JPH0314664Y2 - - Google Patents

Description

[Detailed Description of the Invention] (Field of Application of the Invention) The present invention relates to an improvement of a film unit for diffusion transfer in which a photosensitive sheet and an image-receiving sheet are overlapped and processed.

(Prior Art) One of the photographic methods by which photographic images can be easily obtained is the diffusion transfer method known as instant photography.

The silver complex diffusion transfer method for obtaining a black and white image generally uses a photosensitive sheet in which a silver halide emulsion layer is formed on a support as a photosensitive layer, an image receiving sheet in which an image receiving layer containing physical development nuclei is formed on a support, and It consists of a processing solution containing a silver halide solvent. The principle of the silver complex diffusion transfer method is that the silver halide in the exposed areas of the exposed photosensitive layer is developed by the developing agent in the processing solution or the photosensitive sheet, and at the same time, the silver halide in the undeveloped areas is developed in the processing solution. It reacts with the silver halide solvent to form a soluble silver complex salt, which diffuses into the image-receiving sheet and is reduced and deposited by physical development nuclei in the image-receiving layer to form a silver image.

On the other hand, in the color diffusion transfer method for obtaining color images, after exposing an image-forming layer containing at least one silver halide emulsion layer combined with a dye image-forming substance coated on a support, an alkaline processing solution is applied. and developing to form an imagewise distribution of the diffusible dye or its precursor, forming an imagewise distribution of the dye or its precursor, and forming at least a portion of the imagewise distribution of the dye or its precursor. A color image is formed by diffusion transfer to an image-receiving layer that is superimposed or adapted to be superimposed on the surface of the image-providing layer.

Instant photography differs from regular black-and-white or color photography in the method of forming photographic images.While ordinary photographs undergo a complex process of developing, bleaching, and fixing, instant photography requires only one process.
It has the characteristic that a positive image is formed during the process, and therefore, it has been used as a so-called in-camera photo, where you can enjoy the image immediately after taking it with a camera.

The film unit for diffusion transfer method has been known for a long time, and after image exposure of a photosensitive sheet,
When pulled out from the camera, pressure is applied to the rupturable container containing the processing agent composition in contact with the sheet having the image-receiving layer to rupture the container, releasing the processing agent and spreading it between both sheets. However, so-called "peel-off" type film units in which both sheets are peeled off after a predetermined period of time to form an image on a sheet having an image-receiving layer are disclosed, for example, in U.S. Pat.
No. 3362821, Special Publication No. 44-2528, No. 44-9502,
It is disclosed in No. 42-7823, No. 47-14655, No. 48-15870, etc.

Also, U.S. Patent No. 3415644, U.S. Patent No. 3415645, U.S. Pat.
No. 3415646, No. 3594164, No. 3594165, No.
No. 3573043 and No. 3647437, etc., disclose a so-called "integral" film unit in which a photosensitive layer and an image-receiving layer are coated on the same support, and there is no need to remove the developing solution. ing.

Diffusion transfer film units are generally packed into cameras and processed on the spot immediately after imaging, and are handled under a variety of climatic conditions. Therefore, in both cold regions and extremely hot regions,
It is necessary to always obtain good and stable photographic images under any temperature conditions, that is, it is necessary to have a wide processing temperature latitude.

In general, it is known that silver halide development and related image formation processes are greatly affected by the temperature during processing. Alternatively, it has a function to control the image forming process and has a wide processing temperature latitude.

By the way, for example, Polaroid Type-107
It is known that the time it takes to peel off the photosensitive sheet and image-receiving sheet differs greatly depending on the temperature in the "peel-off" type diffusion transfer film unit found in Type-108 or Fuji Instant Color Film FP-100 manufactured by Fujifilm. It is being

If the time required to peel off both sheets is short or long, good photographs may not be obtained, or the photographs may be uneven or visually undesirable. Therefore, when processing a "peel" type diffusion transfer film unit, temperature measurements have been essential to determining the timing for peeling off both sheets.

However, these "peel away" type diffusion transfer film units have instructions or explanatory notes printed on the container containing the film unit indicating the relationship between processing temperature and peeling time, that is, development time. ,Although it was inserted, the only way to check the processing temperature was to monitor it with a thermometer. Attaching a thermometer to the diffusion transfer film unit is not desirable in terms of operability and safety, and is also disadvantageous in terms of cost.

(Purpose of the invention) An object of the invention is to provide a diffusion transfer film unit in which the peeling time of the diffusion transfer film unit can be immediately determined.

A second object of the present invention is to provide a novel temperature display method during processing of a diffusion transfer film unit that does not affect the runnability of the diffusion transfer film unit.

(Structure of the invention) The above purpose is to visually identify the peeling time of photographic materials used in the diffusion transfer method, in which a photosensitive sheet and an image-receiving sheet are overlapped and brought into close contact, and after transfer processing, both sheets are peeled off. This was achieved with a diffusion transfer photographic material having a characteristic temperature sensor with peel time.

The temperature sensor used in the present invention may be any means that can display the temperature range in question using colors, numbers, letters, or figures, such as thermophysical properties such as thermal expansion, thermal deformation, thermal breakdown, or decomposition, electrical resistance, electric potential, etc. Any method that utilizes electromagnetic physical properties or optical physical properties such as color tone, turbidity, and refractive index may be adopted, but a method that utilizes color change is preferable from the viewpoint of cost, safety, and especially strong notification effect. . and. Among the means based on color change, the method using liquid crystal is the most effective and practical.

As is well known, liquid crystals include smectic liquid crystals, nematic liquid crystals, and cholesteric liquid crystals, and the liquid crystals used in the present invention are those that exhibit unique color changes in the temperature range that causes problems in the photographic materials for diffusion transfer. Any of the above three states of liquid crystal can be used.

In addition, mixed liquid crystals in which the color tone and coloring temperature range can be adjusted by mixing multiple types of liquid crystals at a fixed ratio are useful, and guest-host type liquid crystals to which dichroic dyes are added are also useful.

Examples of liquid crystals according to the present invention include a-n-butylsorbic acid, p-ethoxybenzylidene-p'-butylaniline, cholesteryl myristate, methoxybutylazoxybenzene, p-hexyl carbonate, etc. p'-Heptylphenylbenzoate, 2-n-tridecylpyridinium salt, o-carbutyloxy-p-oxybenzoic acid, 7-n-heptyloxy-2-fluorenic acid propyl ester, p-methoxybenzal −
Examples include p-amino-α-methyl cinnamic acid propyl ester, butyric acid sitosterin ester, etc. For mixed liquid crystals, if the mixed weight percentage is shown in parentheses, p-azoxyanisole/anicylidene-p-amino Phenyl acetate (60/40 and
80/20), 4-cyanophenyl-4-n-heptylbenzoate/4-cyanophenyl-4-n-
Butylbenzoate (66/34), 4-(4'-n-hexylbenzylideneamino)benzonitrile/4
-(4'-n-propylbenzylideneamino)benzonitrile (66/34), cholesteryl cinnamate/cholesteryl nonanoate/cholesteryl oleyl carbonate (20/30/50), cholesteryl nonanoate/cholesteryl acetate (80/
20), cholesteryl nonanoate/cholesteryl propionate (80/20), etc.

These liquid crystals generally change as the temperature increases.
Liquid crystal changes to isotropic liquid, and the color of liquid crystal generally changes from the long wavelength side to the short wavelength side from low temperature to high temperature, such as red, green, blue, and violet, but there is a mixture that changes color in the opposite way. There is also an LCD. Therefore, if a liquid crystal exhibiting a general color change and a liquid crystal exhibiting a reverse color change are used side by side with respect to temperature, the temperature can be detected from two directions, high and low, and the detection accuracy can be increased.

The liquid crystal according to the present invention can be used in the form of a thermofilm or thermopanel in which a cell is constructed by sandwiching thin liquid crystal layers, and if necessary, the inner surface of the cell may be subjected to an alignment treatment for the liquid crystal, or an alignment agent may be applied to the liquid crystal. may be added to align the liquid crystal molecules parallel to or perpendicular to the cell surface. In addition, for orientation processing,
Treatments include rubbing the inner surface of the cell with cotton or other material in a certain direction, coating it with lecithin, or embossing the inner surface to create minute irregularities, and as alignment agents, benzoic acid derivatives, polyamides, etc. have been developed. Available for use.

The thermofilm, thermopanel, etc. having a liquid crystal cell structure can be prepared as a liquid crystal adhesive tape by providing an adhesive layer having a removable cover layer on the back side, thereby contributing to convenience of use.

Moreover, if the liquid crystal according to the present invention is made into liquid crystal microcapsules using a method such as core cell vasion,
Handling becomes extremely convenient, coloring brightness can be increased, preservability and durability are improved, and practicality is greatly improved. Of course, liquid crystal microcapsules can be used in the liquid crystal thermofilm or panel described above.

Furthermore, liquid crystal printing ink can be prepared by suspending liquid crystal microcapsules in a water-soluble binder, and can be used by directly printing by screen printing or stencil printing, or by pasting a printed sheet. It can be served.

For microencapsulation of liquid crystal, the method described in detail in Chiba Faculty of Engineering Research Report (40) 21 (1970) p163 (Kubo, Arai) can be used.

(Example) Next, the present invention will be explained with reference to examples.

Although FIG. 2 shows a diffusion transfer film unit 10 according to the present invention, it will be appreciated that the thickness of each component is exaggerated for clarity. Film unit 10
includes a photosensitive element 18 and an image receiving element 12 . The two elements are both sheet-like and matched in size and shape and are in contact with each other. The photosensitive element 18 has a holding sheet 22, a photosensitive sheet 20 joined at one end to the holding sheet 22, and an excess processing liquid collection sheet 26 joined to the other end. The generally rectangular photosensitive sheet 20 has a layer of photosensitive material, such as silver halide, coated on a suitable support.
The support of the photosensitive material is generally made of any flexible material used as a film substrate, and is either one that does not transmit active light such as visible light, ultraviolet rays, or X-rays, or is made of a combination of such materials. It is made by The retaining sheet 22 and the collecting sheet 26, which are joined to each end of the photosensitive sheet 20, are made of any flexible sheet material that does not transmit active light that causes a chemical action on the photosensitive sheet 20. Collection sheet 26, which is generally rectangular in shape, has a width equal to photosensitive sheet 20 and has sufficient structure to collect and retain any excess liquid used in photographic processing.

The retaining sheet 22 is also substantially rectangular, and its width is the same as the width of the photosensitive sheet 20, except that the opposite end of the photosensitive element 18 that is joined to the photosensitive sheet 20 is provided with a cleavage member, which will be described later. narrowed to facilitate insertion into the The retaining sheet 22 connects the photosensitive element 18 and the image receiving element 12, provides an introduction to the cleavage member, etc., provides a purposeful aligned arrangement of each element, and provides a substrate for mounting a container 30 containing a processing composition. , and has several functions, such as spreading a predetermined amount of a layer of processing composition between the photosensitive element and the image receiving element.

The image receiving element 12 has a holding sheet 14 and an image receiving sheet 16 that are substantially the same in size and shape as the photosensitive element 18, and the periphery of the image receiving sheet 16 is adhered to a frame provided on the holding sheet 14. In addition, the holding sheet 14
is joined to the retaining sheet 22 in a hinge-like manner at the joint 11 so that the door can be opened freely, and when the photosensitive element 18 and the image receiving element 12 are overlapped, the photosensitive sheet 20 and the image receiving sheet 16 are aligned with each other. face to face.
The retaining sheet 14 is made of a relatively thin but strong flexible sheet material and includes elongated rectangular spacers 15 that overlap the edges of the image receiving sheet 16, which are formed when the image receiving sheet 16 and the photosensitive sheet 20 are polymerized. , the area of these sheets in contact is limited, and thereby a white frame portion is formed in the transferred image. Image receiving sheet 16 typically has an image receiving layer coated on a suitable support. The support is generally rectangular, generally composed of any flexible material useful as a support for photosensitive materials, and is opaque to the actinic radiation of the photosensitive sheet.

The holding sheet 22 and the holding sheet 14 are adhered to each other to form the joint 11. This joint 11 opens the image receiving element 12 and the photosensitive element 18, which were separated by opening the door while the photosensitive sheet 20 is not exposed to the active light, while the processing composition is spread between the two elements and subjected to development processing. The positions are controlled so that they are superimposed on each other.

In the film unit configuration shown in FIG. 2, the processing solution typically includes a silver halide developer,
The photosensitive element 18 and the image receiving element 1 contain a silver halide solvent and an alkaline agent as a non-viscous or viscous condensing agent.
2 is housed in a cleavable container 30 attached to the surface of the retaining sheet 22 which becomes the inner side when the joint 2 is closed around the joint 11.

Next, a plurality of the film units described above are stored in a cassette that conforms to the camera specifications, and a photograph is taken.
Film pack 40 for in-camera development
I will explain about it.

FIG. 3a shows the cassette, and FIG. 3b shows the shape of the film unit housed in the cassette, with one film unit taken out as a representative, and shown separately as cross-sectional views.

Note that the same symbols as those mentioned above have the same meanings as above, and the same applies hereafter.

In FIG. 3a, 41 is a flat rectangular parallelepiped in the illustrated example of a cassette, and a canopy 42 having an exposure window 44 and a housing 4 for housing the film unit 10.
3. Press the photosensitive sheet 20 of the film unit 10 to the exposure window 44 in the operation outlet 45 of the film unit 10 and the cassette 41, and reverse the direction of the exposed photosensitive element 18 and move it to the operation outlet 45. It has a pressure plate 46 having a curved portion 461 directed toward.

To store a plurality of films 10 in the cassette 41, the image-receiving element 12 and the photosensitive element 18 are extended flat from the joint 11, and then the joint 11 and the image-receiving sheet 16 are separated as shown in FIG. 3b. The edge portion holding sheet 14 holds the image receiving sheet 16 and the leader 70.
A predetermined number of film units 10 are folded in a zigzag manner so as to be sandwiched between the film units 10 and 10, and are stacked in a predetermined number. Next, the curved portion 461 of the pressure plate 46 is applied between the joint 11 of the retaining sheet 22 and the container 30, and the photosensitive element 18 is folded back and stored in the cassette 41 with the leader 70 exposed from the operation outlet 45. .

When the film pack 40 arranged as described above is exposed and the reader 70 is pulled out from the operation outlet 45 as the first stage of in-camera operation, the image receiving sheet 16 remains stationary and the flexible holding sheet 14 is moved. The turning point at the initial joint 11 is placed on the image receiving sheet 1.
6 and follow the leader 70,
It is exposed to the outside through the operation outlet 45. Meanwhile, at the same time, the photosensitive element 18 also moves while reversing the direction of movement at the curved portion 461 of the pressure plate 46, and the container 30 passes the edge of the stationary image receiving sheet 16, and the container 30 installed in the camera is moved. When the tearing member (not shown) is reached, the leader 70 is torn off, and the tip 24 of the holding sheet 22, which is strong against tensile stress, is exposed to the operation outlet, and the photosensitive sheet 20 containing the exposure agent and the image receiving sheet 16 are brought face to face. placed in alignment with and in contact with.

When the tip 24 is pulled out as the second stage of the in-camera operation, the container 30 is split open by a tearing member (not shown), and the spacer 1 is opened by the pulling force.
Photosensitive sheet 20 and image receiving sheet 16 separated by 5
During this time, development and diffusion transfer of the image-forming material begin, and when both sheets are peeled off after a predetermined period of time, a transferred image is obtained on the image-receiving sheet 16.

The film pack 40 is a shielding member that shields the exposure window 44 and wraps the outside of the film unit stored in the film pack to expose its tip to the operation outlet 45 until it is loaded into the camera or camera bag. Optically protected, the shielding member is pulled out and removed from the operation outlet 45 prior to exposure.

The development and diffusion transfer are functions of temperature and time, and the present invention attempts to obtain good image quality by detecting the temperature that fluctuates with the outside air and adjusting the time.

The visually observable temperature sensor used in the present invention can be easily and inexpensively manufactured without significantly increasing the cost of the photographic material for diffusion transfer, and furthermore, the visually observable temperature sensor used in the present invention can be manufactured easily and inexpensively without significantly increasing the cost of the photographic material for diffusion transfer, and furthermore, it has a practical effect on the effective operation of the film unit, film package, and camera. It can be installed at any part of the film unit or film pack as long as it does not have an adverse effect on the film. For example, a thermo film made of liquid crystal or the like on the side of the photosensitive sheet 20 or the image receiving sheet 16 opposite to the side on which the photographic layer is coated, or on the end of the holding sheet or the holding sheet, Although it can be used by attaching a thermo panel or printing liquid crystal microcapsules by a printing method, in particular, as shown in FIGS. It is preferable to provide it in the cassette 41 that is used.

The temperature sensor may be placed anywhere on the photographic material for diffusion transfer; however, it may be attached together with the photographic material in the photosensitive material package that stores the photographic material, and the temperature sensor may be attached at the time of use. You may also do so.

FIG. 1a shows an example in which a digital thermo tape 90 (trade name, manufactured by Nihon Yu Giken Kogyo Co., Ltd.), which serves as a temperature sensor and displays the temperature as green numbers, is attached to the reader 70. By printing the appropriate peeling time for the photosensitive sheet and image-receiving sheet for each temperature, you can visually measure the appropriate peeling time for the photosensitive sheet and image-receiving sheet under any temperature conditions without having to look around for a thermometer. I was able to do that.

FIG. 1b shows a thin film using mixed liquid crystal microcapsules on the bottom surface of the casing 43 of the cassette 41.
91 LCD adhesive panels consisting of a 30 μm liquid crystal thin layer
showed that. In this case, the camera would require a window to view the temperature display.

Up to now, we have described a film unit for diffusion transfer method in which a processing composition stored in a cleavable container for an exposed photosensitive sheet is spread between the photosensitive sheet and an image-receiving sheet. , US Patent No. 3485628, UK Patent
A photosensitive sheet used in the diffusion transfer method described in No. 1496363, etc., in which one or both of a photosensitive sheet and an image-receiving sheet are immersed in a bath such as a tray or tank containing a developing solution. It is within the scope of the present invention to provide the sheet or image-receiving sheet with the temperature sensor of the present invention.

[Brief explanation of the drawing]

Figure 1 is a diagram showing an example of a temperature sensor according to the present invention attached to a reader or cassette;
The figure is a perspective view illustrating the structure of a film unit according to the present invention, and FIG. 3 is an exploded explanatory view of the film pack. 90 and 91...Temperature sensor, 70...Reader, 43...Cassette housing, 10...Film unit, 12...Image receiving element, 16...Image receiving sheet, 14...Holding sheet, 18...Photosensitive sheet,
20... Photosensitive sheet, 22... Holding sheet, 30
...Cleasable processing agent container, 40...Film pack, 41...Cassette, 42...Canopy, 43...
...Housing, 44...Exposure window, 45...Operation drawer opening.

Claims (1)

[Scope of utility model registration request] A temperature sensor with a peeling time, which is used in the diffusion transfer method in which a photosensitive sheet and an image-receiving sheet are overlapped and brought into close contact with each other and then both sheets are peeled off, is capable of visually identifying whether the photographic material is peelable. A photographic material for diffusion transfer.