JPH0571083B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a method for producing photographic materials. More specifically, the present invention relates to a method for producing a photographic material by coating a photographic layer containing a specific hardening agent on a continuously running elongated support. (B) Prior art and its problems Usually, silver halide photographic materials are made of halogen-based materials coated on a support such as a film base such as cellulose ester, polyethylene terephthalate, or polystyrene, paper, waterproof paper, or synthetic paper. A silver oxide photographic emulsion layer, and if necessary an emulsion protective layer, a filter layer, an intermediate layer, an undercoat layer, an antihalation layer,
It is composed of auxiliary layers such as a bucking layer. Photographic materials such as image-receiving elements without a silver halide emulsion layer are also known in the diffusion transfer process. The layers constituting these photographic materials often mainly contain gelatin and/or gelatin derivatives. However, a layer containing gelatin and/or a gelatin derivative (hereinafter referred to as a gelatin-containing layer) is poor in abrasion resistance, dimensional stability, flexibility, and water resistance during photographic processing, and therefore constitutes a photographic light-sensitive material. In order to maintain a practical physical strength as an element, these layers require the use of various additives, including gelatin hardeners. A hardening agent for hardening the gelatin-containing layer is
Many are known. Among them, active halogen type hardeners are well known as a group of hardeners that have high hardness and are excellent. For example, various active halogen type hardeners and their usage are described in Japanese Patent Publication No. 39-16928,
Showa 43-2602, Showa 47-6151, Showa 47-33380,
13709, 1970, 3527, 1973, 3527, 1972,
31937, Showa 51-9434, Showa 51-78788, Showa 52-
60612, Showa 52-127229, Showa 54-15958, Showa 56
-27135 etc. However, the above-mentioned Special Publication No. 13709
51-9434, etc., the gelatin hardening speed of active halogen type hardeners cannot be said to be fast enough, and even after reaching saturated hardness, , it took a long time or required heating in a heating room for a certain period of time. However, it has been found that the maximum degree of hardening that can be obtained varies depending on the period of time between coating and heating the gelatin-containing layer containing an active halogen type hardener on the support. Ivy. This is thought to be because the active halogen hardener undergoes some kind of change and expires during the heating period, but since this change occurs in a relatively short period of time, the specified degree of hardening is always maintained. This poses a serious problem in that it cannot be obtained stably. Furthermore, when a long photographic material that is several thousand meters long is heated in a roll (usually called a mill roll), the time required to reach a predetermined temperature is different on the outside and inside of the roll, so one mill roll This results in photographic materials with different maximum degrees of hardness, which is still a serious drawback. (C) Object of the invention The object of the invention is to solve the above-mentioned drawbacks due to active halogen type hardeners, and to provide a photographic material having a uniform and highly hardened gelatin-containing layer over the entire length of the photographic material. An object of the present invention is to provide a method for producing a photographic material that can produce the material with good reproducibility. Another object of the present invention is to provide a method for producing a photographic material that can shorten the heating period, relax the heating conditions, or substantially eliminate the heating step. (D) Structure of the Invention The above object of the present invention is to provide a method for producing a photographic material in which a coating solution containing an active halogen type hardener is coated on a running support, dried, and rolled up. This was achieved by a method for producing a photographic material, which is characterized by winding the material in a heated state. The present invention will be further explained in detail below. As is well known, current photographic materials are
One or more photographic coating liquids are applied onto a moving support by various coating methods, such as a dip method, an air knife method, an extrusion method, a curtain method, etc., and after drying, it is wound around a core. Manufactured using Drying takes advantage of the sol/gelation phenomenon of gelatin, and immediately after it is applied to the support, it is solidified (so-called set) in a cooling zone.
After that, the temperature is gradually raised, and there is a material preheating period, a constant rate drying period in which the amount of solvent evaporation per unit time, that is, the evaporation rate of the solvent is constant, and a period where the evaporation rate of the solvent gradually decreases until almost no evaporation occurs. The process is completed after a lapse rate drying period (in which the coating film reaches an equilibrium moisture content under the temperature and humidity conditions of the outside air). usually,
The drying zone is set to have a maximum drying temperature of about 40°C to about 60°C. The photographic material leaving the drying zone is optionally conditioned and sent to a winding chamber where it is wound onto a core in a roll. Normally, the winding chamber is kept at room temperature (e.g.
It is air conditioned to constant conditions of normal humidity (e.g. 40-60% relative humidity) (15-25℃), and the photographic material sent here is cooled and wound at a temperature close to that of the winding room. was. The present invention is characterized in that the temperature of the photographic material is kept high during winding. In other words, by winding the photographic material in a heated state into a roll for several thousand meters, the photographic material in the mill roll is kept warm for a considerable length of time, so it takes longer to heat it than in the conventional method. There is no possibility that the active halogen type hardener will expire during the process, resulting in low hardness or inability to produce reproducible products, and it takes a considerable amount of time for the heat to reach the inside of the mill roll due to heating. A photographic material having a gelatin photographic layer with a uniform and high hardness over the entire length of the long photographic material, without the disadvantages of low hardness due to the hardness of the film or differences in maximum hardness depending on the location of the mill roll. is obtained. The outermost part of the mill roll is prone to heat dissipation, but with the heat dissipating from the inside, it can be kept warm for a relatively long time.Especially, if the mill roll is wrapped in an insulating packaging material immediately after winding, the outermost part can also be easily dissipated. It can keep you warm enough. If the mill roll photographic material produced according to the present invention is heated in a heating chamber at about 35°C to about 50°C for one day or several days, it will be perfect, but the mill roll will remain warm even without special heating. During this time, the active halogen type hardener undergoes a rapid curing reaction, making it possible to obtain a high degree of saturated hardening. Therefore, it has the advantage that a heating chamber is not required, the heating conditions can be relaxed, and the heating period can be shortened. One way to keep the photographic material in a heated state when it is wound onto a core is to raise the temperature from the drying zone to the winding chamber to a high temperature, for example, about 35°C or higher, to prevent the temperature of the photographic material after drying from dropping. Alternatively, heating means may be provided before the winder. The heating means may include blowing hot air, applying high frequency waves or ultrasonic waves, bringing it into contact with a heated roller, etc., as long as the internal temperature of the rolled photographic material can be preferably from about 35°C to about 50°C. The film temperature of the photographic material when it is rolled up is approximately 35
There is no need for the coating to be heated above ℃, and even if the film temperature is lower than that, warmed air can be brought in and rolled up, so the temperature after winding is approximately 35℃.
The coating film temperature can be increased to or above. One or more heating means may be provided, and heating may be performed from the coating side of the photographic material, from the support side, or from both sides. The heat capacity imparted to the photographic material depends on the application speed of the photographic material,
It varies depending on many other conditions. The active halogen type hardener used in the present invention is
It can be a known compound as described in the patent specifications mentioned above. A preferred active halogen type hardener is dichloro-
S-triazine, such as 2,4-dichloro-6-hydroxy-1,3,5-triazine (alkali metal salt), 2,4-dichloro-6-methoxy-1,3,5-triazine, 2, 4-dichloro-6-ethylamino-1,3,5-triazine,
Representative compounds include 2,4-dichloro-6-hydroxyethylamino-1,3,5-triazine. Active halogen type hardeners can be used in one or more photographic layers and can also be diffused into adjacent photographic layers. The amount used is generally about 0.005 to 5 mmol per gram of gelatin.
The addition time may be any time before the photographic coating liquid is applied. The addition method may be any known method. It may be combined with other hardeners, such as aldehyde type, activated olefin type, epoxide type, aziridine type, methylol type, etc. Hardening agents may also be used. of a gelatin-containing layer containing an active halogen type hardener.
The PH may be in any range, generally from about 3.5 to about 7. In addition to lime-processed gelatin, which is commonly used as gelatin in gelatin-containing compositions referred to in the present invention,
It can contain acid-treated gelatin, modified gelatin, and derivative gelatin, and can also contain water-soluble derivatives such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose, and starch, as well as polymeric substances such as latex. In addition to silver halide, there are various additives necessary to compose photographic materials, such as stabilizers, antifoggants, toning agents, spreading agents, photosensitive dyes, coating aids, matting agents, developing agents, and halation agents. In addition to anti-irradiation dyes and fixing agents for these dyes, physical development nuclei, color photographic materials, etc. can contain couplers, high boiling point oils, antioxidants, color staining and color mixing preventive agents, etc. . (E) Examples and Reference Examples The present invention will be specifically explained below with reference to Examples. Reference Example This Reference Example shows a model experimental example for understanding the present invention. Stabilizers, sensitizing dyes, surfactants and gelatin per gram of chemically sensitized silver halide emulsion,
Add 0.2 mmol of the sodium salt of 2,4-dichloro-6-hydroxy-S-triazine and adjust the pH
I adjusted it to 5.5 and finished it. This emulsion was coated on a polyethylene resin-coated paper support with 2 g/m ² of silver and 4 g/m of gelatin.
g/m ² , dried and cut into sheets. Immediately after cutting (sample A), aged for 8 hours at 20°C and 60% RH (sample B), and aged for 24 hours (sample C), each sample was incubated at 80°C for 1 day, 3 days and 7 It was heated for several days. These samples were immersed in a 2% sodium carbonate aqueous solution at 20°C for 10 minutes, and a ball point needle with a sphere diameter of 0.5 mm was placed on the emulsion film surface.
When the sample surface is moved in parallel at a speed of 1 cm/sec,
The load (g) of the ball point needle that caused damage to the gelatin film was measured. The results are shown in Table-1.

[Table] Sample A reaches saturated hardness in a short heating time, but Samples B and C reach saturated hardness more slowly, and the level is also low. I understand. That is, when a similar test is conducted on a mill roll sample, the phenomenon between the sheet-like samples A to C almost corresponds to the outermost sample. However, when heating a mill roll sample, it takes several hours to several tens of hours, or even several days, for the inner roll side to reach the temperature of the outermost roll, so the inner roll side and the outer roll side of the mill roll sample On the side, the above sample A ~
This means that a phenomenon similar to that between C and C occurs. Example 1 A gelatin (3 g/m ² ) subbing layer containing carbon black, hydroquinone, and phenidone and an ortho-sensitized silver chloride gelatin emulsion layer (2 g/m 2 silver) were prepared on a corona discharge treated polyethylene resin coated paper support.
m ² and gelatin (2 g/m ² ) were simultaneously coated in multiple layers using an extrusion method. The undercoat layer contains a formalin hardener, and the emulsion layer contains 0.1 mmol of 2,4-dichloro-6-hydroxy-S-triazine (Na salt) per gram of gelatin. After leaving the drying zone, the photographic coating is sent to a winding chamber and wound onto a core. It was applied over a length of 3000m. The surface temperature of the coating film when it is rolled up is
It was 22℃. Product A is obtained by immediately heating this mill roll in a heating chamber at 40° C., and Product B is obtained by heating it in the same manner after being rolled up at room temperature for 24 hours. On the other hand, a pair of heating rollers (metal rolls with an outer diameter of 260 mm made by pouring hot water inside to bring the temperature of the outer surface of the rollers to 70 to 95°C) is installed just before the winder, and the photographic coating material is passed between the pair of heating rollers. A photographic material was produced in the same manner as above except for winding. The surface temperature of the coating film when it was rolled up was 37°C. This mill roll is immediately heated in a heating room at 40℃ and is called Product C. After being rolled up, it is wrapped in a heat-insulating packaging material.
Product D is obtained by heating at room temperature for 24 hours and then heating under the same conditions as Product C. All of the products A to D were heated in the heating chamber for 7 days. The outer side (approximately 50 m from the end) and the inner side (approximately 50 m from the end) of products A to D heated in this way
The degree of hardness was measured according to the test method of the reference example. The results are shown in Table-2.

[Table] Product C and Product D according to the present invention exhibit a high degree of hardness, and can obtain a degree of hardness with almost no difference between the outer side and the inner side. Also, product A and product B
The fact that there is virtually no difference between Product C and Product D is due to the fact that the dura mater of Product D rapidly progresses over the course of 24 hours after being rolled up and reaches almost saturated hardness. I can understand. Example 2 0.2 mmol of 2,4-dichloro-6-hydroxy-S-triazine (Na salt) per gram of gelatin
A silver halide emulsion containing the above and a gelatin protective solution were coated on the support of Example 1 in a multilayer manner. The silver halide emulsion contains silver iodobromide containing 2 mol% silver iodide, 10% by weight polymer latex with respect to gelatin, stabilizers, surfactants, cyanine sensitizing dye, and contains 3 g/m ² of silver. The coverage of the protective liquid was 5 g/m ² of gelatin, and the coverage of the protective liquid was 0.8 g/m ² of gelatin. Using the heating roller pair of Example 1, the coated material was heated and wound up to a length of 3000 m. The surface temperature of the rolled coating film was 41°C. This mill roll is wrapped in heat-insulating packaging material and heated to 25°C.
After leaving it at room temperature for 3 days,
2% for samples at 1500m and 2500m
As a result of investigating the melting point in an aqueous sodium carbonate solution,
All samples had a temperature of 90°C or higher, and a very high degree of hardness was obtained in a short period of time without heating. Example 3 A gelatin back layer containing formalin was provided on the back side of a subbed polyester film, and then a matting agent, physical development nuclei, and gelatin (2.5 g/m ² ) were placed on the opposite side.
0.15 mmol/g of 2,4-dichloro-6-
A gelatin image-receiving layer containing hydroxy-S-triazine (Na salt) was coated, dried, and rolled up in the same manner as in Example 2 to produce an image-receiving material. Thereafter, as a result of following Example 2, similar results were obtained. (F) Effects of the Invention According to the method of the present invention, it is possible to obtain a uniform and highly hardened photographic layer over the entire length of a long photographic material using an active halogen type hardener, and It has now become possible to produce a photographic material that is extremely superior in industrial production, such as not requiring substantially any heating process.

Claims (1)

[Scope of Claims] 1. A method for producing a photographic material in which a coating solution containing an active halogen type hardener is applied onto a moving support, dried, and rolled up, wherein the photographic material is heated. A method for manufacturing a photographic material, which is characterized by winding. 2 The internal temperature of the rolled photographic material is approximately 35℃~
Claim 1: heating to about 50°C
Manufacturing method described in section.