JPH02146032A - Silver halide photographic sensitive material having improved transportability and suitable characteristic for rapid processing - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material capable of processing rapidly by providing at least one packing layer contg. non- photosensitive silver halide particles to a side opposite to a substrate and processing the photographic sensitive material under a specified condition. CONSTITUTION:The silver halide photographic sensitive material is provided with at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer to one packing layer contg. non-photosensitive silver halide particles to another side of the substrate. The photographic sensitive material is processed under conditions defined by the formula I. In the formula I, l is a length of processing (unit: m) when the silver halide photographic sensitive material is processed; T is a time (unit: sec) required for passing the photographic sensitive material through a distance l. Thus, a silver halide photographic sensitive material having suitable characteristic for rapid processing and improved detectability and transportability is obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

The present invention can be used as a photosensitive material in various fields, such as an X-cotton photosensitive material and a photosensitive material for CR'r photography.

[Background of the invention]

Conventionally, in the field of silver halide photographic light-sensitive materials, materials with good suitability for rapid processing have been desired.

As a silver halide photographic light-sensitive material, a so-called single-sided light-sensitive material having a silver halide emulsion layer on only one side of a support and a backing layer on the other side is known. Recently, the demand for such devices has been rapidly increasing in the field of, for example, CRT imaging, and there is therefore a strong desire to speed up the processing even more than before.

Incidentally, a single-sided photosensitive material is sometimes constructed by coating one side of a support with as much silver as both sides of a double-sided photosensitive material. When such a large amount of silver exists on one side, when the processing is accelerated, so-called omission during the fixing processing becomes difficult, and a large amount of residual silver results. As a result,
Preservability may deteriorate, resulting in deterioration in the quality of images obtained through processing.

This problem can be solved by reducing the amount of silver on the emulsion side to prevent defective extraction.

However, when the amount of silver on the emulsion surface is reduced in this manner, the total amount of silver in the light-sensitive material is reduced, which may cause other problems.

A significant problem is that the reduced amount of silver makes it difficult to detect the photosensitive material.

For example, in CRT photography, an infrared sensor is used to detect the photosensitive material in the image. However, when the amount of silver is low,
It will no longer be detected by the sensor. If the sensor cannot detect it, it will be impossible to carry out any operations after detection, such as transporting the photosensitive material.

In order to solve such problems in detectability and transportability, it is of course possible to increase the amount of silver, but this would lead to problems such as defects in the above-mentioned fixed forms, which goes against the basic requirement of rapid processing.

One possibility is to adjust the sensor of the CRT camera, but this would take too much effort and is practically impossible. There is an idea to make the sensor of the CRT camera more sensitive, but this is not preferable because it increases the cost and increases malfunctions.

[Purpose of the invention]

The present invention solves the above problems, allows rapid processing even when made into a single-sided photosensitive material, and improves detectability and transportability even when embodied as a photosensitive material for CRT photography, for example, which is detected by a sensor. The object is to provide a good silver halide photographic light-sensitive material.

[Structure of the invention]

In order to achieve the above object, the silver halide photographic light-sensitive material of the present invention has at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on one side of the support. The structure is characterized in that it has at least one backing layer containing non-photosensitive silver halide grains on the other side of the body, and is processed under conditions corresponding to the following formula.

l'・''×T=50-130 0.7〈β〈4.0 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the length of the light-sensitive material This is the time (unit: seconds) required for the above l to pass through.

Further, the composition is characterized in that it is processed by a roller conveyance type automatic developing machine under conditions corresponding to the following formula.

10・75×T=50~130 0.7 < 1 < 4.0 However, l is the 10th - of the insertion opening of the roller conveyance type automatic developing machine.
The length from the core of the roller to the core of the final roller at the drying outlet (spray position: m), and '1' is the time (unit: seconds) required for the photosensitive material to pass through the above l.

The present invention will be explained below.

In the present invention, the term "banking layer" refers to a non-photosensitive hydrophilic colloid layer formed on the side opposite to the side having the silver halide emulsion layer.

The photosensitive material of the present invention has at least one backing layer containing non-photosensitive silver halide grains.

In the present invention, the non-photosensitive silver halide grains contained in the backing layer are preferably completely non-photosensitive, but may be substantially non-photosensitive.

Here, the term "substantially non-photosensitive" means such a degree of photosensitivity that even if it is exposed to light, it will not have a latent image that is blackened by development. The term "non-photosensitive" in the present invention includes such cases of substantially non-photosensitive.

Such non-photosensitive silver halide grains are not particularly limited in their halogen composition, and include, for example, silver bromide, silver chlorobromide,
Any of silver iodobromide and the like can be used. Silver bromide or silver iodobromide is preferably used, and when silver iodobromide is used, it is particularly preferable that it contains 1.5 mol % or more of iodine. These silver halide grains are preferably not subjected to chemical ripening.

When the non-photosensitive silver halide grains used in the present invention are expected to have the additional effect of reflecting or scattering light,
It is preferable that the particle size is 0.3 μm or more. Further, from the viewpoint of influence on photographic properties, the thickness is preferably 1.9 μm or less. Particularly preferred is a range of 0.5 to 1.7 μm. However, in the present invention, the particle size of the non-photosensitive silver halide grains is not necessarily an important issue.

(Particle size means the diameter when the particle is spherical, and the diameter when the projected image is converted into a circle with the same area when the particle is non-spherical.)

The amount of non-photosensitive silver halide contained in the banking layer is preferably from 3.0 to 20 mg/dm'', more preferably from 4.0 to 10 m/dIII2.

In the present invention, the non-photosensitive silver halide is contained in the banking layer, but if the backing layer is composed of two or more layers, it may be contained in any of the layers. Moreover, it may be added separately to each layer.

The backing layer may contain a water-soluble dye or the like, if necessary.

Next, the silver halide photographic material of the present invention has at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on one side of the support.

The composition of the silver halide used in the photosensitive silver halide emulsion layer is arbitrary, and examples of the silver halide include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloride. Any material commonly used can be used as appropriate. Preferably, silver iodobromide is used.

The crystal habit and grain size of the silver halide grains are also not limited and are arbitrary.

In one preferred embodiment, the average particle size is 0.1 to 1.
Silver iodobromide of 0 μm is used.

The average grain size (F) referred to here means the diameter in the case of spherical silver halide grains, or the average diameter when the projected image is converted into a circular image of the same area in the case of grains with other shapes. value, where the diameter of each individual particle is ri and the number of particles is ni
, t is defined by the following formula.

Σni ri Σni Wavelength range to which the photosensitive silver halide emulsion layer is sensitive (photosensitivity)
is also optional. For example, arbitrary spectral sensitization can be performed using an appropriate spectral sensitizing dye or the like.

In the light-sensitive material of the present invention, the amount of silver on the side where the photosensitive silver halide emulsion layer is formed is preferably 37II1 g/dm2 or less, more preferably 35 mg/dl.
l+2 or less, more preferably 34 mg/dm" or less.

The side of the support having the photosensitive silver halide emulsion layer has at least one hydrophilic colloid layer separate from the emulsion layer. This hydrophilic colloid layer may be a separate emulsion layer or a non-photosensitive layer (eg, a protective layer, an interlayer, or any other layer).

Various hydrophilic colloids are used as the hydrophilic colloid used in the hydrophilic colloid layer and as a binder used in the photosensitive silver halide emulsion layer, but gelatin is typically preferably used. . As gelatin, in addition to lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin hydrolysates, enzymatically decomposed products, and other gelatin derivatives can be used. Materials made of synthetic polymers such as polyvinyl alcohol can also be used.

The same applies to the hydrophilic colloid used in the backing layer.

For the purpose of improving the physical properties of a film containing a hydrophilic colloid as a binder, it is preferable to use various film property improving agents, such as hardening agents, as necessary.

In the present invention, as the support used, it is preferable to use a transparent flexible support commonly used for photographic light-sensitive materials. Useful flexible supports include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
These include films made of semi-synthetic or synthetic polymers such as polycarbonate. The support may be colored using dyes or pigments.

The surface of these supports may be subjected to a subbing treatment, as is generally done, to improve adhesion to photographic emulsion layers and the like. The support surface is treated with corona discharge,
Ultraviolet irradiation, flame treatment, etc. may also be applied.

The photosensitive material of the present invention may contain other arbitrary additives, and these are listed in Research Disclosure 1.
768. Yang 17643 (December 1978) and 1
It is described in Volume 87, Itl 18716 (November 1976), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in preparing the emulsion of the light-sensitive material of the present invention are also described in the above two Research Disclosures, and the conditions under which the light-sensitive material of the present invention is processed will be described next.

The processing length l when processing the photosensitive material of the present invention is 0
．． The range is more than 7 and less than 4.0 (color: m). l
If it is less than 0.7, each processing step becomes smaller and the sensitivity may decrease. Also, if it is applied to a device that uses rollers to transport photosensitive materials, the number of rollers used will become smaller, resulting in poor transportability. may become worse. On the other hand, when p is 4.0 or higher, the conveyance speed becomes too high and the film may be easily scratched.

Further, the product of 1°·75 and T is 50 or more and 130 or less.

If this value is less than 50, the sensitivity of the photosensitive material may decrease, or residual color may become a problem. More preferably, the product of 10.15 and T is 76 or more.

On the other hand, if the product of β0.75 and T exceeds 130, the graininess of the photographic image may deteriorate and fog may become high, although the sensitivity hardly increases.

According to the above processing conditions, it is possible to obtain good results that have high sensitivity, good graininess, and are less prone to poor fixing, poor washing, and poor drying.

When processing using an automatic developing machine, it is preferable to use a roller conveyance type automatic developing machine, and in this case, the total number of conveyance rollers is such that the value obtained by dividing l, which is the processing section, by the number of rollers is 0.01 to 0. It is preferable that it be in the range of 0.04. Further, the time for each treatment site is preferably within the following range.

Inserter development + crossing 25-40% Fixing + crossing 12-25% Washer crossing 10-25% Squeeze + drying 25-45% The rollers used have a conveyor diameter of 12n~60mm and a length of 30cm. The length is preferably between 110 cm and 110 cm, and various materials can be used. For example, Bakelite-based materials (which may contain glass powder, metal powder, and plastic powder) or rubber-based materials are used for the developing, fixing, washing, and drying parts. (neoprene, isoprene, silicone rubber, etc.) can be used. It is preferable to use a water-repellent and elastic silicone rubber or the like, or highly water-absorbing synthetic leather under the trade name ``Tararolla'' (manufactured by Kuraray ■) for the transition and cross sections.

It should be noted that appropriate processing liquids such as a developer and a fixer can be used during processing depending on the photosensitive material.

〔Example〕

The present invention will be explained below using examples. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 Silver iodobromide monodispersion containing 2.0 mol% of silver iodide with an average grain size of 0.25 μm was prepared by double jet method at 60°C, pAg=s, o, and pH=2.0. I got a small pill. A portion of this emulsion was used as a core and grown as follows. i.e. contains core particles and gelatin? At 40°C, an ammoniacal silver nitrate solution and a solution containing potassium bromide and potassium iodide were added using a double jet method at 40°C, pAg = a, o, pH = 9.5, and silver iodide was added at 40 mol%.
A first coating layer was formed containing:

Note that the addition rate was gradually increased as the particles grew.

The resulting emulsion was an octahedral monodisperse emulsion with an average grain size of 0.27 μm. Using this emulsion grain as a core, the pA g
= 11.0 and pH = 9.0, ammoniacal silver nitrate solution and potassium bromide solution were added by double jet method to obtain a second solution.
A coating layer was formed. A semi-dispersed emulsion with an average grain size of 0.41 μm was obtained. The average silver iodide content of the resulting emulsion was 2.0 mol%.

The following sensitizing dyes (a) and (b) were added to the above emulsion, and after stirring for 10 minutes, thiocyanate was added at 3.4X 10-3 mol per mol of silver and the optimal star chlorauric acid. Hypo was added to perform chemical ripening, followed by addition of potassium iodide (1.3XlO-' mol/mol) and ripening for 15 minutes. Furthermore, so that the composition includes the additives described below,
A photosensitive silver halide emulsion coating solution was prepared.

(Sensitizing dye) (CL)nsOJa (CHz)3SO3 Amount added: 320 nw/A g A coating solution having the following composition was prepared as a coating solution for a backing layer phase to be formed on the side opposite to that on which the silver emulsion coating solution was applied.

In addition, the banking layer contains non-photosensitive silver halide grains, which are used in the backing layer used for each sample so that the grain size shown in Table 1 is in the amount shown in Table 1. The coating solution was prepared by incorporating it into a layered coating solution.

The non-photosensitive silver halide grains to be contained in the backing layer were prepared in the same manner as the photosensitive silver halide grains described above, except that the average grain size was as shown in Table 1. It was prepared so that the average silver iodide content was 2.0 mol%.

The compositions of the backing layer coating solution, the photosensitive emulsion layer coating solution, and the protective layer solution for forming the protective layer which is a hydrophilic colloid layer formed on the photosensitive emulsion layer side are shown below.

(Composition of coating solution for backing) (a) 60 g of lime-treated inert gelatin per lIl of coating solution (b)
) C3Hv CJtsCON-f-CHtellzO)2-←C)I
t-+5SOJag (C) (d) (e) (f) CsF+tSOJ(CJt) (C)lzcIh O
+DH (g) (h) (C) Silver halide grains (d) 0.6 mol (i) (j) N,N ethylene bis-(vinylsulfonylacetamide) (10%) 6-(k) Sodium chloride Ig (Emulsion coating liquid composition) Coating liquid IJ! Per (a) Lime-treated ossein gelatin 51g (b
) 5-Methyl-1,3,4,7a Tetrazainden-7-ol 0.8g (e) Nitron 0.05g (f) Styrene and butadiene copolymer fine particles (average particle size 0.03μ)
m) (g) Copolymer of styrene and maleic acid 2.5 g 1.5 g (h) 2,2-dihydroxymethylbutanol (protective layer liquid composition) 46 lime-treated inert gelatin ports per 11 coating solution, acid-treated gelatin 8 g \.

C3H? CtF+scO+CLC+I□0 )2-←CHz→-H5O3Na Ho.

NaO, 5 CH2COO(CH□) 9CH3 C) ICOO (C) If) tcH (CI+3) gg to C9F + 90 (Ctl□CH□0),. C
1l□C1l□0■1.5g Horse chestnut, C4F9S03K
1 g, 2-4-dichloro-6-hydroxy 1.3
．． 5-1-Ryazine sodium salt aqueous solution (2%)
5m/m/Nurmarine aqueous solution (3
5%)" 0,8 mZ, glyoxal aqueous solution (40% > 0.9aJ, sodium chloride 1g) Using the above coating solution, the emulsion layer was coated with a protective layer so that the amount of hydrophilic colloid was 2.2g/rrf. is 1.1g/m as gelatin amount
The backing layer was simultaneously coated on both sides of the polyethylene terephthalate film support using two slide hopper type coaters at a speed of 65 m/min so that the amount of hydrophilic colloid was 4.3 g/m. did.

This support consists of a 175 μm polyethylene terephthalate film, 50-t% glycidyl methacrylate,
A copolymer aqueous dispersion obtained by diluting a copolymer consisting of three monomers, 10 wt% methyl acrylate and 40-t% butyl methacrylate, to a concentration of 10-t% was used as a subbing liquid. It has been painted.

The amount of silver on the emulsion layer side (the amount of photosensitive silver halide grains coated) was adjusted to 33 mg/dmz.

A camera transport test was performed on the obtained sample. That is, using KIC-G (manufactured by Konica Corporation), 10 sheets of each sample were continuously transported, and the number of sheets that could be reliably transported was determined. The CRT camera used here has a pair of infrared light-emitting element and light-receiving element, and when the transported film passes between the elements, it sufficiently blocks infrared rays.
This is a mechanism for detecting the presence of film.

The results are shown in Table 1.

Separately, each sample was developed using an automatic developing machine shown in FIG. Processing time T-46 seconds, processing length 1 = 2.14m
And so.

In FIG. 1, 1 is the 10th roller at the photosensitive material insertion port, 2 is the final roller at the drying outlet, 3a is the developing tank, 3b is the fixing tank, 3
C is a washing tank, 4 is a photosensitive material to be processed, 5 is a squeeze section, 6 is a drying section, and 7 is a drying air outlet. Exposure and Processing Used Table 1 "a/10" indicates the number of films that were detected and could be transported without problems when a transport test was carried out for 10 consecutive films.

The axis o indicates a sample according to the present invention, and xtt indicates a comparative sample outside the present invention.

As is clear from Table 1, even with a small amount of photosensitive silver halide, the sample based on the structure of the present invention can detect and transport the film, which is problematic for CRT cameras. .

In addition, samples in which the non-photosensitive silver halide grains added to the backing layer of sample level 6 in Table 1 were mixed with the photosensitive silver halide in the emulsion layer and coated, and non-photosensitive silver halide grains and As a result of testing a sample coated with the same amount of photosensitive silver halide grains, the film could be detected without any problems, but in rapid processing like this example, the amount of residual silver was large and the image quality It was found that there was a problem with the storage stability of

Example 2 In a reaction vessel having a volume of 41, an aqueous gelatin solution (11 water, 20 g of alkali-treated gelatin, 3 g of potassium bromide, 1
Adjust pH to 9°0 with 10ml of normal KOH solution, pB
r 1.6), and while keeping the solution temperature at 52°C, add 150 ml of silver nitrate aqueous solution (containing 332.6 g of A g NO3) and 150 ml of halide aqueous solution (K B r
1B, 8 g and K I 16.37 g) at the same time for 5 minutes, flow rate: 30 mj? /min, then stirred for 3 minutes, and then the precipitant and 1N nitric acid solution were added.
The emulsion was precipitated at pH 4.0 and washed with water.

350 ml of the collected iif70 omz was used as a seed crystal emulsion, and an aqueous gelatin solution (11 water, 2 g of potassium bromide, 25 g of alkali-treated gelatin) was added thereto, the pH was adjusted to 9.0, and the temperature was raised to 65°C. After aging at 65°C for 20 minutes (silver potential -18mν), 300ml of silver nitrate aqueous solution
(containing 326 g of A g N) and 300 mj2 of an aqueous potassium bromide solution (containing 18.94 g of KB r) were added simultaneously over 25 minutes. After the addition, after stirring for 4 minutes, the pBr was adjusted to 2.3 with a silver nitrate solution of the same concentration, and N
Hz (25 int%) solution 2.0m7! , N Ha N
03 (50wt%) solution to 3.0+yj! In addition, 72 “
After raising the temperature to 30° C. and aging for 50 minutes, the temperature was lowered to 30° C., and the emulsion was washed with water and dispersed.

In this case, the gelatin concentration during nucleation is 2.0 wt%, the silver salt addition rate is 4.8X l O-''mol 7 min, the halide addition rate is 4.94X 10-''/min, and the pBr value was 1.6.

The characteristic values of the obtained emulsion were as shown below.

Average particle size: 0.56μm Average thickness
0.055μm average aspect ratio
Proportion of 1O12 tabular grains (projected area)
98.2% On the other hand, when X-ray diffraction of sampled emulsion grains was measured after nucleation and ripening, the (22
0) plane (X-ray diffraction profile is approximately 20 mol% A
It showed a homogeneous composition of gBrI.

Core size: 0.39μm core Al
The obtained emulsion having a l content of 20 mol % was subjected to chemical ripening in the same manner as in Example 1. However, the amount of sensitizing dye used was as shown below.

Sensitizing dye (a) -450 mg/AgX 1 mol Sensitizing dye (b) = 5.0 ■/Ag A coating solution was prepared and coated on both sides of a polyethylene terephthalate film support at the same time in the same manner as in Example 1.

The non-photosensitive silver halide grains used in the backing layer were the same as in Example 1. In addition, the grain size and coated silver star of the grains used are shown in Table 2 and refer to Table 1.1 = 2.74 Cm] As is clear from Figure 1 and Table 2, the above-mentioned photosensitive silver halide grains are Even in the system using tabular grains, good results similar to those of Example 1 were obtained for the sample based on the structure of the present invention.

Furthermore, the sample of Example 2 using tabular grains was exposed to high temperature,
There was little decrease in sensitivity when left under high humidity (45° C., 75% RH) for 3 days.

[Effects of the Invention] As described above, the silver halide photographic material of the present invention has the effects of being suitable for rapid processing, and having good detectability and transportability.

[Brief explanation of the drawing]

FIG. 1 is a configuration diagram showing an automatic developing machine used in Examples. 1... Tenth roller of photosensitive material insertion port 2... Final roller of drying outlet 3a... Developer tank, 3b... Fixing tank, 3C... Washing tank, 4... Photosensitive material, 5...
Squeeze part, 6...Drying part, 7...Dry air outlet. Procedural author's letter (spontaneous) 1. Indication of the case Patent Application No. 300267 of 1988 2. Name of the invention Silver halide photographic light-sensitive material with improved transportability and suitability for rapid processing 3. Person making the amendment relationship

Claims (1)

[Claims] 1. The support has at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on one side, and a non-photosensitive silver halide emulsion layer on the other side of the support. 1. A silver halide photographic material, characterized in that it has at least one backing layer containing silver halide grains, and is processed under conditions corresponding to the following formula. l^0^. ^7^5×T=50~130 0.7<l<4.0 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the length of the light-sensitive material This is the time (unit: seconds) required for the above l to pass through. 2. Having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on one side of the support, and containing non-photosensitive silver halide grains on the other side of the support. 1. A silver halide photographic light-sensitive material, which has at least one backing layer, and is processed in a roller conveyance type automatic developing machine under conditions corresponding to the following formula. l^0^. ^7^5×T=50~130 0.7<l<4.0 However, l is the length from the core of the first roller at the insertion port of the roller conveyance automatic developing machine to the core of the last roller at the drying outlet. (unit: m), and T is the time (unit: seconds) required for the photosensitive material to pass through the above l.