silver by diffusion transfer.

In such methods, a light-sensitive silver halide emulsion is exposed to light, producing a latent image of exposed silver halide grains.

This latent image is developed to form a negative image of the subject in silver in the layer containing silver halide grains.

Silver halide grains that were not exposed during photographic exposure are...
It is dissolved by a silver halide solvent and diffusely transferred to a superimposed silver receiving or image-receiving layer, where the transferred silver ions are deposited, for example as metallic silver, and an image, which is a positive image of the subject, is formed of silver. .

In commercially available diffusion transfer films, the image receiving layer containing the positive silver transfer image is physically separated from the developed silver halide emulsion layer containing the negative silver image.

It is recognized that color images can be formed using silver diffusion transfer based on additive principles.

In such applications, the silver halide emulsion is exposed through an additive screen and the resulting positive silver transfer image is viewed through the properly aligned additive screen.

In the most effective embodiment, the same additive screen is used for exposure and viewing.

U.S. Patent No. 2614, issued October 21, 1952
No. 926, U.S. Pat. No. 2,707,150 issued on April 26, 1955, U.S. Pat.
U.S. Patent No. 294,489, published July 12, 960
No. 4 (all by Endwin Etch Rand) and U.S. Pat. A diffusion transfer color addition method is disclosed in which the image is observed in alignment with a color addition screen that has been subjected to the process.

The developed photosensitive layer is removed to allow observation of the resulting additive color transparency.

However, two of the aforementioned patents note that such additive transparencies can be observed without removing the developed silver halide emulsion layer.

Specifically, U.S. Pat. No. 2,726,154 states: ``It has been found that the density of the positive image produced in carrying out the silver halide photographic transfer process is much greater than the density of the negative image. Ta.

The density increase of this positive image is about 5 to 6 times,
This is the reason why the negative image and the positive image can be assembled in contact with each other.

Of course, under these circumstances the highlights of the positive image will be gray to some extent, but this is not so much that it is unacceptable, especially for projection purposes, as there is generally a considerable density difference between the positive and negative images. .

''Also, U.S. Pat. Intended to be retained.

Nidwinetch Land U.S. Patent Application No. 265,413 (later U.S. Patent No. 2) filed January 8, 1952
No. 65413) and U.S. Patent Application No. 466 of Nidwin Etch Land, filed November 4, 1954.
No. 889 (later U.S. Pat. No. 2,861,885) discloses the formation of transfer-reverse images having a density five or six times that of the silver image developed in the photosensitive layer.

As taught in the above-mentioned patent application, high covering power of reverse image silver can be used to avoid separation of sand-inch structures.

The highlights of the reversal image will be gray to some extent under conditions in which the light-sensitive and positive image-receiving layers are superimposed and held in a sand-inch structure, but this result is generally unacceptable, especially when image-containing products are to be projected. It's not so bad that I can't enter.

The cited patent application Ser. No. 2,654,13 was published as the aforementioned U.S. Pat. No. 2,726,154.

The cited patent application No. 466,889 was published as U.S. Pat. It is therefore clear that the minimum density of the composite positive image depends to a substantial extent on the maximum density of the negative image.

If the above-mentioned ratio of positive to negative silver coverage is achieved in a composite print to be observed by reflection, this maximum negative density even as large as 0.3 has a significant influence on the quality of the composite image. does not affect

Substantially greater maximum density is possible in the negative image when the composite positive is used as a transparency.

This is because the brightness of the highlights in a composite positive is a function of the illumination intensity.

It has been found that maximum densities as high as 1.0 in the negative image are acceptable if the maximum density of the composite positive is at least four times greater.

Preferably, in composite images of the type described above, the silver halide layer has a density of about 0.3 or less if the composite positive, when fully developed in the conventional manner, represents a reflective image; If presented as a transparency, it has a density of about 1.0 or less.

Another diffusion transfer method that provides a positive silver transfer image that is visible without separation from the developed negative image was introduced in 19701.
It is disclosed in U.S. Pat. No. 3,536,488 to Nidwin Etch Rand, published on October 27, 1971, and in U.S. Pat.

In U.S. Pat. No. 3,536,488, the positive silver transfer image and the developed negative image are in the same layer, and the silver halide emulsion layer includes a silver depositing agent.

Placing a silver precipitant in the silver halide emulsion layer is effective in keeping the developed negative density low by suppressing the physical expansion of exposed silver halide grains during development.

In U.S. Pat. No. 3,615,488, two positive silver transfer images are formed, one on each side of the silver halide emulsion layer.

Although the positive silver transfer images formed by these techniques have relative minimum and maximum densities with desirable density differences for use as positive transparencies without the need to remove the developed negative image, such methods Silver statues cannot be used effectively.

The foregoing considerations have led the industry to recognize, on the one hand, the possibility of retaining the developed silver halide emulsion layer as a final added color transparency, but on the other hand, to reduce the density of the developed negative image in such a way. It can be seen that the author recognizes concrete embodiment as an obstacle that makes it unattractive.

Additionally, as illustrated by the last-mentioned US patent, positive silver images often do not utilize silver in its most effective form, i.e. positive image silver is not a particularly dense form; Even if a maximum density of 3.0 is obtained in the image, it becomes very difficult to obtain transparencies with highly saturated colors.

The resulting additive images often appear to have "gray" highlights due to undesirably high negative densities, and have poor quality or unsaturated colors due to the ineffective use of positive silver. As can be seen, using a higher intensity light projection to compensate for the gray highlights only further reduces color saturation.

On the other hand, other means of removing developed silver halide emulsions to avoid these drawbacks give rise to other problems, and yet the diffusion transfer coloration process must be adopted commercially.

The most effective use of silver is to deposit it very densely in a thin image receiving layer separate from the silver halide emulsion layer.

A basic feature of the invention is that the positive silver transfer image is formed from very densely deposited silver, and that such dense positive silver is obtained without sacrificing the desired low negative silver image density; The result is a diffusion transfer color image with excellent highlights and excellent color resolution and saturation.

The present invention is directed to providing a silver diffusion transfer film and diffusion transfer process that provides a high quality positive transfer image that is viewable by transmitted light without the need to separate the developed negative silver image.

The diffusion transfer film and diffusion transfer process of the present invention are particularly suited for use in combination with suitable optical screens to provide excellent additive transparency, so the invention is particularly relevant in connection with additive applications. Describe it.

Accordingly, a principal object of the present invention is to provide a novel diffusion transfer film and diffusion transfer method that is effective in forming transferred images, particularly color-added transparencies, including positive silver transferred images.

Other objects of the invention include silver halide emulsion layers and silver acceptance, the silver halide emulsion layers being particularly effective in providing low covering power developed negative images and high covering power positive silver transfer images. containing silver halide grains in an amount and nature;
The object hereby is to provide a novel photosensitive element by which the images can be held together for the purpose of viewing as a positive image.

It is further an object of the present invention that the silver halide emulsions are of predominantly uniform grain size and provide a characteristic curve or photographic response independent of grain size, and that said grain size characteristics result in highly efficient utilization of silver and in positive images. A novel, particularly suitable for meeting the minimum and maximum density and other requirements of high quality additive images of the type in which the and negative images are in separate layers and held together as part of a permanent laminate. An object of the present invention is to provide a diffusion transfer color additive photosensitive element.

Another object of this invention is to provide a diffusion transfer color-added transparency film in which the grain size characteristics of the silver halide emulsion are related in a unique way to the dimensions of the color filter element.

Furthermore, another object of the present invention is a large dynamic range (dyn
amie range).

It is also another object of the present invention to provide a diffusion transfer color addition film and a diffusion transfer color addition process using a substituted-halide hybrid silver halide emulsion having a grain size distribution and properties suitable for producing excellent color addition transparency. The goal is to provide the following.

It is another object of the invention to develop a silver halide emulsion containing silver halide grains of a particular nature and silver coverage to give a negative image having a maximum transmission density of about 0.3 or less, Development of the silver is used to give a positive transfer image in a separate layer, and the negative and positive images are separated or separated by an intermediate mask layer (which can be seen as a positive image in the original machining process) using the diffusion transfer method. It is to provide.

The objects of the invention will be partly apparent, and partly will become apparent from the description below.

Accordingly, the invention encompasses products having the features, properties and relationships of the elements and methods including the steps and relationships between steps as exemplified in the following detailed description, and the scope of the invention is defined by the claims. Shown in range.

For a further understanding of the nature and purpose of the invention, reference is made in detail to the accompanying drawings.

As mentioned above, the present invention relates to a diffusion transfer process that provides high maximum density diffusion transfer positive silver images and low maximum density negative silver images, and also takes advantage of the fact that the images are carried on a common support. It is directed to photographic films and methods that can be viewed together as high-quality positive transparencies regardless of the image quality.

Maximum transmission density of each positive and screw image, e.g. 3 each
．． A suitable relationship between densities of 0 and 0.3 has been recognized in the aforementioned US patents, and positive transparencies with satisfactory density relationships have in fact been obtained in certain cases.

However, conventionally separate silver image-receiving layers and silver halide emulsion layers carried on the same support have been used to achieve a certain degree of color resolution or separation, color saturation, silver utilization efficiency, dynamic range, contrast, and/or ) It was not possible to obtain the desired positive and negative maximum densities without sacrificing other desired sensitometric properties.

The compromise in sensitometric performance that occurs in the implementation of prior art proposals is substantially reduced if not eliminated by the present invention.

It has already been mentioned that the present invention is particularly useful for producing additive transparencies by silver diffusion transfer.

It is also true that the unique features of the present invention are most easily explained and understood in the context of additive transparencies.

Accordingly, a more detailed description and discussion of the invention, particularly with respect to the foregoing embodiments, includes a transparent support, an optical screen such as an additive screen, a negative silver image and a negative silver image-containing layer separated from the transparent support as part of an integral film structure. The present invention relates to the provision of color additive transparencies containing a positive silver transfer image in a coated layer.

In such additive transparencies, a particularly effective additive screen includes a combination of fine color filter elements, each individual filter element of a set having a predetermined range of wavelengths of visible light, preferably the so-called trichromatic wavelength range. Transmits one light.

Particularly useful additive screens are therefore red, green, and blue filter elements, i.e., color filter elements that transmit red, green, and blue light, respectively; absorb light.

These color filter elements are interspersed and juxtaposed to provide a regular repeating pattern, commonly referred to simply as an additive screen, well known in the art.

In a particularly advantageous embodiment, the screen is formed from interspersed red, green and blue lines.

The finer the filter elements or lines, the less the additive screen will be resolved by the viewer's eye (i.e., the less the additive image will be when magnified many times when viewed as a transparency). The viewer "sees" or perceives less of the additive color screen.

Diffusion transfer positive images according to the present invention include positive diffusion images and negative silver images, where the two images are in separate layers on a common support and viewed as a single positive image.

There is no mask layer between the positive and negative images.

For convenience, such a positive image can be referred to as an "integrated positive-negative image", and more specifically, an "integrated positive-negative transparency".

In such composite images, the maximum density of the negative silver image by definition determines the lowest minimum density that the integral positive negative image can exhibit.

Therefore, the density of the negative silver image in the maximum exposure range must be kept as low as possible.

Conventional camera speed silver halide emulsions have a relatively broad grain size distribution, which is easily seen in the electron micrographs of FIGS. 5 and 6.

In camera speed silver halide emulsions, large silver halide grains are usually desirable because they have greater "speed".

The covering power of a given amount of silver halide decreases as the size of the individual silver halide grains decreases, a fact that indicates that large grains are desirable in silver halide emulsions that are retained in positive silver transfer images. be.

Despite this, large grain silver halide emulsions lead to undesirably high "graininess" and other undesirable sensitometric results when used in integral negative-positive transparency films.

In fact, if the silver halide grains are large and the additive screen is formed from a very fine filter element, i.e. if the silver halide grains are large relative to the filter element width, an undesirably large number of The silver halide grains are now located at the boundaries of two different filter elements and are therefore exposed to light of either of two different wavelength ranges.

This results in decreased color separation and saturation.

Small silver halide grains avoid the latter problem, but provide much greater negative silver image coverage for the same amount of silver.

Furthermore, the photographic speed of small particles is much smaller than that of large particles, which is a very normal situation;
Small particles are not effective in this method because, instead of contributing to the sensitometric sensitivity of the film, they are transferred to increase the inappropriate positive density, thereby adversely affecting dynamic range, latitude, film speed, and contrast. Not used for

The present invention provides an integrated negative-positive diffusion transfer transparency that effectively utilizes a minimum amount of silver to obtain high quality images having the desired minimum and maximum densities and exhibiting wide dynamic range and improved color quality. The present invention is directed toward providing images, particularly additive transparencies.

The number of silver halide grains available for recording information is minimized, while the total projected area of the silver halide grains is minimized.

According to the present invention, by using a silver halide emulsion with a largely homogeneous grain size distribution, these objectives can be met, and the positive silver transfer image and the unmasked negative silver image can be produced in separate layers. It has now been found that it is possible to obtain improved integral negative-positive images, particularly additive transparency images, which can be constructed from and viewed together as a positive image.

This emulsion is coated with low silver coverage and is an emulsion whose characteristic curve or photographic response is independent of grain size, thereby giving the desired long dynamic range.

Furthermore, there is an important, hitherto unrecognized relationship between silver coverage, coverage area of silver halide grains, coverage area of silver grains forming negative silver images, and grain size distribution of silver halide emulsions. It has been found that this relationship is particularly satisfied by using silver halide emulsions of largely uniform grain size.

In additive embodiments, it has been found that an important and previously unrecognized relationship exists between the grain size characteristics of the silver halide emulsion and the minimum dimension (width) of the individual optical filter elements that is useful for improving color resolution. Served.

Given these relationships, the average silver halide grain that is most effective for obtaining a certain combination of negative and positive transmission maximum densities from a certain amount of silver halide and having a certain additive color screen. It was found that a diameter and particle size frequency distribution exists.

More specifically, such an integral positive-negative transparency with a very satisfactory relationship between the maximum transmission density of each positive and negative silver image is based on a silver halide emulsion in which the silver halide grains have a predominantly uniform diameter. By coating the emulsion with a single layer of silver halide grains in an amount such that the total covered area of the silver halide grains is about 50% or less of the surface area of the silver halide emulsion layer, It has been found that a combination of desirable sensitometric properties can be obtained.

Additive embodiments require that the silver halide grains have an average diameter of about % to % of the color filter element.

Generally, silver halide grains should have an average diameter of about 0.7 to 1.5 microns.

When the additive screen is a very fine screen, such as in the case of Super-8 movie image size, the average diameter of the silver halide grains is preferably in the range of about 0.7 to 1.0 microns, most preferably about 0.9 microns, with at least 90% of the silver nosulogenide grains having a diameter ±
It has a diameter within 30%.

When the image size is large, as in the case of 35 or 3 x 43A transparencies, a coarser screen is sufficient and the average diameter of the silver halide grains is larger, for example about 1.
It can be in the range of 2 to 1.4 microns.

(Silver halide emulsions satisfying the above criteria will be recognized by those skilled in the art as having a "narrow" grain size distribution;
In fact, such silver halide emulsions have a much narrower particle size distribution than the camera speed silver halide emulsions used commercially.

) The silver halide emulsion is preferably coated as a "single grain layer" or "monolayer" of silver halide grains, i.e. the silver halide emulsion contains substantially overlapping silver halide grains. do not have.

However, the silver halide emulsion layer itself can be thicker than the silver halide grains.

Advantageously, the silver halide grains in the coated emulsion layer are relatively uniformly distributed and do not contain groups of grains having a diameter close to the width of the color filter element.

The silver halide emulsion has a silver to gelatin ratio of about 1:1 to 1:1.
5 (based on weight) is desirable.

Individual silver halide grains of course have finite dimensions;
Silver halide emulsions are often described in terms of, among other things, the "average diameter" of the silver halide grains.

The silver halide grains of the silver halide emulsions used in the present invention are "regular" in crystal habit, that is, they are generally polyhedra with three-fold symmetry, such as spheres, solids, octahedrons, and bispheres with rounded edges. The resulting octahedron is, for example, a liquid body or a platelet body.

Here, "triple symmetry" means symmetry about three mutually perpendicular axes.

The "coverage area" of an individual silver halide grain or developed silver grain is the area of the largest cross-section that can be drawn through the grain parallel to the plane of the layer in which the grain is placed.

Therefore, the covered area of a particle, which can also be called the projected area, corresponds to the area of the shadow cast when light is projected through a layer containing said particles, which is the area where the particles impede the transmission of light through said layer. The measurement is accurate.

The total coverage area of all silver halide grains in a silver halide emulsion layer is the sum of the coverage areas of the individual grains minus the overlapping coverage area of overlapping grains.

According to the present invention, as described above, the total coverage area of the silver halide grains in the silver halide emulsion layer must be about 50% or less of the surface area of the silver halide emulsion layer.

Furthermore, the total coverage area of silver particles that have been sufficiently exposed and developed (which provides the maximum density of a negative silver image) must be approximately 60% or less of the surface area of the corresponding portion of the silver halide emulsion layer. .

If the total area coverage of developed negative silver particles in the fully exposed area is about 60%, that portion of the negative image will transmit about 40% of the projected light and have an optical transmission density of about 0.4. has.

If the sum of the projected areas of developed negative silver grains in fully exposed areas is about 50%, then that portion of the negative image transmits about 50% of the projected light and has an optical transmission of about 0.3 It has concentration.

In a preferred embodiment of the invention, exposed silver halide grains are developed under conditions such that grain growth during development is limited to no more than about 10% of the covered area.

Preferably, the "delta" or difference between the maximum density of the positive silver transfer image and the maximum density of the negative silver image is at least 2.4 to 2.7 density units (transmission).

However, the maximum densities of individual red, green, and blue dye records are, for example, about 0, especially if the image silver toning is not intermediate.
．． It should be understood that it can vary very slightly within 1 to 0.3 concentration units.

Despite these changes, the minimum concentration is below 0.3,
Satisfactory additive transparencies can still be obtained as long as at least two of the three dye records exhibit a delta of 2.0 or greater, especially when the maximum density is about IO or greater than the minimum density.

As previously mentioned, in a preferred embodiment, the silver halogenide emulsion has a grain size of about 0.7 to 1. O microns, preferably about 0.0 microns.
It has an average particle diameter of 9 microns.

Assuming that the 0.9 micron diameter silver halide grains are spherical, such grains have a coverage area of 0.64 square microns.

A 0.87 micron diameter silver halide sphere will have a coverage area of 0.6 square microns.

Therefore, the grain size characteristics of a silver halide emulsion can be expressed as the average coverage area of silver halide grains.

According to such expressions, the average coverage area of the silver halide grains of the primarily homogeneous emulsion used in the preferred embodiment of the invention is about 0.6 microns squared, and at least one of the silver halide grains of the emulsion is 90% needs to have a coverage area about 0.5 to 1.7 times the above coverage area.

The silver halogenide emulsions used in the present invention were described as being primarily uniform in grain size, and preferred grain size distributions were mentioned.

Silver halide emulsions with narrow particle size distributions are not new per se, and techniques for obtaining such silver halide emulsions are well known.

smaller than desired and/or such as technique
Physical separation and removal of large particles is included.

Processes for producing silver halogenide emulsions suitable for producing narrow grain size distribution emulsions are also known.

However, it must be understood that the silver halide emulsion must not only have a largely uniform grain size distribution, but also one in which the characteristic curve or photographic response is substantially independent of the grain size distribution. It is.

In broad grain size distribution emulsions, the characteristic curve is the result of the individual responses of multiple grain size groups.

In fact, when specific size groups of grains are isolated, the resulting silver halide emulsions are often high contrast emulsions.

However, the present invention primarily utilizes silver halide emulsions that are uniform in grain size (and thus have the same solubility properties) and have a photographic response that is substantially independent of grain size.

This latter property can be thought of as intended for mixtures of silver halogenide grains of the same diameter but varying sensitivity or response to the diffusion transfer method.

(Particularly effective silver halide emulsions satisfying the above criteria) are substituted-halide mixed silver halide emulsions, and such emulsions will be described in detail later.

) In fact, by using such a predominantly uniform grain size silver halide emulsion one can have a satisfactory maximum density of the positive and negative images, so that these images can be processed without sacrificing the desired sensitometry. It has been found that significantly improved additive transparencies can be obtained which can be maintained at a high temperature.

Such uniform grain size silver halide emulsions maximize the ability of the silver halide layer to record information during photographic exposure without increasing the total coverage area for a given silver halide coverage.

Techniques for removing silver halide grains below and/or above a predetermined size or size range from a silver halide emulsion, such as by centrifugation, are known in the art and are primarily used to obtain silver halide emulsions of uniform grain size. It can be used.

The species of silver halide emulsions used in the present invention may be a mixture of several silver halide emulsions or emulsion portions each having substantially the same grain size but sensitized to different levels or "speeds". It can also be created by

As mentioned above, the desirable maximum transmission density of a positive silver transfer image is about 3.0.

It can be used, for example, to deposit silver substantially uniformly on a transparent support.
It has been determined that 100 silver per square high covering power by vacuum evaporation into a 1-0.15 micron thick layer is sufficient to give a transmission density of 3.0.

Furthermore, 100 cm of silver per square foot is approximately 0.8 cm in diameter.
When coated with a layer of 7 micron silver halide spheres 1 Blen thick (i.e., the silver halide layer contains substantially no overlapping silver halide grains), the silver halide grains cover the surface area of the silver halide emulsion layer. It was determined to have a total coverage area of 50% or less.

When this silver halide layer is given a full or maximum density exposure and the exposed silver halide grains are developed to provide silver grains having substantially the same coverage area as the silver halide, the fully exposed and developed halide The emulsion layer will have a maximum transmission density of 0.3.

Depending on the degree to which overlap of silver or silver halide grains is present, the total coverage area is reduced and the transmission density of the negative silver image is also reduced.

In reality, silver halide grains are not perfect spheres, so -
Reference to 0.87 microns as the desired diameter when using 100 m9 of silver per square foot shall guide those skilled in the art in selecting and coating silver halide holes in the practice of this invention.

- When using 100 μg of silver per square foot in the form of silver halide grains of various diameters, the effect on total area coverage is 11th
As can be seen in the figure, assuming that the grains are spheres, the percentage of the covered area (total covered area of silver halide grains) of silver 10 Qmy of silver halide is expressed as the grain size (microns).
is plotted as a function of .

With particles having a diameter of about 0.9 microns or greater, the percentage area covered decreases, and conversely, the total area covered increases as the particle size decreases.

(It is assumed that there is no overlap of particles.

) It is particularly important that as the average particle size decreases, the rate of increase in total coverage area is rapid, whereas as the average particle size increases, the rate of change is much slower.

As previously stated, 100 mg silver per square foot is sufficient to provide a transmission density of about 3.0.

Furthermore, positive image silver can be made very thin, for example, with a thickness of about 0.1 to
0.3, preferably about 0.25 microns when deposited in high coverage form in the image-receiving layer - about 90 microns per square foot.
It has been found that a positive silver transfer image with a transmission density of 2.5 to 3.0 can be obtained using a silver halide emulsion layer containing silver of 2.5 to 125 Å.

Figure 11 shows 100 silver halides per square note.
The relationship between the total covered area of silver halide grains and the grain size is shown by selecting the case where the silver halide grains are coated at a ratio of 7/lp.

Silver halide silver 100mI? /ft2, the average silver halide grain size should be about 0.86 to ensure that the total area covered by a single layer of silver halide grains is no more than about 50% of the surface area of the emulsion layer. It is clear from FIG. 11 that it is necessary to choose particles larger than microns.

Therefore, as mentioned above, when 100 m9 of silver is used, silver halide grains have a desired diameter of 0.87 microns or more on average.

As can be estimated from Figure 11, silver 100 of silver halide
If the emulsion layer is coated with a single layer of silver halide grains in an amount greater than m9/ft2, the total area covered will naturally be larger, and the curve in Figure 11 will be shifted to the left by no more than about 50%. In order to obtain total coverage, it becomes necessary to select silver halide grains having an average grain size larger than the average grain size shown in FIG.

Similarly, as can be deduced from FIG. 11, if the emulsion layer is covered with a single layer of silver halide grains in an amount smaller than 100 m9/ft2 of silver, the total covered area will automatically become smaller. The curve in the figure is also shifted to the right and silver halide grains can be chosen with an average grain size smaller than the grain size shown in FIG. 11 to obtain a total coverage of no more than about 50%.

In the present invention, as mentioned above, 90 to 125 µm of silver halide is used per square foot of the emulsion layer. It is sufficient to select a minimum mean grain size defined by the present invention of about 0.7 microns or more for the silver halide grains to obtain a total coverage area of the silver halide grains of no more than about 50% of the total coverage area of the silver halide grains.

In the present invention, the average grain size of silver halide grains is specified to be a maximum of about 1.5 microns, but by specifying the silver coating amount of silver halide from 90 to 125 μm/ft2, the minimum size of silver halide grains to be selected is The covered area is also determined.

In short, in order to cover silver halide grains with a total coverage area of no more than about 50% of the emulsion layer, approximately 90 m9 to 125 m
By using a silver coating amount in the range of ■/ft2, approximately 0
．． Average particle sizes ranging from 7 to 15 microns can be chosen.

A discussion of this point with reference to some of the accompanying drawings will further facilitate understanding of the invention.

FIG. 1 schematically shows a film unit 30 for forming a diffusion transfer colored transparency 30b.

The film unit 30 comprises a transparent support 10 carrying an additive color screen 12 consisting of alternating red, green and blue filter sections or elements (referred to as R, G and B, respectively);
It includes an image receiving layer 14 and a silver halide emulsion layer 16.

(Silver halide emulsion layer 12 has an average diameter of 0.9 microns, with about 10 silver halide grains per square foot having at least 90% within ±30% of said average diameter.
Assume that it contains 0 ■ silver.

) In step A, the silver halide emulsion 16 is exposed through the additive color filter 12 to only red light,
The intensity is sufficient to completely expose the silver halide.

Under these conditions, the silver halide after the red filter element A will be exposed by the red light transmitted through the filter element, while the silver halide after the edges and blue filter elements G and B will be exposed to the red light when the red light halides. It is absorbed before it reaches the silver, so it is not exposed to light.

As a result, the exposed silver halide emulsion layer 16a (step B
) contains the latent image of the red record.

Silver halide emulsion 111 of exposed film unit) 30a
Development and diffusion transfer processing can be performed by applying processing composition 18 to.

As shown in step B, the processing composition 18 is stored in a reservoir having a slot or nozzle installed to meter a predetermined amount of processing liquid as a function of the rate at which the exposed film is fed past the nozzle in the container 20. It is applied from a vessel or container 20.

The processing composition develops the latent image into a low covering power (approximately 0.3 maximum transmission density) negative silver image 16b in register with the red filter element R.

The unexposed silver halide after green and blue filter elements G and B is not developed, but is dissolved and transferred by diffusion to the superimposed image-receiving layer where silver complexes precipitate to form a positive silver image 14a of high coverage silver. is formed.

Positive image silver is deposited in register with green and blue filter elements G and B.

When viewing the final additive transparency 30b with white light projected through the developed silver halide emulsion layer 16b, a positive silver image 1
4a and the color additive screen 12 provide a correctly readable positive red image which reproduces the red record of exposure step A.

(The low covering power negative silver image does not block the passage of light through the red filter element R during subsequent viewing, while the high covering power positive silver blocks the passage of light through the green and blue filters.

) FIG. 2 is a reproduction of an optical micrograph (100 OX) of the same unexposed diffuse transfer color addition film shown in FIG. 1 as film unit 30.

The silver halide grains appear to have red, green and blue filter elements (lines) visible.

Figure 3 shows the second image after exposure to red light and processing as in Figure 1.
This is a reproduction of an optical micrograph (1ooox) of the film shown in the figure.

The dark density or solid areas 40 in FIG. 3 are high covering power positive image silver areas (corresponding to the unexposed areas after the blue and border lines).
brought about by.

The low density areas 42 are brought about by low L/covering power negative silver areas (responsible for the red exposed areas), and the fact that the silver particles cover less than 50% of the surface of these fully exposed areas is noticeable. be proven.

Figure 4 shows the electrons in the area of the same diffusion transfer coloring film as shown in Figure 2, which is subjected to intermediate exposure to red and blue light and expanded density exposure to green light, and then processed by diffusion transfer to create an additive color transparency. This is a reproduction of a microscopic photograph (100OOX).

(The film was manufactured and processed as described in Example 2 below.

) Visual inspection of the central broad diagonal band (running from the top corner of the photograph) reveals a combination of many small silver particles (positive image silver) and a small number of relatively large silver particles (negative image silver).

This band is located below the red and blue filter elements and between the fully exposed areas below the green filter element, which contains many relatively large silver particles and no small silver particles, and is located between these intermediate density boundaries and Inspecting the pre-exposure and development areas,
It can be seen that there is a combination of high covering power positive image silver and low covering power negative image silver, thus producing an intermediate transmission density.

As mentioned above, the silver halogenide emulsions used in the present invention are primarily uniform in grain size.

The silver halide emulsion used in the present invention can be any photosensitive material.
Silver halides or mixed silver halides can be included, preferably dispersed in a gelatin binder.

Particularly useful silver halides are silver iodobromide, silver iodochlorobromide, and silver chlorobromide.

If iodide is present in the silver rodanide, it is preferably about 1 to 10% by weight of silver.

Particularly preferred silver halide emulsions are chemically sensitized substituted-halide hybrid silver halide emulsions containing 1 to 50% chloride and 0 to 10% iodide, the balance being bromide.

Particularly useful predominantly homogeneous grain silver halide emulsions form silver chloride emulsions in which a portion of the chlorine anions are bromine and (
or) is an emulsion made by substitution with iodine anions.

In this process, for convenience, such non-rogenated emulsions are
It is called a silver halide emulsion.

average grain diameter of about 0.7 to 1.5 microns, preferably about 0.7 to 1.2 microns and at least 90% of silver halide.
A predominantly homogeneous substituted silver halide emulsion having a diameter within ±30% of the above average diameter forms grains of silver chloride, replacing a portion of the chlorine anions with bromine and/or iodine anions. It is caused by something.

In a particularly advantageous embodiment, not all of the chloride is substituted, and the substituted-halide silver halide emulsion is a silver iodochlorobromide emulsion.

The substituted halide silver halide grains of this invention have a halide content of O to about 10 mole % iodide and about 1 to 50 mole % chloride, preferably about 10 to 50 mole % chloride, balance bromide.

) The logenide is conveniently introduced in the form of an alkali metal halide salt.

If both iodide and bromide are to be included in the silver halide emulsion, the corresponding...ride salts can be added to the silver chloride simultaneously or separately in either order.

A dual jet addition technique for simultaneous introduction of silver and halogen ions is particularly suitable for controlling the particle size distribution within the desired range for the practice of this invention.

An initial silver chloride emulsion is formed by performing rapid simultaneous double jet additions of soluble silver salts and chloride solutions, with subsequent additions of bromide and/or iodide salt solutions to effect the desired halide substitution. done rapidly.

In practice, solution addition within about 3 to 20 minutes has been found to be desirable and advantageous in obtaining the desired particle size characteristics.

The temperature of the solution during the production of silver halide grains, during the no-ride substitution step, and during the manufacturing and ripening steps is at least 50°C.
°C, and in the most effective embodiments at least 70 °C,
Preferably it is about 80°C.

The substituted halide silver halide emulsion of the present invention is used as a negative working emulsion, and development of the substituted halide silver halide emulsion into a negative silver image is carried out in the presence of a silver halide solvent. Particularly useful in diffusion transfer methods.

Under these conditions, both the surface latent image and the internal latent image can be utilized to provide the desired negative image.

The following example describes the preparation of such an emulsion.

Example 1 205I? A solution of gelatin and potassium chloride (solution A) was prepared by dissolving phthalic anhydride-derived inert bone gelatin and 205 g of potassium chloride in 5750 ml of distilled water.

A solution of potassium chloride (solution B) was prepared by dissolving 1026 S' of potassium chloride in 5336 ml of distilled water.

A silver nitrate solution (Solution C) was prepared by dissolving 2000 grams of silver nitrate in 5336 ml of water.

Solution A was heated to 80°C and solutions B and C were heated to 70°C.

Solutions B and C were then added to solution A simultaneously over 8 minutes (by double jet addition).

The resulting mixture was aged at 80°C for 5 minutes.

After this aging period, 133'l of potassium bromide and 60
Dissolve potassium iodide in 5336 ml of water at 70°C.
The heated solution was added over 8 minutes while maintaining the temperature at 80'C.

This mixture was then aged at 80°C for 35 minutes.

After this aging, the mixture was cooled to 20° C. and the pH was adjusted to about 2.7 using 10% sulfuric acid.

The silver halide-gelatin linear precipitate was formed when the conductivity of the surface liquid was 5.
Washed several times with cold distilled water until 0-100 μm hos.

After final decantation of excess wash water, 950
P. dry activated bone gelatin was added and allowed to swell for 20 minutes.

The temperature was then raised to 38°C and held at that temperature for 20 minutes to dissolve the gelatin.

After adjusting the pH to about 5.7, the temperature was raised to 54° C. and 24771 ffl of the solution of gold ammonium thiocyanate complex was added.
was added.

(This chemical sensitizer solution contains ammonium thiocyanate 1.
A solution of 05' dissolved in 99ml of water and 0.97? in 99ml of water. of a solution containing gold chloride.

) This emulsion was then post-ripened at 54°C for 120 minutes.

This emulsion was cooled to 38°C, an optical sensitizer was added, and the
It was aged for 5 minutes, then cooled and hardened.

The resulting silver iodochlorobromide emulsion contained approximately 85 mole percent bromide, 12 mole percent chloride, and 3 mole percent iodide (as determined by X-ray fluorescence analysis).

The silver iodochlorobromide grains had an average diameter of about 0.86 microns, with 90% of the grains having diameters of about 0.63 to 1.08 microns or within ±26% of the average diameter.

It has been previously stated that the preferred embodiment of the present invention utilizes a predominantly uniform grain size silver halide emulsion with an average grain size of about 0.9 microns coated with a silver coverage of 100 sq.ft.

FIG. 9 shows an unprocessed silver halide emulsion layer (1.5:1 gelatin/silver weight) containing 101.7 μm of silver per square foot of the 0.86 micron average diameter silver halide emulsion prepared in the Examples. This is an electron micrograph (100OOX) obtained by transmitting observation of a specimen coated with a carbon fiber.

Visual inspection reveals that the silver halide grains are largely uniform in size, that there are substantially no overlapping silver halide grains, and that the total coverage area of the silver halide grains is less than about 50% of the surface area of the silver halide emulsion layer. It is easily obvious that.

Figure 10 is a similar electron micrograph (100OOX) of another portion of the same silver halide emulsion layer as in Figure 9 after full density exposure and development.

It can be seen that the particles have not grown much and the total coverage area is kept low by the present invention.

Grain size distribution curves or grain size frequency curves as they are sometimes called are often used to describe and define silver halide emulsions.

``Theory of Photographic Methods'', published by Macmillan Company, New York, 3rd edition, Mie 2 and James, 1966, pp. 36-44, describes the measurement of the dimensions of silver halide grains and the size of certain silver halide emulsions. A technique for measuring the frequency of particles of a certain size is described.

In the case of grains that are too small to be sufficiently resolved by a light microscope, electron microscopic grain size frequency analysis of silver halide emulsions is a particularly effective measuring method.

The gBa diagram is obtained using Zeiss TGZ-3 to obtain counts from the electron micrograph of the silver halide emulsion prepared in Example 1.
This is a particle size frequency distribution curve of particle sizes measured using a particle size analyzer.

The horizontal axis of the curve in FIG. 8a represents the relative log diameter of the silver halide grains in microns, the vertical axis represents the relative number of grains, and the dotted line represents the cumulative percentile.

For the silver halide emulsion prepared in Example 1, the average grain size was 0.86 microns.

The ratio of 90% of the silver halide grains deviating from the average diameter was discussed in Example 1, but visual comparison of the grain size frequency distribution curve in Figure 8a shows that the substituted halide emulsion prepared in Example 1 has a narrow distribution, i.e., a uniform distribution. The grain size is clearly demonstrated graphically.

Dispersion number of particle size frequency distribution curve
mber) or the particle size of the 16th percentile of 84
The grain size distribution of a silver halide emulsion can also be characterized by subtracting from the grain size in the second percentile and dividing the resulting number by the average diameter.

The smaller the number of applications, the narrower the width of the particle size frequency distribution curve.

The scattering number of the silver halide emulsion prepared in Example 1 was 0.3.
5 (see Figure 8a).

Silver halide emulsions useful in the practice of this invention using additive screens having 1000 or more color triplets per inch should have an average grain size of about 0.7 to 1.0 microns. In addition, it is characterized by a dispersion number of 0.4 or less, preferably 0.35 or less.

By examining the electron micrograph (100OOX) shown in FIG. 7 of the grains taken with a carbon-platinum replica, the uniform grain size distribution of the silver iodochlorobromide emulsion prepared in Example 1 can be visually and realistically confirmed. be proven.

The silver halide grains in this emulsion are much more uniform in size than the silver halide emulsions used in commercial silver diffusion transfer processes.

This fact is demonstrated by comparing Figure 7 with Figures 5 and 6, which show electron micrographs (1oooox) of the same carbon-platinum replicas of silver iodobromide emulsions used in Polaroid Landquip 42 and Type 47 films, respectively. This becomes easily clear.

As described above and shown in FIG. 1, the diffusion transfer color-adding transparent film of the present invention comprises a transparent support carrying a color-adding screen;
It includes a silver receiving layer and a silver halide emulsion, which layers are held together in registered relationship as a permanent laminate after processing.

The additive screen itself can be produced by techniques well known in the art, such as by sequentially printing the desired filter pattern by photochemical methods.

Additive screens are colored gamuts or filter elements, usually two
or an array of four different color sets, each of said sets of colored gamuts being capable of transmitting visible light within a predetermined wavelength range.

In the most common case, additive screens are tricolor, with each set of color filter elements transmitting light in one of the so-called primary wavelength ranges, ie red, green and blue.

Additive screens can be constructed by mixing small colored particles, such as starch particles or hardened gelatin particles, and dispersing them in a regular or diagonal arrangement into a mosaic.

Regular mosaics of this type can be made by the alternating relief and adjustment techniques described in Howardsey Loggers, US Pat. No. 3,019,124, issued January 30, 1962.

Another method of forming suitable color screens was published in 1962.
No. 3,032,008 to Nidwin Etch Rand, Davitnis Gray, and Otsutoey Filter, issued May 1, 2008, the colored wires are a single colored wire. placed next to each other in the coating operation.

A particularly effective and preferred additive color screen includes red, green and blue stripes or lines in a regularly repeated pattern.

The "width" of each color filter element can vary depending on the usage of placing the last additional color transparency.

In general, the greater the expected magnification of an additive color transparency when projected onto a viewing screen, for example, the more likely a viewer will be able to "see" or resolve the color screen independently of the additive image. The filter elements need to be that small.

The width of the filter element therefore limits the allowable magnification for viewing the final image.

Generally 35mm (24X 36mm) or 3V//
x4V // If transparency is desired, approximately 550 tricolor sets of red, green, and blue lines per inch (i.e., 550 lines per color per inch, each tricolor set of lines having a combined width of approximately 45 microns. It has been found that a screen consisting of about 750 tricolors per inch when the film is of the 16-screen type, and about 1000 tricolors per inch when the film is of the Super 8 type, is effective. It was done.

In a typical additive screen, particularly useful for providing additive motion picture film with a standard Super 8 image area, each field, the green and blue lines are approximately 8 microns wide, and each tricolor set of red, green and blue lines is approximately 8 microns wide. It is approximately 24-25 microns wide.

A particularly preferred method of manufacturing color screens is described in U.S. Pat.
284208,
The method consists of sequentially coating the smooth surface of a biconvex lenticular film with a plurality of photosensitive layers and subsequently selectively exposing the coatings to radiation focused by a biconvex lens. Become.

After each exposure, the unexposed portions of the coating are removed and the resulting resist is dyed to provide a set of colored filter elements before the next subsequent photosensitive layer is applied.

Each such exposure is made by radiation incident on the biconvex lenticular film at a calculated angle such that the desired plurality of sets of color filter elements effective to filter out a given wavelength of light are substantially Delivered side by side or in screen connection.

When the additive screen is tricolor, for example plain red, green and blue, the exposed area of each sensitive area generally comprises about % of its layer.

All three exposures can be made by radiation incident on the biconvex lenses of the biconvex lenticular film at three separate angles calculated such that each exposure exposes approximately % of the rear area of each biconvex lens. However, it has been found that final color filter element formation can be accomplished by exposing the final photosensitive coating to diffuse radiation, relying on the previously formed color filter element to prevent unwanted exposure. There will be.

After forming the first and second series of filter elements, the biconvex lens configuration is reconstituted as a continuous smooth surface.

If the biconvex lens includes a separation layer temporarily fixed to the surface of the support forming the color screen, the separation layer can be peeled off from the support.

If the biconvex lens is integral with the film base or support and is imparted by pressure and/or solvent deformation of the base, a suitable solvent to relieve the deformation pressure built up during the manufacture of the biconvex lenticular film base. can be applied to reconstitute a continuous smooth tensioned surface, and if desired, for example for optical transmission purposes, the reconstituted surface can be polished, e.g. by contact with a suitable rotating abrasive cylinder or drum, to form a film. Desired optical properties can be imparted to the base surface.

The outer surface of the color screen is coated with an alkali-resistant protective polymer composition such as cellulose acetate butyrate, polyvinyl butyral, polyvinylidene chloride, etc. to protect the screen filter dyes from attack by the diffusion transfer processing compositions used in processing the film. It is preferable.

A suitable apparatus for carrying out the above-mentioned exposure of biconvex lenticular films is described, for example, in US Pat. No. 3,318,220.

The transparent support or film base used may be any of the known types of transparent, photographically effective, rigid or flexible supports such as glass, polymeric films derived from synthetic and natural products, etc. It can be something.

Particularly suitable film bases include polymeric films derived from polyesters such as ethylene glycol and terephthalic acid, commercially available under the trademarks Mylar and Nystar, and polymeric cellulose derivatives such as cellulose triacetate or cellulose acetate butyrate.

As mentioned above, preferred image-receiving layers contain one or more silver precipitating agents that provide a strong silver precipitation system suitable for providing very thin and high coverage silver transfer images.

This layer is preferably located between the silver halide emulsion layer and the additive screen, but it is also within the scope of the invention to locate the silver halide emulsion layer between the image-receiving layer and the additive screen.

The receiver layer should exhibit almost no swelling during processing, thereby producing a dense silver deposit that gives a high coverage silver transfer image and minimizes lateral diffusion of transfer-soluble silver complexes. formation, resulting in increased resolution and maximized color separation and saturation.

A large number of binders or carrier materials suitable for silver precipitating agents are known in the art.

A particularly effective image-receiving layer includes a layer of deacetylated chitin containing a silver precipitant;
It is described in detail in US Pat. No. 3,087,815 published on the 0th, and the description of this patent is cited as a reference.

It is also advantageous to further help limit swelling of the silver halide emulsion layer to minimize lateral diffusion of soluble complexes, increasing image and color resolution and saturation.

Suitable curing and/or crosslinking agents are well known in the photographic industry.

It is also advantageous for the film unit to contain an antistatic agent or coating.

Wetting agents can be used according to normal practice.

Suitable silver precipitating agents are well known in the art and are described, for example, in several of the aforementioned patents describing silver transfer processes.

Particularly effective silver precipitating agents are those described in the above patents and e.g.
These include the heavy metal sulfides and selenides and colloidal metals described in Nidwin Etch Rand, U.S. Pat. No. 2,698,237, published Dec.

Solubility product in aqueous medium at about 20°C is 1023-10
Preference is given to using sulfides of -30, especially sulfides or selenides of zinc, copper, cadmium and lead.

Silver precipitants are used at low concentrations, such as about 1-25.times.10' moles/square note.

When the silver precipitant is one or more heavy metal sulfides or selenides, the processing agent has a substantially higher concentration than the heavy metal sulfide or selenide used as a silver precipitant in the silver precipitation layer or in another layer adjacent thereto. It is desirable to prevent the diffusion and wandering of excess sulfur or selenium ions that may also be present by including at least one metal salt that is highly soluble in and non-reducible during processing.

This more soluble salt has as a cation a metal whose ion is less soluble in the processing agent and forms a sulfide or selenide which upon displacement transfers sulfur or selenium ions to the silver.

Thus, in the presence of sulfur or selenium ions, the more soluble salt metal ions have the effect of immediately precipitating the sulfur or selenium ions from solution.

These ion-trapping salts include cadmium, cerium (ceric), cobalt (cobalt), iron, lead, nickel,
Can be soluble salts of manganese, thorium and tin.

Satisfactorily soluble and stable salts of the above metals may be present in their acetates, nitrates, borates, chlorides, sulfates, hydroxides, formates, citrates or dithionates. discovered.

Preference is given to acetates and nitrates of zinc, cadmium, nickel and lead.

In general, it is also preferred to use white or light colored salts.

In addition to the above-mentioned characteristics, the above-mentioned ion-trapping salt has the following characteristics:
The properties described in U.S. Pat. No. 2,584,030 to Nidwin Etch Land, published on May 29, also serve to improve the stability of positive images.

For example, if the ion-trapping salt is a metal salt that gradually forms an insoluble or slightly soluble metal hydroxide with the hydroxyl ions in the alkaline processing solution, it will act to reduce the alkalinity of the film unit, resulting in Helps prevent unwanted developer stains.

Silver halide solvents effective to form the desired soluble complexes with unexposed silver are well known and can be chosen, for example, from alkali metal thiosulfates, particularly sodium or potassium thiosulfates, or silver halide solvents containing nitrogen-containing groups. (as taught in U.S. Pat. No. 2,857,274 to Nidwin H. Rand, issued October 21, 1958), such as uracil, in combination with a cyclic imide such as uracil.

Preferably, the silver halide solvent is initially present in the processing composition, but no silver halide solvent is added to the layer of the film unit, preferably as a precursor which releases or generates the silver halide solvent upon contact with an alkaline processing solution. It is also within the scope of the present invention to initially locate it in the form of a substance.

The treatment composition can contain a thickening agent such as alkali metal carboxymethyl cellulose or hydroxyethyl cellulose in an amount and viscosity suitable to facilitate application of the treatment composition.

The processing composition can be left on or removed from the processing film by known techniques as most appropriate for the particular film use.

Preferably, one or more alkali metal hydroxides such as sodium, potassium and/or lithium hydroxides are used to provide the treatment composition with the necessary alkalinity, eg a pH of 12-14.

It is advantageous to include a wetting agent in the treatment composition to facilitate its application when the treatment composition is applied as a very thin layer of a low viscosity liquid.

Suitable silver halide developers may be selected from those known in the art and may be used to initially develop the layers of the photosensitive element and (
or) can be located in the treatment composition.

Organic silver halide developers, such as organic compounds of the benzene or naphthalene series containing hydroxyl and/or amino groups in the para or ortho position with respect to each other, such as nohydroquinone, t-butylhydroquinone, toluhydroquinone, p-aminophenol, 2・6-
Dimethyl-4-amino-phenol, 2,4,6-triaminophenol, etc. are commonly used.

If the additive transparency is a transparency that is not cleaned after processing to remove unused silver halide developer, development reaction products, etc., the silver halide developer will stain the image or react even if unreacted. No colored reaction products should be produced which would adversely affect the stability and sensitometric properties of the final image.

Particularly effective silver halide developers with good stability in alkaline solutions are substituted reductin acids, especially tetramethylreductinic acid (Stanleyem Bloom and Richard Day Kramer, U.S.A., published October 26, 1971). described in Patent No. 3615440) and α
- β-enediol (described in U.S. Pat. No. 3,730,716 of Nidwin Etch Rant, Stan Rayem Bloom and Leonard C. Huney, published May 1, 1973).

It is also within the scope of the present invention to use antifog agents and/or toning agents in concentrations well known in the art in photosensitive elements and/or processing compositions using well known techniques.

The provision of a layer (sometimes referred to as a "protective layer" or "top coat") that is transparent to processing compositions that does not contain silver halide or silver precipitating agents as the outermost layer has been found to provide a number of beneficial advantages. Served.

Such layers can be used to carry one or more processing-effective agents such as antihalation dyes and/or image stabilizers.

This protective layer, especially when coated directly over the silver halide emulsion, provides an effective control effect on the rate and/or concentration at which the components of the processing composition come into contact with the silver halide and provides a more uniform processing composition. wave front of an object
) and are believed to promote permeation.

One can easily choose a polymer that is permeable to the appropriate treatment composition to provide the specific properties and desired controlled dust.

Examples of preferred materials include gelatin and cellulose hydrogen phthalate acetate.

The former can be deposited onto the emulsion layer from an aqueous solution, while the latter can be deposited from a suitable solvent, such as an organic solvent such as an acetone/ethanol mixture.

Other suitable polymers include polyvinyl alcohol and polyvinylpyrrolidone.

The polymer layer can be crosslinked or cured to control permeation rate and degree of swelling.

Examples of hardening agents that have been found to be particularly useful for gelatin layers useful in the practice of this invention include chromium alum and hyalginates such as propylene glycol alkinate.

The presence of the protective layer also has the advantage of minimizing "salting out" of components of the processing solution on the surface of the developed film from which the processing solution is not removed.

A particularly effective protective layer is a gelatin coating of about 80 to 250 .mu./ft.sup.2.

The particular dyes used to provide the individual color screen filter elements can be selected according to principles well known in the art and do not themselves form part of the invention.

It is also known in the art that individual filter elements need not be equal in area and that some variation in the relative area occupied by individual colors is desirable to achieve color balance as a result of the color transmission properties of the individual pigments. .

Examples of suitable dyes for use in forming additive screens are found in the aforementioned patents and other patents relating to additive photography, such as U.S. Pat. No. 3,730,725 and U.S. Pat.
No. 969120.

The following example of an additive transparency preparation according to the present invention is included for illustrative purposes only.

Example 2 A transparent polyethylene terephthalate film carrying an additive screen consisting of approximately 1000 triplicate sets of dichromate-containing gelatin filter lines dyed red, green, and blue was prepared as described in the aforementioned U.S. Pat. No. 3,284,208. Made according to the method described.

A thin layer of cellulose acetate butyrate was coated over the color-additive screen, followed by an image-receiving layer containing about 4.4 cm/ft2 of deacetylated chitin and about 25 m/ft2 of cupric sulfide.

Next, a chemically sensitized silver halide emulsion (average diameter 0.70 micron), and the above-mentioned
- A light-sensitive silver halide layer was formed on the image-receiving layer using a silver halide emulsion that had been panchromatically sensitized and had substantially the same grain size characteristics.

The silver halide layer is about 120 m9/ft2 of gelatin and about 102 mfI/ft2 of silver and 0.2 mfI/ft2 of gelatin.
% propylene glycol alginate by weight.

The silver halogenide emulsion layer was then coated with a 7-ration prevention layer.

The photosensitive element was exposed to a multicolor step wedge and coated with an antihalation layer and a polyethylene terephthalate sprayer (S p
A layer of treatment composition approximately 0.0014 inch thick was applied between the reader) sheets.

The treatment composition consisted of: Sodium hydroxide 4.43'?
Lithium hydroxide 1.48P Sodium carboxymethyl cellulose 3.13'? vinegar(
(medium viscosity) 2,6-dimethyl-4-aminophene 0.441 nortetramethylreductinic acid 4.71? Sodium sulfite 5.17 Sodium P thiosulfate 9.10P2・4・
6-triaminophenol 0.22 f6-nitrobenebuimidazole 0.69y Wetting agent (reaction product of nonylphenol and glycid 2.25S'-ol) After about 1 minute, remove the polyester spreader sheet,
The additive positive transparency in the developed additive film was projected without separating the silver halide emulsion layer and the image-receiving layer.

Additive transparency middle column (neutral colu)
mn ) had the following transmission densities: Example 3 Additive diffusion substantially as in Example 2 using a silver iodochlorobromide emulsion with an average grain size of 0.94 microns but without an antihalation layer. A transfer film was prepared.

This emulsion has a molar percentage of added bromide (silver base ratio) of 85
It was prepared in the same manner as in Example 1 except that %.

The scatter number of the grain size frequency distribution curve (shown in Figure 8b) of this emulsion was 0.33.

The silver coverage was 10 1 /ft 2 and the silver to gelatin ratio was about 1:1.2.

The treatment composition used was as follows: Sodium hydroxide 4.44S'
Lithium hydroxide 1.48f Sodium carboxymethyl cellulose 2.84S' (intermediate viscosity) 2,6-dimethyl-4-aminophene 0.45P-nortetramethylreductinic acid 4.96f Sodium sulfite 5.18f Sodium thiosulfate 9.11P2・4・6
-triaminophenol 0.22 P6-nidrobenzimidazole 0.46f2-mercaptobenzothiazole 0.16 P wetting agent (reaction product of nonylphenol and glycide 3.75?) Red, green and blue concentrations in the middle column The characteristic curve of is shown in FIG.

Example 4 8001 inert bone gelatin was swollen in 8800 ml of distilled water for 20 minutes.

The temperature was raised to 40° C. and the gelatin was dissolved with stirring.

The pH of the gelatin solution was adjusted to 1 with 50% sodium hydroxide.
It was adjusted to 0.0.

While maintaining the temperature at 40°C, 81' phthalic anhydride dissolved in 6161 rLl of acetone was gravity fed into the gelatin solution over 30 minutes while the pH was maintained at 10.0 with 50% sodium hydroxide. The solution was slowly stirred for a further 30 minutes at 40°C, after which the pH was adjusted to 6.0 with sulfuric acid.

A gelatin solution (solution A) was prepared consisting of 6000 ml of distilled water, 2560 f of the above phthalic anhydride-derived gelatin, and 2051 of potassium chloride.

A potassium chloride solution (solution B) was prepared by dissolving 1026 S' of potassium chloride in 5336 ml of distilled water.

A silver nitrate solution (Solution C) was prepared by dissolving 2000 grams of silver nitrate in 5331' of distilled water.

Solution A was heated to 80°C.

Solutions B and C were heated to 60°C and added to solution A held at 80°C for 3% min at a rate of 1750 ml/min.
It was added by the heavy jet addition method.

This mixture was aged at 80°C for 5 minutes. After this aging, 13
37P potassium bromide and 4C1 potassium iodide
A solution dissolved in 336 ml of water was heated to 60°C and added over 3% minutes while maintaining the temperature at 80°C.

This mixture was then aged in SO'C for 35 minutes.

After aging, the mixture was cooled to 20°C and the pH was adjusted to approximately 2.7 using 10% sulfuric acid.

Silver halide gelatin linear precipitates are formed when the conductivity of the surface liquid is 50.
Washed several times with cold distilled water until -100 μmhos was reached.

Finally, after removing excess wash water by decantation, 950 grams of dry activated bone gelatin was added and allowed to swell for 20 minutes.

The temperature was then raised to 38°C and held at that temperature for 20 minutes to dissolve the gelatin.

After adjusting the pH to about 5.7, the temperature was raised to 54° C. and 24 ml of gold ammonium thiocyanate complex solution was added to Example 1.
It was added in the same way.

The emulsion was then post-ripened for 150 minutes at 54°C.

The emulsion was cooled and hardened.

The resulting silver iodochlorobromide emulsion contained approximately 85 mole percent bromide, 13 mole percent chloride, and 2 mole percent iodide.

The silver iodochlorobromide grains had an average diameter of about 0.92 microns, and the grain size frequency distribution curve of the emulsion had a scattering number of 0.36.

An additive color photosensitive element was prepared in substantially the same manner as in Example 2.

The silver halide emulsion layer is panchromatically sensitized before coating,
And about 92.1■/ft2 of silver, 2001ru? /ft
2 of gelatin and a coverage of 4.81 n9/ft2 of propylene glycol alginate.
．． It contained a 92 micron average diameter silver iodochlorobromide emulsion.

(There was no antihalation layer.

) After exposure, the film was processed as in Example 1 using the following processing composition.

Sodium hydroxide 3.94P sodium carboxymethyl cellulose 3.77? -su(
Medium viscosity) Sodium thiosulfate 10.01'Sodium sulfite 4.08S'6-nidrobenzimidazole 0.26? Toluhydroquinone 2,4,6-triaminophenol wetting agent (reaction product of nonylphenol and glycidol) 3.14f O, 23P 2.28P Add water to 100cc Red and green in the middle column of the resulting additive transparency and the blue characteristic curve are shown in FIG.

The intermediate column had the following transmission densities: Red Green Blue Dmax 3.013.263.34 Dmin O,300,360,32 The following example shows color 3 with 750 per inch or less.
The preparation of a predominantly uniform grain size silver halide emulsion useful in additive screens with double-grained grains is described.

Example 5 Sooy inert bone gelatin was swollen in 8800 ml of distilled water for 20 minutes.

The temperature was raised to 40° C. and the gelatin was dissolved with stirring.

Adjust the pH of the gelatin solution to 10.0 with 50% sodium hydroxide.
Adjusted to 0.

While maintaining the temperature at 40° C., a solution of 88 grams of phthalic anhydride in 616 ml of acetone was gravity fed to the gelatin solution over 30 minutes while the pH was maintained at 10.0 with 50% sodium hydroxide.

The solution was slowly stirred for an additional 30 minutes at 40°C, after which the pH was adjusted to 6.0 with sulfuric acid.

6000ml of distilled water, 2260'? of the aforementioned phthalic anhydride-derived gelatin, 1011 of potassium bromide and 61
A gelatin solution (solution A) consisting of potassium iodide was prepared.

A potassium bromide solution (solution B) was prepared by dissolving 1470P of potassium bromide in 13,600 ml of distilled water.

A silver nitrate solution (solution C) was prepared by dissolving 200 Or of silver nitrate in 13601' of distilled water.

Solution A was heated to 80°C.

Solutions B and C were heated to 60°C and added to solution A held at 80°C at a rate of 233 mV min for 60 minutes by double jet addition.

The mixture was cooled to 20°C and adjusted to pH 2.0 with 10% sulfuric acid.
Adjusted to 7.

The silver halide-gelatin linear precipitate was washed with cold distilled water until the conductivity of the supernatant was 50-100 μmhos.

893 grams of dry activated bone gelatin was added and allowed to swell for 20 minutes.

The temperature was raised to 38°C and held at that temperature for 20 minutes to dissolve the gelatin.

The pH was adjusted to 5.70 with 10% sodium hydroxide and gold sensitizer was added as in Example 1.

The temperature was raised to 51°C and the emulsion was aged after 180 minutes.

The emulsion was cooled to 38°C, a panchromatic optical sensitizer was added,
The emulsion was aged for 45 minutes, then cooled and hardened.

The resulting silver iodobromide emulsion contained approximately 97 mole percent bromide.

The silver iodobromide emulsion had an average diameter of about 0.93 microns and a 8c
The particle size frequency distribution curve shown in the figure had a scatter number of 0.47.

80% of silver halide grains have an average diameter of +33% to -30
It had a diameter in the range of %.

As mentioned above, the present invention is particularly valuable for providing color-additive motion picture films because it does not require removal of developed silver halide emulsion layers or layers to which processing compositions have been applied.

In this embodiment, the film is preferably exposed, developed and projected without being removed from the cassette.

The cassette has a feed reel, a take-up reel, a reservoir for processing liquid, and appropriate holes for exposure and projection.

After exposing the entire film reel, the exposed film is advanced to a liquid application position (see vessel 20 in FIG. 1, step B) where the processing liquid is applied as the film is re-wound, i.e. returned from the take-up reel to the feed reel. The applied processing liquid is trapped within the film vortex.

After a suitable period of time after the film has been rewound to complete development and transfer image formation, the film is again advanced from the feed reel to the take-up reel and into the projection position to enable viewing of the final color-added motion picture film. .

The processing solution is not removed from the developed film, and the wet developed film is dried during the projection process.

In a typical embodiment of this type, the processing liquid is about 0.0005
"Applied as a thick layer, the elapsed time from application of the processing liquid to the edge of the exposed film to projection of that portion of the film is approximately 10".

It is understood that development and transfer imaging must be completed within this time despite the fact that there is a longer time between application of the processing solution and projection of the other end of the motion picture film strip. Good morning.

Details of such in-cassette processing can be found in U.S. Pat. No. 3,608.
455; 3615127; 3616740; 3643579 and 3687051, which may be referred to for details.

Of course, if desired, such films can be developed and viewed in continuous operation without intervening winding operations by providing a suitable dark storage area for the developing film between the processing solution application location and the viewing or projection location. I can do it.

Diffusion transfer processing in the presence of quaternary ammonium compounds such as N-benzyl alpha-picolinium bromide has been found to be advantageous in keeping the maximum density of the developed negatives low.

In fact, developed silver grains are developed in the presence of quaternary ammonium salts, especially when the predominant silver halide developer is α and β.
- There is evidence that enediols, such as tetramethyl reductinic acid, have a smaller coverage area.

The following example illustrates this embodiment and the use of the invention in forming additive color movies.

Example 6 A transparent polyethylene terephthalate film base carrying approximately 1000 triple sets of dichromate-containing gelatin filter lines dyed red, green, and blue was prepared as described in the aforementioned U.S. Pat. No. 3,284,208. It was prepared by the following method.

1.5 micron thick “Saran” on top of the additive screen
A layer of polyvinylidene chloride polymer ("Saran" is a trademark of the Dow Chemical Company) is coated, followed by a 0.5 micron thick layer of "Formvar" polyvinyl formal polymer ("Holmvar" is a trademark of the Shawinigan Product Company). ) and about 4.41ru? An image-receiving layer was coated containing deacetylated chitin/ft2 and copper sulfide at approximately 0.125 cm/ft2.

Next, a sample with an average diameter of 0.8 made in the same manner as in Example 1 was prepared.
6 microns, particle size frequency distribution curve (Fig. 8d), scattering number 0.
34, panchromatically sensitized predominantly homogeneous substituted-halide hybrid halide chemically sensitized silver halide with 90% of the grains having diameters ranging from 0.62 to 1.09 microns or +27% to -28% of the average diameter. A light-sensitive silver halide layer was applied over the image-receiving layer using an emulsion.

The silver halide layer contains about 120 µ/ft 2 of gelatin and about 98.5 µ/ft 2 of silver and about 0.5 µm of gelatin.
It contained 2% by weight propylene glycol alginate.

The silver halide emulsion layer was then coated with an antihalation layer containing 250 .mu./ft" of gelatin.

The photosensitive element was cut to Super 8 projection size, punched and placed in a cassette similar to the aforementioned patent.

After exposure, the following processing composition was applied over the antihalation layer at a coverage of about 1.15 S'/ft2 and the film was wound onto a take-up reel on its own.

Sodium hydroxide 6.871 Hydroxyethylcellulose (su) 0.69P Lozole 250, high viscosity) Tetramethyl reductin acid Sodium sulfite Sodium thiosulfate Potassium bromide N-benzyl-α-picolinium furomide (50% solution) Water Approximately 10 seconds after applying the treatment composition to the edge of the exposed film, the film is rewound onto the feed reel and the applied treatment is removed. The composition was projected without washing or removal.

A high quality additive color motion picture film was obtained.

The red, green and blue characteristic curves of the intermediate column of an additive film thus processed are shown in FIG. 14 and have the following transmission densities:

Red Green Blue Dmax 2.012.352.47 Dmin O, 250, 250, 25 Sodium thiosulfate used in the above example was pentahydrate.

In a particularly advantageous embodiment, the additive transparency film includes an anti-nolation layer as the outermost layer terminal from the transparent support.

Providing such an antihalation layer on a diffusion transfer coloring film is disclosed in Japanese Patent Application No. 49-85586 (Japanese Unexamined Patent Publication No. 50/1989) of Nidwin Etch Land, which was filed at the same time as the present invention.
No. 45633).

Antihalation dyes are selected for their ability to become colorless upon contact with processing compositions such as sodium sulfite.

The transmission density of the anti-nolation layer used in the above examples was about 0.5-0.6 for red, green and blue light.

In Examples 2 and 3, the antihalation dye was placed in a layer of cellulose hydrogen phthalate acetate, while gelatin was used as the binder in Example 6.

It has been found that the anti-noration layer provides enhanced color separation, particularly in the toe of the positive image characteristic curve.

The antihalation layer, as used in the above embodiments, is disclosed in U.S. Pat.
Noble metal image stabilizers, ie substantially water-insoluble gold compounds, of the type described in the above specification may also be included.

Although the additive film has been described as including an additive screen, the concepts of the present invention can be used in combination with a biconvex lenticular screen to obtain an additive image.

The prior art is silent on the desirability or advantage of using largely uniform grain size silver halide emulsions as described above.

In fact, as illustrated by the previously cited U.S. Pat. No. 3,536,488, the prior art has shown that approximately
We believe it is desirable to use a silver halide emulsion with a grain diameter of 5 microns, whereas in the present invention we have a uniform grain size with an average diameter of 0.7 to 1.5, preferably 0.7 to 1.0 microns. Silver halide emulsions are used.

All facts contained in the foregoing description or shown in the drawings are intended to be illustrative only and limiting, since certain modifications may be made to the products and methods described without departing from the scope of the invention. It's not something.

[Brief explanation of drawings]

FIG. 1 is a schematic enlarged sectional view of a diffusion transfer color photosensitive element showing an embodiment of the present invention regarding the three steps of diffusion transfer processing, that is, exposure, processing, and formation of a color additive transparent image with a final image;
Figure 2 is an optical micrograph at 1000x magnification of a transmission view through an unexposed diffusion transfer color addition film, which is an embodiment of the present invention, and Figure 3 is an optical micrograph at 1000x magnification after exposure to red light (maximum) and diffusion transfer processing. Optical micrograph at 100OX magnification of transmission view through diffusion transfer color film in Figure 2, Figure 4 after maximum exposure to green light, intermediate level exposure to blue and red light, and diffusion transfer processing. Figure 2 is an electron micrograph at 10,000x magnification of a portion of the diffusion transfer color-added film shown in Figure 2, and Figure 5 shows undeveloped silver iodobromide grains in a halide emulsion used in a commercial silver diffusion transfer process. Figure 6 is an electron micrograph at 100OOX magnification of a replica of undeveloped silver iodobromide grains of other silver halide emulsions used in other commercial silver diffusion transfer processes. Figure 7 shows undeveloped silver iodochlorobromide grains in films according to embodiments of the present invention, particularly useful largely uniform grain size substituted-light silver halide emulsions (emulsion preparation is described in Example 1). FIG. 8a is a graph of the grain size frequency distribution of the substituted silver halide emulsion of FIG. FIG. 9 is a graph of the grain size frequency distribution of a silver halide emulsion with a silver coverage that is particularly effective in the practice of the present invention. Transmission diagram of 1000o through the silver oxide layer
Figure 10 is an electron micrograph at 100OOX magnification of the transmission diagram through the silver halide layer of Figure 9 after exposure (maximum) and development; The total coverage area of the single layer is calculated as follows: silver 1 of silver halide
Figures 12, 13 and 14 are characteristic plots of the red, green and blue densities of the middle column of an additive transparency obtained in accordance with certain examples, as a function of their particle diameter in the amount of 00m97ft2. . 20... Processing liquid storage device, 30... Film unit.

Claims (1)

[Scope of Claims] 1. Consists of a transparent support carrying a photosensitive silver halide emulsion-containing layer, a silver receiving layer and an additive color screen, through which the developed negative can pass through without separating the silver image and the positive transferred image. A photosensitive element for forming a positive transparent image by a diffusion transfer process, which provides the negative silver image and the transferred image that can be seen as a positive image when exposed to light; The silver halide grains are mostly uniform in crystal diameter, about 0.7 to 1
．． having an average diameter in the range of 5 microns and being coated with a substantially monolayer, the area covered by the (I[) silver halide grains is
Greater than about 50% of the surface area of the silver halide emulsion layer (
and (6) the silver halide emulsion layer contains about 90 to 1251 n9 of silver halide per square note.