JPS6016611B2 - Heat treatment method for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for substantially flattening a sheet-like silver halide photographic light-sensitive material with curls, which is cut into a predetermined size after winding a strip film into a roll. The present invention relates to a heat treatment method.

More specifically, a silver halide photographic light-sensitive material having gelatin-containing photographic component layers on both sides of a photographic support is heat-treated under specific conditions before being used in a sheet sealed package. The present invention relates to a heat treatment method for a substantially flat sheet-like silver halide photographic light-sensitive material. In general, silver halide photographic materials are manufactured by continuously coating a strip support with a photographic component layer, drying it, and then winding it up into a roll for storage, which results in curls. I end up. For this reason, even after the strip IJp support is cut into sheets, it is bent due to curling curls, and this bending is difficult to eliminate. It is difficult to insert a sheet-shaped silver halide photographic material (film) that is bent due to the winding curl into a photographic film frame, and moreover, the film may be damaged.

In addition, when the film is inserted into an automatic photographing device or an automatic developing device, film transport defects may occur, and the faulty transport of the film may have an adverse effect on many other films, making many films unusable, resulting in economical problems. In addition, in the case of X-ray photography, it can cause serious problems that can even threaten human life. Therefore, there have been strong demands for improvements to eliminate the curvature of sheet films, but there are various limitations in the case of photosensitive materials with silver halide emulsion layers, and very few technologies have been put to practical use. I couldn't see it. For example, a method has been proposed in which curling is reduced by so-called reverse winding of a film that has been coated, dried, and wound. However, the current situation is that strip films that have been rolled for a long period of time still have curls in the winding direction, and even when cut into sheets, they are curved and do not become flat. Furthermore, a method has been proposed in which a rolled strip film with curls is squeezed for a short time at high temperature before being cut into sheets to remove curls. However, this method requires the installation of very expensive heating and ironing equipment, and although it reduces the degree of curvature after ironing, it is difficult to flatten it, and the temperature is too high for photographic performance. This is not a practical method as it degrades the In addition, as a simple way to reduce curling, there is an attempt to increase the diameter of the winding shaft to reduce the degree of curvature in the rolled pillow state as much as possible, Although the curvature of the curve becomes smaller, it does not become completely flat, so this cannot be a fundamental solution. Therefore, as a result of extensive research into a method for substantially flattening a sheet-like silver halide photographic light-sensitive material in which gelatin-containing photographic component layers are coated on both sides of a photographic support, the present inventors discovered that the emulsion layer and other The present invention has been completed by successfully making the sheet film substantially flat without any adverse effect on the photographic component layer.

That is, an object of the present invention is to provide a method for heat processing a silver halide photographic material having gelatin-containing photographic component layers on both sides of a photographic support.

Another object of the present invention is to form gelatin-containing photographic element layers on both sides of a photographic support during heat treatment without any adverse effect on the photographic properties of the emulsion layer or other photographic element layers. An object of the present invention is to provide a method for heat-treating a sheet-shaped silver halide photographic material, which substantially flattens a sheet film having the following properties.

Furthermore, another object of the present invention is that the process is easy, inexpensive, and mass-producible; An object of the present invention is to provide a method for heat processing a sheet-like silver halide photographic material, which can be made substantially flat without deforming the material.

The present inventor coated a silver halide photographic emulsion layer on at least one side of a photographic strip support, coated a gelatin-containing photographic component layer on both sides of the support, and wound the support into a roll. A silver halide photographic light-sensitive material is cut into a sheet, and the sheet is laminated in an atmosphere with a relative humidity of 20 to 80% in a psychrometric chart, a dry bulb temperature of 10 to 40 pm, and a fog point temperature of 25q0 or less. Stacked and packaged, 20-65
It has been found that the above objective can be effectively achieved by heat treatment at qo for 1 hour or more.

Next, before giving a detailed explanation of the present invention, the meanings of terms used in this specification will be explained.

Generally, when a photosensitive material that has been kept wound at a certain curvature is unwound, the strip film is bent in the length direction of the strip film, and this is called a strip film with curls. The degree of bending is called the degree of curl. This winding pattern is caused by the fact that when a strip film that has been wound to a certain curvature M is unwound as shown in Figure 1, the strip film suddenly opens in the length direction by a point A immediately after unwinding. Then, the curvature state is restored by the length of the straight line a, and once the curvature strip film has a curvature of P. Thereafter, as time passes, the curved state gradually decreases like curve b, and from point B after a certain period of time, the curved state almost maintains equilibrium, and the curved strip film having the value of curvature Q becomes. A curved strip film having a value of curvature Q is cut into a predetermined size to form a curved sheet film. The bent sheet film is in the state shown in Figure 2, where the radius of curvature r from the center of curvature ○ is
(The unit is shown in meters) is the reciprocal of the curvature, and this curvature is called the degree of waviness of the sheet film. Therefore, in this specification, the term "curvature" refers to the curved state of a strip film that has a value of curvature Q when equilibrium is reached after a certain period of time has elapsed since the strip film was unwound. In the present invention, the sheet film becomes substantially flat by heat treatment.

Here, "substantially flat" is ideal if the curvature is ○ or almost 0, but in reality, if the curvature is in the range of 0 to 2.0, preferably in the range of 0 to 1.0. good. Incidentally, the curvature of 2.0 corresponds to the degree of curl of the sheet film in a circular arc having a radius of curvature of 0.5, and is such a degree that it appears flat at first glance. Furthermore, when the curvature is 3.0, it looks clearly curved, and if a sheet film with a curvature of 3.0 is actually inserted into the conveyance system of an automatic photographing device, conveyance failure may occur. Furthermore, such troubles frequently occur with sheet films having a curvature of 3.0 or more.
However, for sheet films with a curvature of approximately 2.0 or less,
The above-mentioned conveyance system operates normally without causing any conveyance defects. The present invention is characterized in that a sheet-shaped silver halide photographic light-sensitive material (hereinafter referred to as a sheet film) is heat-treated under specific conditions. The sheet film is required to be stacked in an atmosphere with a temperature of 10 to 40 qo and a fog point temperature of 25 qo or less, packaged and sealed, and heat-treated at 28 to 65° C. for 1 hour or more.

That is, the present invention makes it an essential condition to heat-treat the packaged and sealed sheet film, and cools the sheet film after this heat treatment, so that if unspecified air exists between the stacked sheet films in the package, , there is a risk of development in which the sheet films adhere to each other (so-called sticking phenomenon). Furthermore, even if the sheet film is cooled down to, for example, room temperature (approximately 25 degrees centigrade) or lower after being heat-treated, there is a risk that the air inside the package may form on the inside of the packaging material. Therefore, if the cooling temperature after heat treatment is to be lower than room temperature, packaging must be carried out in an atmosphere with humidity conditions such that dew condensation does not occur between sheet films or between film packaging materials at this cooling temperature. For this purpose, it is sufficient to find an atmosphere suitable for the conditions from an psychrometric chart and use it.
The preferred range must be determined in consideration of the working environment and the manufacturing cost of obtaining the necessary air. For example, low-temperature air of 10 q or less not only creates a poor working environment but also increases the cost of cooling the air, which increases the cost of the film and is not practical. In particular, it is extremely expensive and impractical to obtain low-temperature air. As mentioned above, the air used in the present invention has the following characteristics in the psychrometric diagram:
Although the air is limited to a relative humidity of 20 to 80%, a dry bulb temperature of 10 to 40 oo, and a dew point temperature of 25° C. or less, it is preferable to select air with a fog point temperature of 0 to 200° C. from the viewpoint of actual processing. In the present invention, any means may be used to provide air under the above conditions when sealing the package. For example, there is a method of air conditioning the entire packaging work room with air under the above conditions, a method of forming a room surrounding the packaging storage area and air conditioning only this room with air under the above conditions, and a method of using air blowers such as nozzles in the packaging area. Any method may be used, such as providing an outlet and wrapping and sealing the sheet film while blowing air under the above conditions onto at least the sheet film surface or the packaging material surface. The heat treatment of the present invention is carried out by heating the packaged and sealed sheet film obtained under the above conditions to a specific degree of overflow while still being packaged.

This heating temperature is limited to a range of 28 to 65°C. The heating time can be shortened as the heating temperature is increased; however, if the heat treatment is performed at a temperature higher than the above upper limit temperature, the emulsion layer, etc. of the sheet film will be affected, and the photographic properties of the sheet film will be adversely affected. In the present invention, the object can be sufficiently achieved by heating below the above-mentioned upper limit temperature. It seems that there is almost no difference in the above lower limit temperature compared to room temperature (23 to 25°C), but if heating is performed for a slightly longer time than in the case of heating at a high temperature, the present invention can be achieved as described above. can fully achieve its objectives. The present inventor found that a sealed and packaged sheet film that had been stored at room temperature for three months at 23:00 o'clock had considerable curling, but did not become flat even after a further extension of the time. However, 28
The sheet film heat-treated for two months at a temperature of 0.degree. C. became substantially flat. The discovery of such an effect was made at room temperature (2
This was surprising considering that the heating temperature was thought to be almost no different from 3 to 25q0). The heating temperature for the heat treatment in the present invention is generally 28 to 65°C, but it can be mass-produced industrially at low cost, shortens the processing time, and has no effect on photographic performance regardless of the type of film. 30-50 in order to prevent
Preferably, the temperature is qC.

In the present invention, any method may be used to heat the tightly packaged sheet film as it is packaged, as long as it can uniformly heat the sheet film.

For example, the entire heating chamber in which the packaging sheet film is heat-treated may be adjusted to the above-mentioned heating temperature conditions, or the packaging may be covered from above and below with a heating medium. As the heating medium, a heating plate, a combination of a heat generator and a thermally conductive metal, a thermally conductive metal cover containing a fluid such as a thermally conductive liquid, etc. can be used, and other heating media may be used. Also good. Sheet films that have been hermetically packaged may be heat-treated directly in their packaging containers (bags), or by stacking several packaging containers (bags) and placing them in an outer container (for example, a cardboard box). You can also heat it in that form. Note that each packaging container (bag) or outer packaging container may be independent, or a plurality of packaging containers (bags) or outer packaging containers may be stacked. Preferably,
It is best to place the container with the film side horizontal. In the present invention, it is desirable to cool the packaging sheet film to room temperature after the above heat treatment, and this cooling method may include cooling the packaging sheet film as it is at room temperature or at a temperature lower than that. .

Sheet films to which the processing method of the present invention can be applied include all silver halide photosensitive materials that are prepared by coating gelatin-containing photographic component layers on both sides of a photographic support and drying them, and which are used as sheet films. is included.

The support for the sheet film may be polyester containing an aromatic carboxylic acid ester, such as polyethylene terephthalate, copolyethylene terephthalate-butylene terephthalate, poly 1,4-cyclohexylene dimethylene terephthalate, or copolyethylene terephthalate-1,4-cyclohexyl terephthalate. Silenedi〆ethylene terephthalate, polyethylene 2,6 naphthalate, copolyethylene terephthalate-ethylene 2,6 naphthalate; cellulose
Examples of lower fatty acid esters include cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate; polystyrene; polyolefin: polypropylene, polyethylene-polypropylene mixture; polycarbonate, and the like. The support may contain conventional photographic additives, such as plasticizers, dyes, white inorganic pigments, and the like. The sheet film may be any type of photographic film as long as it has the above-mentioned support, such as a film for printing plates, a film for X-ray photography, a film for still photography, a film for aerial photography, a film for copying, a film for duplication. The present invention is applicable to all color and black and white films. The following examples are given to illustrate the invention.

Example 1 '11 An X-ray photographic emulsion was coated on both sides of a polyethylene terephthalate support that had been undercoated on both sides and had been stretched and heat-set in a 180mm diameter, and then dried to produce a film with a diameter of 105mm.

This film was cut into 254 legs x 305 sides in air conditioned to a relative humidity of 45% and a dry bulb temperature of 2°C.
q Align the sheets of sheet film in step 5 from the top and bottom using thick cardboard (the humidity has been adjusted to the above conditions).
), the bag was inserted into a barrier bag made of polyethylene on the inside and aluminum foil on the outside, and the mouth of the barrier bag was sealed with a heat sealer to seal and package the packaged sheet film. Next, the wrapped sheet film was heated to a dry bulb temperature of 50q.
The samples were stored flat for 4 days in a heat-treated box held at 0.000 C.
Thereafter, the sheet film [A] was taken out and cooled to room temperature (approximately 25° C.). '21 The same film as above was used in air at a relative humidity of 45% and a dry bulb temperature of 2 ○.
After cutting and packaging in the same manner as in step 1}, the sheet was flattened and stored in a heat treatment box maintained at a dry bulb temperature of 3 to 0 for 21 days. ] was obtained.

[3'] A sheet film [C] was obtained which was cut and packaged under the above conditions, flattened and left at room temperature (approximately 25° C.) for 100 days.

In addition, the degree of curling of the sheet film immediately after cutting and after 2 hours, that is, the curvature, is 5 and 3, respectively.
．． It was 5.

Take out the sheet film one by one from the middle of each heavy mirror sheet (approximately 2 g from the top) of each of the obtained sheet films [A], [B], and [C].
The sheet films were kept in a room adjusted to a relative humidity of 55%, and their curvatures were measured 24 hours later.

The above measurement results are as shown in Table 1 below, and the sheet films [A] and [B] according to the method of the present invention have almost no curls remaining after processing, and are substantially flat and extremely flat. It turns out that it has become.

Furthermore, when these sheet films were subjected to a transport test of 100 sheets using an automatic X-ray imaging device, sheet films [A] and [B]
All 0 sheets could be transported without any trouble, but [C] had a trouble at the 15th crosscut and was defective in transport. Table-1 Example 2 The X-ray photographic sheet film obtained in the same manner as in Example 1 was divided into 10q sets, and the humidity was conditioned for 2 days under the conditions shown in Table-2 and Table-13 below. I wrapped it up and got multiple bags.

Each packaging bag was the same as in Example 1. The packaging bags containing these 10 women were heat-treated under different conditions shown in Table 4 below, and then opened in an atmosphere of 23 qo and 55% RH. The curvature, presence of adhesion and deformation, photographic properties, presence of static marks, and whether or not the film could withstand use were investigated for five of the female sheet films. The results are shown in Table 5 below.
Shown below. Table-2 Table-3 Table-4 Table-4 Table-5 Note 1...Deformation of gelatin surface Note 2...Unmeasurable Note 3...
Desensitization Note 4...Definition example of fog ○△
Next, on the other side, a cyan-forming red-sensitive silver halide emulsion layer, a gelatin intermediate layer, a magenta-forming green-sensitive blue-sensitive halide emulsion layer, a gelatin intermediate layer, a yellow-forming blue-sensitive silver halide emulsion layer, and a gelatin protective layer are sequentially formed. It was coated and dried to produce a medium 1000 silver halide color negative film.

The curvature of this film after unwinding was 8. This film was divided into 6 parts in the length direction, and each 2 parts were heated at 23°C and 55% R.
A room adjusted to the conditions of H (room D), a room adjusted to the conditions of 15°C and 90% RH (room E), 3 is 0, 55% RH (room F)
They were each cut into 100 ribs x 125 sides, and after conditioning the humidity, they were sealed and packaged in a polyethylene-aluminum barrier bag as a set of 12 women.One portion of each was kept flat and heated for 40 days, and the other portion was heated. One portion was left flat in the package at room temperature (23 qo) for 30 days. Each sample was numbered as shown in Table 6 below. Table 6 Sheet film heat-treated at 40°C at 23°C, 55%
After cooling in a room under RH conditions, open the package and
The curvature of the sample that had been left for 30 days was measured, and the degree of adhesion failure between films (so-called sticking phenomenon) and deformation of the film surface was observed, and the degree of difficulty in inserting the sheet film was determined.

The results are shown in Table 7 below. Table 7 As is clear from Table 7, the sheet film obtained by the treatment method according to the present invention is almost flat and can be easily inserted into the sheet film sheath without problems of adhesion or deformation. was completed.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the change in curvature after the roll film is released, and FIG. 2 is a perspective view showing a piece of bent sheet film. Ne figure O 2 legs

Claims (1)

[Claims] 1. A silver halide photographic material having a photographic support coated with a silver halide emulsion layer on at least one side, gelatin-containing photographic component layers coated on both sides of the support, and wound into a roll. The sheets are cut into sheets, and the sheets are piled up in an atmosphere with a relative humidity of 20 to 80% in the psychrometric chart, a dry bulb temperature of 10 to 40°C, and a dew point temperature of 25°C or less, sealed and packaged, and 1. A heat treatment method for a silver halide photographic material, comprising heat treatment at 65° C. for 1 hour or more.