JP2903406B2 - Silver halide photographic light-sensitive material with small curvature and capable of rapid processing and processing method thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly, to a support having at least one silver halide emulsion layer on one side and the other side on the other side. And a silver halide photographic material having a backing layer.

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

[Conventional technology]

A light-sensitive material having a silver halide emulsion layer on one side of a support and a backing layer on the other side (hereinafter sometimes referred to as "one-sided light-sensitive material" as appropriate) does not have the same composition on each side. In addition, the photosensitive material is likely to bend. Although there are some inconveniences associated with the curving, for example, it is important that when transported by an automatic transporting apparatus, transport troubles are likely to occur.

Further, the degree of curvature (hereinafter, also appropriately referred to as “curl degree”) may vary depending on conditions. For example, when the temperature or humidity changes, the single-sided photosensitive material has various layer configurations on both sides, and thus exhibits various curves, and thus the curl degree varies. Variations in curl make it more difficult to counteract curvature.

On the other hand, silver halide photographic materials are desired to be capable of rapid processing. However, since a single-sided photosensitive material has a photosensitive emulsion layer formed on only one side, it is often necessary to increase the amount of silver on one side as compared with the case where a silver halide emulsion layer is formed on both sides. . In such a case, the amount of the hydrophilic colloid in the emulsion layer must be increased, so that the dryness of the photographic material during processing is deteriorated, which is disadvantageous for rapid processing.

In order to improve the drying property, it is preferable to reduce the amount of the hydrophilic colloid in the silver halide emulsion layer and to increase the hardening degree to reduce the water absorption of the emulsion layer. However, such means alone results in deterioration of photographic characteristics, for example, high fog, reduced graininess, and poor scratch resistance.

As described above, it is desired that the fluctuation of the curl degree of the photosensitive material with respect to the change in temperature and humidity is small. For this purpose, it is important to balance the film thickness of the backing layer and the emulsion layer. It is conceivable to achieve a balance by increasing the thickness, but when the backing layer is too thick, the water absorption increases, which causes poor drying. Therefore, it is against the demand for quick processing.

As described above, there has been a demand for a single-sided photosensitive material to prevent bending (and fluctuation in curl degree) and to perform rapid processing, but it is difficult to achieve both.

[Object of the invention]

The present invention solves the above-mentioned problems of the prior art, the curvature is small, and even when the curvature occurs, the variation in the curl degree with respect to the change in temperature or humidity is small, and the rapid processing suitability is good. It is an object of the present invention to provide a single-sided photosensitive material having excellent photographic characteristics such as sensitivity even when subjected to rapid processing, and a processing method therefor.

[Configuration of the invention]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, wherein the silver halide emulsion layer is The ratio T _E / T _B of the total dry film thickness T _E on the side having the film and the total dry film thickness T _B on the side having the backing layer is
0.8 or more and 1.5 or less, and the water absorption of the surface having the silver halide emulsion layer is 8.5 g / m ² or less, and the backing is determined based on the water absorption of the surface having the silver halide emulsion layer. This has been attained by a silver halide photographic material characterized in that the surface having the layer has a smaller water absorption.

With the above configuration, a single-sided photosensitive material having a small curvature and its fluctuation and suitable for rapid processing was obtained.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the above-mentioned light-sensitive material is processed under conditions corresponding to the following formula.

l ^0.75 × T = 50-124 0.7 <l <3.1 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the light-sensitive material passing through the above l (In seconds).

In another method of processing a silver halide photographic light-sensitive material of the present invention, the above light-sensitive material is processed by a roller transport type automatic developing machine under conditions corresponding to the following formula.

l ^0.75 x T = 50 to 124 0.7 <l <3.1 where l is the length (unit: m) from the core of the first roller at the insertion port of the roller-type automatic developing machine to the core of the last roller at the drying outlet. Here, T is the time (unit: seconds) required for the photosensitive material to pass through the above l.

 Hereinafter, the present invention will be described in more detail.

The silver halide photographic light-sensitive material of the present invention is a so-called single-sided light-sensitive material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side.

Light-sensitive material of the present invention, the total dry film thickness T _E of the side having the silver halide emulsion layer, the ratio T _E / T _B of the total dry film thickness T _B of the side having the backing layer, at least 0.8 1.5 or less.

In the present invention, the film thickness means a dry film thickness of the photographic constituent layer on each side, and is not an average thickness of a local convex portion such as a matting agent, but an average thickness.

That is, theoretically, the weight X ₁ [g / cm ² ]... Xn [g / cm ² ] of each additive contained per 1 cm ^{2 of} the photographic constituent layer is determined by the density of the substance (D ₁ [g / cm ² ]). ³ ] The quotient divided by Dn [g / cm ³ ]) can be used to calculate the film thickness occupied by the additive. Therefore, the total film thickness is obtained by the following equation.

In the case of actual measurement, it can be known by tomographic observation with a microscope or measurement with a micrometer.

The light-sensitive material of the present invention takes both the thickness T _E, is T _B, it is those satisfying the above condition.

Preferably, T _E / T _B is 1.1 or more and 1.3 or less.

The silver halide photographic light-sensitive material of the present invention has a water absorption of 8.5 [g / m ² ] or less on the side having the silver halide emulsion layer. Further, the water absorption of the surface having the backing layer is smaller than the water absorption of the surface having the silver halide emulsion layer.

Preferably, the water absorption of the side having the emulsion layer is 5.8
8.28.2 [g / m ² ]. Further, the water absorption of the surface having the backing layer is preferably 4.0 to 7.5 g / m ² .

In the present invention, the water absorption of the photosensitive material as a whole is 15
[G / m ² ] or less. More preferably,
It is preferably 13.5 [g / m ² ] or less.

In the present invention, the water absorption means the difference between the weight under the condition of water absorption and the dry weight. This is a value obtained under the following conditions.

That is, at a temperature of 20 ° C. to 26 ° C. and a relative humidity of 50 to 70%, Is used to develop the photosensitive material. However, in order to measure the amount of water brought into the drying section (water absorption), the drying section is removed, the dryer is not operated, and the wet weight is measured immediately after coming out of the squeezing section (within 10 seconds). Further, the dried material is dried at a temperature of 23 ° C. and a relative humidity of 55% for 5 hours, and the dry weight is measured. The difference between the wet weight and the dry weight is the water absorption. Specifically, it is obtained by the following method.

MG-SR film (manufactured by Konica Corporation) was processed continuously for 100 sheets in a bright room at a rate of 1 sheet every 7 seconds (the short side of the film is the processing direction), and similarly measured. The sample to be processed should be the same size, the same concentration, and processed at the same interval.
Wet weight was measured immediately after coming out of the squeeze rack. The water absorption according to the present invention is obtained by drying the same sample as described above, calculating the difference between the dry weight and the wet weight, and expressing the unit as the water absorption per 1 m ² .

The water absorption of the side having the emulsion layer (hereinafter, appropriately referred to as “emulsion side”) and the side having the backing layer (hereinafter, appropriately referred to as “back side”) is represented by the following equation. Desired.

That is, for each sample, three types of samples were prepared by dissolving and removing the emulsion surface only, the back surface only, and both surfaces with a proteinase-decomposing enzyme solution, and measuring the water absorption of each sample.

Here the water absorption of the sample water absorption amount leaving water absorption of the sample leaving only H _W emulsion surface water absorption of the sample leaving only H _E back surface only H _B support of the sample having the emulsion surface and the back surface When the weight of the B _W support and B _O, water absorption of the water absorption of the emulsion surface _{H W -H B -1/2 (B W} -B O) Batsuku plane H _W -H _E -1/2 ( B _W −B _O ).

Various technical means can be used to make the water absorption of each surface within the range of the present invention.For example, by adjusting the degree of hardening of the layer on each surface side, the desired water absorption can be obtained. Can be. Further, for example, by making the back surface harder than the emulsion surface, the water absorption of the back surface can be made smaller than that of the emulsion surface.

The amount of silver in the light-sensitive material of the present invention is preferably 3.5 [g / m ² ] or less. This is because rapid processing suitability can be further improved.

The silver halide emulsion used in the light-sensitive material of the present invention is preferably spectrally sensitized in terms of sensitivity. For example, ortho sensitization, panchromatic sensitization, and infrared spectral sensitization can be performed.

In addition, the general formula [I] described in JP-A-59-192242
And / or the infrared spectral sensitizing dyes represented by [II] and the spectral sensitizing dyes described in JP-A-63-56652, pages 325 and 326, are used as the light-sensitive material for laser printers. Application is also a preferred example.

The composition of the silver halide to be used is arbitrary, and any silver halide, such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloride, which are used in usual silver halide emulsions, is appropriately used. be able to. Preferably, silver iodobromide is used.

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

In one preferred embodiment, the average particle size is 0.1-1.0μ
m of silver iodobromide.

The average particle size in parentheses means the diameter of a spherical silver halide grain, or the average of the diameter when the projected image is converted to a circular image of the same area for a grain of any other shape. Ri, the particle size of each particle is ri, and the number is ni
Is defined by the following equation:

The backing layer in the light-sensitive material of the present invention preferably contains a water-soluble backing dye. In some cases, a water-insoluble dye described in JP-A-62-276539 may be added to adjust the color tone. If the performance is not necessary, the dye may not be used.

In the light-sensitive material of the present invention, the silver halide emulsion layer and the backing layer are formed on separate sides of the support, respectively. It is preferable to use a compliant support. Useful as flexible supports are films composed of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta paper or α-olefin. Paper or the like coated or laminated with a polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like. The support may be colored using a dye or content. It may be black for the purpose of shading.

The surface of these supports may be subjected to a subbing treatment to improve adhesion to a photographic emulsion layer or the like, as is generally performed. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

In the practice of the present invention, a photosensitive silver halide or the like can be dispersed in an appropriate binder to be present in a photographic component layer. Various hydrophilic colloids are used as the binder, and typically, gelatin is preferably used. As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, hydrolyzate of gelatin, oxygen-decomposed product, and gelatin derived from gelatin can also be used. Those made of synthetic polymers such as polyvinyl alcohol can also be used.

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

For the purpose of improving the physical properties of the coating film using a hydrophilic colloid as a binder, various film physical properties, if necessary,
For example, it is preferable to use a hardener. When a hardener is used, the amount of water absorption can be made a desired value by controlling the amount of addition as described above.

The light-sensitive material of the present invention may contain other optional additives, and these may be used in Research Disclosure.
Volume 176, No. 17643 (December 1978) and Volume 187, No. 18716
(November 1976), and the relevant locations are summarized in the following table.

Known photographic additives that can be used in preparing the emulsion of the light-sensitive material according to the present invention are also described in the above two Research Disclosures, and the portions described in the following table are shown.

Next, a preferred embodiment in which the light-sensitive material of the present invention is processed will be described.

L is the processing length when processing the photosensitive multi-material of the present invention.
Is preferably greater than 0.7 and less than 3.1 (unit: m). When l is 0.7 or less, each processing step becomes small, and the sensitivity may be reduced.When the apparatus is applied to an apparatus for transporting a roller-type photosensitive material, the number of rollers used becomes small, and the transportability is poor. May be.
On the other hand, when l is 3.1 or more, the transport speed becomes too high, and the film may be easily scratched.

The product of l ^0.75 and T is preferably 50 or more and 124 or less. If this value is less than 50, the sensitivity of the light-sensitive material may be reduced, or color remaining may become a problem. More preferably, the product of l ^0.75 and T is 76 or more.

On the other hand, if the product of l ^0.75 and T exceeds 124, the sensitivity may hardly increase, but the graininess of the photographic image may deteriorate or fog may start to increase.

According to the above-mentioned processing conditions, good results can be obtained in which the granularity is good while having high sensitivity, and in which poor fixing, poor washing, and poor drying hardly occur.

When processing using an automatic developing machine, it is preferable to use a roller-conveying automatic developing machine, in which case the number of all conveying rollers, the value obtained by dividing the processing length l by the number of rollers is in the range of 0.01 to 0.04. Is preferable. The time of each processing part is preferably in the following range.

Inserting + developing + migratory 25-40% Fixing + migratory 12-25% Washing + migratory 10-25% squeeze + drying 25-45% total 100% The roller used is 12mm-60mm
The length is preferably between 30 cm and 110 cm, and various materials can be used. For example, bakelite-based materials (which may include glass powder, metal powder, and plastic powder) in the areas of development, fixing, washing, and drying are used. And rubber (neoprene, isoprene, silicone rubber, etc.). It is preferable to use water-repellent and elastic silicon rubber or the like, or synthetic leather having a high water-absorbing property, "Kurarino" (manufactured by Kuraray Co., Ltd.) for the transition portion and the squeeze portion.

As the processing solution such as a developing solution and a fixing solution used in the processing, an appropriate one can be used depending on the photosensitive material.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. Naturally, the invention is not limited by the examples.

Example 1 Tabular silver iodobromide grains having an average grain diameter of 1.71 μm and an aspect ratio of about 16: 1 were prepared by the method described in Emulsion 3 (Example) of JP-A-58-113927. An emulsion was prepared. The grains account for at least 80% of the total projected area of the silver iodobromide grains. However, before desalting, 1000 mg per mol of silver halide of spectral sensitizing dyes A and B were added to the grains in a weight ratio of 200: 1.

When the spectral sensitizing dye was added, the pH was adjusted to 7.60. After 15 minutes, phenylcarbamylated gelatin was added, the pH was lowered with acetic acid, the mixture was aggregated, and the supernatant was removed.

Pure water was added to the thus obtained grains so that the volume per mole of silver halide grains was 500 ml, the mixture was heated to 52 ° C., and the spectral sensitizing dyes A and B were added in a weight ratio of 200: 1. , And 10 minutes later, 0.6 g of a copolymer of styrene and maleic anhydride is added, and 2 minutes later, ammonium thiocyanate is added per mole of silver. 2.6 × 10 ⁻³ mol, and appropriate amounts of chloroauric acid and hypo were added to initiate chemical ripening.

 At this time, pH 6.02 and silver potential were 49 mV.

15 minutes before the completion of chemical ripening (80 minutes after the start of chemical ripening), 300 mg of potassium iodide was added per mole of silver,
After 10 minutes, 10% (wt / Vol) acetic acid was added to lower the pH value to 5.6, and the pH value was maintained for 5 minutes, and then a 0.5% (wt / Vol) potassium hydroxide solution was added to raise the pH to 6.15. Then, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 4 × 10 ^-2 mol and lime-treated ossein gelatin to the amount described below, and the chemical ripening was completed. And a photographic emulsion coating was prepared.

The pH after preparation of the photographic emulsion coating solution was 6.30, and the silver potential was 85 mV.
(35 ° C.).

The photographic emulsion coating solution thus prepared was coated on one surface of a support to form a photographic emulsion layer. Here, a polyethylene terephthalate film having a thickness of 175 μm was used as a support.

The photographic emulsion layer was 3.2 g per side of the support in terms of silver.
It was coated to a 2.2 g / m ² as / m ² of gelatin weight. A protective layer was formed on the emulsion layer by using a protective layer solution described later. The protective layer was coated so that the amount of gelatin applied was 1.1 g / m ² . A backing layer is provided on the side opposite to the side having the emulsion layer, and is formed from a lower backing layer and an upper backing layer. That is, the backing layer described below has a backing lower layer of 3.
0 g / m ² , and the backing upper layer was 1.2 g / m ² at the speed of 80 m / min with two slide hopper coaters on both sides of polyethylene terephthalate base at the same time. Obtained.

The obtained sample is sandwiched between fluorescent intensifying screens KO-250 (Konica Corporation) and irradiated with X-rays at a tube voltage of 130 KVP and 20 mA for 0.05 seconds to obtain a penetrometer B type (aluminum steps, Konica). After the exposure through a medical device (manufactured by Medical Co., Ltd.), processing was performed in 45 seconds using a processing agent (developing solution and fixing solution) described later by a Konica automatic developing machine SRX-501 as described below.

Sample 1-9 is the film thickness T _E of the side all the emulsion layer 3.45
[mu] m, the thickness T _B of the side having the backing layer is 3.2 .mu.m, both the ratio T _E / T _B of was 1.078.

 The spectral sensitizing dyes used for sample preparation are as follows.

Additives used in the emulsion solution (silver halide photographic emulsion coating solution) are as follows. The amount of addition is shown in an amount per mole of silver halide.

The additives used in the protective layer solution are as follows. The amount of addition is indicated by the amount per coating solution.

In addition to the above additives, the following compounds (1)
(2) was added in the following amount per mol of silver halide.

That is, Compound (1) is dissolved in an oil composed of Compound (2) and dispersed in a hydrophilic colloid solution according to the method described in Example 1, (3) of JP-A-61-28545. Was added in such an amount that the above amount was added.

The coating liquid for providing the backing layer was prepared as follows.

<Backing layer> Further, the following hardener solution is added to the protective layer solution applied to the emulsion side and the backing upper layer solution applied to the backing layer side, and the water absorption of each layer is adjusted to the amount shown in Table 1. Sample 1 with different water absorption as shown in Table 1.
~ 9 were created.

The amount of water absorption on each side shown in Table 1 was measured by the method defined in the above “Detailed description of the invention”.

(Hardener solution) 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2% (hardener) 10 ml Formalin 35% (hardener) 0.6 ml Glyoxal aqueous solution 40% (hardener) Membrane agent) 1.5 ml of water was added to 50 ml of each sample, and the sensitivity was measured and the drying property was examined.

The sensitivity was converted into a relative sensitivity where the reciprocal of the X-ray dose giving a fogging density of sample No. 1 in Table 1 and a blackening density of 1.0 was set to 100. Dryability was in accordance with the criteria described below.

The processing conditions in the present embodiment are as follows.
That is, the photosensitive material as a sample has a processing length l = 1.95.
In (m), the processing time T was set to 45 (seconds). (L ^0.75 × T
= 74.26).

In this embodiment, a sample was prepared by using Konica Corporation's automatic developing machine.
Processing was performed using SRX-501. The temperature at the place where the automatic developing machine was installed was 25 ° C., and the relative humidity was 62%.

However, in evaluating the drying property, in order to confirm the practical drying property, the processing machine and the processing agent were performed under the same conditions as the sensitivity measurement described above.
The drying property of each sample was confirmed at a temperature of 25 ° C. and a relative humidity of 80.

The processing method, size, and exposure density of the sample were the same as in the case of the water absorption measurement described above.

 Drying was evaluated in five steps according to the following criteria.

Dryness evaluation criteria 1. Completely dry, sample is warm A 2. Completely dry, sample is cold B 3. Slightly wet (less than 1/3) C 4. Wet (2 D / 5 Wet (more than 2/2) E The above evaluation results are shown in Table 1. Evaluation of dryness,
Although it was necessary to check the degree of drying on each sample side, the conditions were the same as those for the above-mentioned water absorption measurement, but the evaluation results correlate with the case of processing in an automatic developing machine under normal conditions.

 The following developer and fixer were used.

<Developer> XD-SR 35 ℃ (SRX-501, XD-SR-S in the development tank
<Fixing solution> XF-SR 33 ° C, 63cc / replenish with 4 pieces <Rinse water> Tap water 18 ° C (3.0 / min supply) As can be seen from Table 1, the samples according to the invention are:
High sensitivity was obtained, and drying property was good. For example, a comparison between Sample 3 (the present invention) and Sample 9 (comparison) shows that excellent results can be obtained when the water absorption of the emulsion surface is within the range of the present invention.

The relative humidity of each sample was continuously changed from 20% to 80% at 23 ° C., and the degree of curl was confirmed. The sample according to the present invention showed good curl with little change and little change.

The melting point for water was 94 ° C. or higher for all of samples 1 to 9.

As regards the graininess, in Samples Nos. 4, 7, 8, and 9 in which the water absorption of the emulsion surface is larger than 8.5, the graininess tends to be improved as the water absorption becomes smaller.
In o.3,2,6,1,5, there was a tendency that the graininess was almost constant with good condition.

Example 2 Using the same emulsion, protective layer solution and backing layer as in Example 1, the coating amount of the emulsion solution and the lower layer of the backing layer and the amount of the hardener were changed during coating, and the emulsion surface side and the backing surface side were changed. In addition to adjusting the dry coating film thickness, the amount of the hardener solution of Example 1 was adjusted to change the degree of hardening, and samples 10 to 22 having different amounts of water absorption were adjusted.
Was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2. The evaluation of the change in the degree of curl was performed as follows.

Measurement of curl degree At a temperature of 23 ° C., the relative humidity was changed from 20% to 80%, and the degree of change in the curl degree during this period was observed.

A Little change B Little change C High change As shown in Table 2, the sample according to the present invention was excellent with high sensitivity and good drying property, with little fluctuation in curl degree.

[Effects of the Invention] As described above, according to the present invention, the effect of good drying property and suitable for rapid processing, small curvature and small fluctuation of the curl degree, and high sensitivity even in the case of rapid processing can be obtained. Have.

Continuation of the front page (56) References JP-A-63-151944 (JP, A) JP-A-63-25649 (JP, A) JP-A-63-23154 (JP, A) JP-A-60-61742 (JP, A) JP-A-61-138950 (JP, A) JP-A-58-93051 (JP, A) JP-A-61-129644 (JP, A) JP-B-40-1698 (JP, B1) JP-B Sho-A 45-32037 (JP, B1) Jiko 36-6547 (JP, Y1)

Claims (3)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a packing layer on the other side, wherein the side having the silver halide emulsion layer is provided. And the total dry film thickness T _E of
The ratio T _E / T of the total dry film thickness T _B of the side having the backing layer
_B is 0.8 or more and 1.5 or less, and the water absorption of the surface having the silver halide emulsion layer is
5.8 to 8.2 [g / m ² ], wherein the water absorption of the surface having the backing layer is smaller than the water absorption of the surface having the silver halide emulsion layer. Photosensitive material. 2. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to claim 1 under conditions corresponding to the following formula. l ^0.75 × T = 50-124 0.7 <l <3.1 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the light passing through the above l (In seconds). 3. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed by a roller transport type automatic developing machine under conditions corresponding to the following formula. l ^0.75 x T = 50 to 124 0.7 <l <3.1 where l is the length (unit: m) from the core of the first roller at the insertion port of the roller-type automatic developing machine to the core of the last roller at the drying outlet. Here, T is the time (unit: seconds) required for the photosensitive material to pass through the above l.