JP2001337428A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brownie film which prevents the increase of cost, the contamination of a processing solution and stain due to a residual color without deteriorating light leaking resistance. SOLUTION: The silver halide photographic sensitive material satisfies D950/D650>=0.65. The D950/D650 expresses the ratio of the transmission type spectral absorption density of the sensitive material in the undeveloped state at 950 nm to that at 650 nm. The sensitive material has 0.10 to <0.21 g/m2 coating weight of black colloidal silver. The transmission type spectral absorption density of the backing layer of the sensitive material in the undeveloped state at 450 nm is 0.5-1.0, that at 550 nm is 0.2-0.5 and that at 640 nm is 0.6-0.8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also referred to as a "light-sensitive material"), and more particularly, to a 120-type or 220-type roll-shaped photographic film (commonly called brownie film).

[0002]

2. Description of the Related Art A 120-type or 220-type roll-shaped photographic film is formed by winding a roll-shaped film together with a light-shielding paper (also referred to as a leader paper or a trailer paper) on a dedicated spool. Or not stored in the cartridge,
The light is shielded by the spool and light-shielding paper.

[0003] Since a 120-type or 220-type roll-shaped photographic film is slightly shielded from light by a spool and a light-shielding paper, improper handling may cause light leakage to cause a defect in a photographed image. In addition, light pulling (light piping) is likely to occur. In other words, the product is commonly called 12
Light having a backing layer of 0 (brownie), 220, 4 × 5 (cut), etc., causes light from gaps in the packaging material to support and hydrophilic in addition to light transmitted through the camera lens system. It was scattered in the colloid layer, giving a photosensitive area with an unclear boundary outside the range of the incident light beam, and impairing the function as a product.

In addition to such light piping, methods for preventing light scattering such as irradiation and halation are described in, for example, JP-A-58-76834. There is a technique of providing a layer containing a light scattering prevention dye between the layer and the support, and further including a dye or pigment which sufficiently absorbs refracted light and scattered light in a backing layer made of a hydrophilic colloid. Are known.

As dyes or pigments used therefor, oxonol dyes having a pyrazolone nucleus described in British Patent No. 506,385, US Pat. No. 3,247,1
Oxonol dye having a barbituric acid nucleus described in No. 27, hemioxonol dye described in British Patent No. 584,609, styryl dye described in U.S. Pat. No. 2,298,733, U.S. Pat. No. 2,493 No. 747 are known, and all of them are decolorized by sulfite contained in the developing solution or under alkaline conditions with the sulfite, for example, as described in British Patent No. 506,385. Things.

However, as a problem, if the dye concentration in the backing layer is increased to prevent light piping, the cost of the dye is increased, the dye flows out into the processing solution, and the processing solution is contaminated. And the like, because the photosensitive material itself remains or becomes contaminated due to the processing with the processing solution.

[0007] It is desired to reduce the amount of the dye, but when the amount of the dye is reduced, the light piping deteriorates.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a brownie film which prevents cost increase, treatment liquid contamination and residual color contamination without deteriorating light leakage.

[0009]

The above objects of the present invention have been attained by the following constitutions.

[0010] 1. At least one each on a transparent support
A silver halide photographic light-sensitive material having a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, and a backing layer on the other side. Before development, D950 / D650, which is the ratio of the transmission spectral absorption density at 950 nm to the transmission spectral absorption density at 650 nm, is 0.65 or more, and the coating amount of black colloidal silver is 0.10 0.
Less than 21 g / m ² , and the transmission spectral absorption density at 450 nm of the backing layer before development is 0.4 nm.
A silver halide having a transmission spectral absorption density at 5 to 1.0 and at 550 nm of 0.2 to 0.5 and a transmission spectral absorption density at 640 nm of 0.6 to 0.8. Photosensitive material.

2. At least one each on a transparent support
A silver halide photographic light-sensitive material having a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, and a backing layer on the other side. Before development, the D950 / D650 optical density ratio is 0.65 or more, the amount of black colloidal silver applied is 0.10 or more and less than 0.21 g / m ² , and the backing layer is developed. In the previous state, the transmission spectral absorption density at 450 nm is 0.15 or more and 0.25 or less and 550
The transmission spectral absorption density at 0.7 nm is 0.7 or more and 1.1 or less and the transmission spectral absorption density at 640 nm is 0.8
A silver halide photographic light-sensitive material having a ratio of at least 1.2.

3. At least one each on a transparent support
A silver halide photographic light-sensitive material having a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, and a backing layer on the other side. Before development, the D950 / D650 optical density ratio is 0.65 or more, the amount of black colloidal silver applied is 0.15 to 0.27 g / m ² , and the backing layer is And the transmission spectral absorption density at 450 nm is 0.13 or more and 0.2 or less and the transmission spectral absorption density at 550 nm is 0.2 or more and 0.5 or less and 6
A silver halide photographic material having a transmission spectral absorption density at 40 nm of 0.11 or more and 0.15 or less.

4. At least one each on a transparent support
A silver halide photographic light-sensitive material having a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, and a backing layer on the other side. Before development, the D950 / D650 optical density ratio is 0.65 or more, the amount of black colloidal silver applied is 0.15 to 0.27 g / m ² , and the backing layer is And the transmission spectral absorption density at 450 nm is 0.2 to 0.3 and the transmission spectral absorption density at 550 nm is 0.3 to 0.6 and 64.
Transmission spectral absorption concentration at 0 nm is 0.4 or more and 0.7
A silver halide photographic material characterized by the following.

5. 5. The silver halide photographic material as described in any one of the above items 1 to 4, wherein the D950 / D650 optical density ratio is 0.7 or more.

6. 5. The silver halide photographic material as described in any one of items 1 to 4, wherein the D950 / D650 optical density ratio is 0.8 or more.

[7] 7. The silver halide photographic light-sensitive material according to any one of the above items 1 to 6, wherein the black colloidal silver is a black colloidal silver having a molar extinction coefficient εAg (950) of 350 or more as defined by the following definition.

ΕAg (950) = D / f D: Spectral absorption density at 950 nm f: Silver coating amount per unit area (mol / m ² ) The present invention will be described in more detail below. There is a strong demand for silver halide photographic light-sensitive materials for photography to provide high image quality as well as high sensitivity. In recent years, the use of tabular silver halide having a high aspect ratio and its improvement have been achieved. Also, from the viewpoint of resource saving and cost reduction, it is required to reduce the amount of silver halide used.

However, in general, the higher the aspect ratio of silver halide grains and the lower the total silver coating amount of silver halide, the higher the parallel transmittance in the visible to infrared wavelength region. However, the automatic developing machine and splicer used in the process of developing the photographed photosensitive material cannot detect the infrared ray of the photosensitive material, and there are problems such as trouble in transporting the photosensitive material and replenishment of the developing solution. is there.

As a method for avoiding these problems, there is a method using black colloidal silver as disclosed in JP-A-11-233954. In the present invention, this method was used for the emulsion surface. Hereinafter, the method will be described in detail.

The D950 / D650 optical density ratio according to the present invention refers to the ratio of the transmission spectral absorption density at 950 nm to the transmission spectral absorption density at 650 nm in the state of a dried coating film before development. It can be determined by the following bleaching / fixing method.

That is, a transmission type spectral absorption density value D _650F at 650 nm and 950 nm of a sample which has been subjected to a fixing process (process after the fixing process in a C-41 color negative developing process manufactured by Eastman Kodak Co.) in a state where the photosensitive material has not been exposed. _950F , and then the light-sensitive material was bleached and fixed in an unexposed state (processes after the bleaching process in the C-41 color negative development process manufactured by Eastman Kodak Co.) at 650 nm and 950 nm. _Determine the absorption concentration values D _650BF and D _950BF ,
The D950 / D650 optical density ratio was determined by the following equation.

D950 / D650 = ( _{D950F-
D950BF} ) / ( _{D650F- D650BF} ) In the present invention, the D950 / D650 optical density ratio is 0.65 or more, preferably 0.7 or more, particularly preferably 0.8 or more and 2.0 or less. is there.

As the D950 / D650 optical density ratio according to the present invention, O.D. As a method for achieving an infrared detection property of at least 65, the use of a silver halide emulsion having a low aspect ratio and a high transmission density in the infrared region is described.
No. 211542, No. 6-11793, No. 9-2742
As described in No. 78 and the like, there are a method of increasing the spectral absorption concentration in the infrared region by a so-called infrared dye having an absorption in the infrared region, a method of using colloidal silver, and the like, among which colloidal silver is used. The method is most preferred.

As colloidal silver, yellow colloidal silver for yellow filters and black colloidal silver for antihalation are generally known. In the present invention, the use of black colloidal silver is advantageous for the present invention. Is preferred because it is efficiently performed. However, in the visible region (400 nm
In the case of colloidal silver (for example, brown gray) having no clear absorption maximum wavelength at about 700 nm), the same effect as that of the black colloidal silver can be obtained. Therefore, the black colloidal silver herein refers to a black colloidal silver usually used for antihalation and a colloidal silver which does not clearly have an absorption maximum wavelength in a visible region.

The black colloidal silver is added to the non-light-sensitive hydrophilic colloid layer between the support and the light-sensitive silver halide emulsion layer closest to the support. The amount of addition is a transmission spectral absorption density characteristic value including a transparent support, which is 0.5 to 1.0 or less, and a transmission spectral absorption density at 950 nm of from 0.5 to 1.0.
0.7 or more and 1.3 in transmission spectral absorption concentration at 0 nm
The transmission spectral absorption density at 950 nm is preferably 0.6 or more and 1.0 or less, and the transmission spectral absorption density at 650 nm is 0.8 or more and 1.2 or less.

The black colloidal silver is generally produced by reducing silver ions in an aqueous gelatin solution. In the present invention, the temperature of the aqueous gelatin solution during the reaction is preferably from 20 to 45 ° C. Is preferably performed at 25 to 45 ° C, more preferably 30 to 40 ° C. At temperatures outside this range, it is difficult to adjust the absorption characteristics of the black colloidal silver to the desired characteristics. Further, the pH of the aqueous gelatin solution at the time of the reaction must be in the range of 8 to 10, and more preferably 8.5 to 10. Similarly, if the pH is too low outside this range, the reduction reaction of the aqueous silver nitrate solution cannot be sufficiently promoted,
Conversely, if it is too high, the reduction reaction proceeds rapidly, and it becomes difficult to adjust the absorption characteristics of the black colloidal silver to the desired characteristics. Temperature and pH of gelatin aqueous solution during reduction reaction of silver nitrate aqueous solution
It is necessary that at least one of them is in the above range, but it is preferable that both values are in the above range.

In the step of preparing fine colloidal silver by reducing an aqueous silver nitrate solution, which is a method for producing black colloidal silver, a method of obtaining black colloidal silver as a final product by a single-step reaction is generally used. In the present invention, for the purpose of improving (stabilizing) the reproducibility of the absorption characteristics of the black colloidal silver or adjusting to the desired absorption characteristics, it is preferable to prepare the black colloidal silver in two steps. Specifically, the method includes a nucleation step of forming a black colloidal silver nucleus and a growth step of growing the nucleus.

According to the two-stage method for producing a black colloidal silver dispersion, it is possible to control the conditions such as temperature and pH in the black colloidal silver nucleation step and the growth step, and to select the kind of gelatin. It is possible to increase the value of the molar extinction coefficient εAg (950) of the colloidal silver, to obtain a preferable spectral absorption characteristic as a black colloidal silver dispersion, and to obtain a black colloidal silver having high storage stability. I can do it.

The black colloidal silver nucleus forming step is a step of forming black colloidal silver nuclei with a small amount of silver ions and a small amount of reducing agent. The black colloidal silver growing step includes a remaining large amount of silver ions and a large amount of reducing agent. Is added to the above-mentioned black colloidal silver nuclei by a double jet method or the like to grow new black nuclei with minimum generation of new nuclei.

In the step of treating the produced black colloidal silver, a desalting step is generally provided to remove excess water-soluble salts. In the desalting method, salts such as magnesium sulfate and a flocculant such as gelatin in which some or all of the amino groups in the gelatin are chemically modified are added, and the supernatant liquid is eliminated through one to plural times of flocculation and sedimentation. There is a method by so-called decantation, a method by so-called ultrafiltration to remove dissolved salts out of the system using a semipermeable membrane having a fine network structure, and the like. It can be applied as a desalination method.

In the present invention, after the desalting step, the black colloidal silver dispersion is cooled to 30 ° C. or lower to gel. The temperature of the cooling gelation is preferably from 0 to 2
The temperature is 5 ° C, particularly preferably 4 to 15 ° C. It has been found that the cooling gelation step increases the stability of the black colloidal silver dispersion. That is, it is important that the black colloidal silver dispersion formed in the aqueous gelatin sol is subjected to a cooling gelation once after the desalting step and then put to practical use. It has been found that when a coating solution is prepared and coated, the storage stability as a silver halide photographic light-sensitive material is slightly lowered.

In the desalted black colloidal silver gelatin sol, a considerable proportion of aggregated black colloidal silver is present. Aggregates are undesirable because they cause filter clogging in the subsequent manufacturing process and cause tailing failure on the coating film in the coating process, and can be reduced by mechanically dispersing the aggregates. However, in general, as the number of aggregates decreases and monodispersion progresses, the absorption characteristics become sharper, and the absorption becomes clearer in a specific wavelength range. In general, the absorption characteristics required for black colloidal silver for that purpose are to have broad absorption characteristics over a wide wavelength range from the ultraviolet to the near-infrared region, which is contrary to the above characteristics. Therefore, it is necessary to appropriately set the dispersion strength in the step of mechanically dispersing and adjust the particle size distribution of the black colloidal silver including the aggregation state. As a dispersion method, a method that can obtain a high collision pressure is preferable, and in the present invention, the Menton-Gaulin method is preferable. The pressure during dispersion was 10~500kg / cm ^2, preferably to set the pressure of the first stage pressure 20~80kg / cm ^{2, 2} stage to 200 to 450 kg / cm ^2. Further, in order to further improve the dispersibility, the above cycle may be performed a plurality of times.

In the present invention, when a silver halide photographic light-sensitive material is left to stand for one week in an atmosphere of 60 ° C. and 80% RH, the spectral absorption density at 950 nm is 9%.
The effect of the present invention is exhibited when the fluctuation from the spectral absorption concentration at 50 nm is within 10%, more preferably within 7%.

[0034] It can be said that εAg (950) is 3
It is achieved by a silver halide photographic light-sensitive material containing 50 or more of black colloidal silver dispersed in the specific gelatin. Conventional black colloidal silver is 60 ° C, 80%
950 nm when left for one week in an atmosphere of RH
Is greater than 10%, that is, the storage stability was poor, and the infrared detection device characteristics were insufficient.

As the gelatin of the non-photosensitive layer containing black colloidal silver of the present invention, the same gelatin as that of the colloidal silver dispersion is preferably used.

In addition, the method of producing black colloidal silver preferably used in the present invention is a method known in the art, for example, as described in US Pat. No. 2,688,601, by dissolving a soluble silver salt in a gelatin solution. Method for reduction with hydroquinone, German Patent 1,096,193
A method of reducing a sparingly soluble silver salt with hydrazine, a method of reducing silver with tannic acid as described in U.S. Pat. No. 2,921,914, and a method described in JP-A-5-134358. As described above, a method of forming silver particles by electroless plating or the like can be used. The method of adding the colloidal silver to the light-sensitive material is described in the above patent and British Patent No. 1,126,797.
Nos. 4,460,679 and 4,56.
No. 3,406, No. 3,333,960, and U.S. Defense Publication T900,010, and the like.

In the present invention, if a layer containing black colloidal silver is coated, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer have the same color sensitivity. It may be composed of two or more layers having different sensitivities, each having a high sensitivity layer, a medium sensitivity layer, and a low sensitivity layer.
It preferably has a layer structure.

In the present invention, examples of the dye used in the backing layer include dyes represented by the following general formulas [I] to [IV].

[0039]

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Wherein R _{1 to} R ₁₇ each represent a hydrogen atom or a substituent, provided that at least one selected from R _{1 to} R _3, at least one selected from R _{4 to} R ₇ , ₈
At least one selected from R ₁₁ to R ₁₁ and at least one selected from R _{12 to} R ₁₇ are a substituent having a sulfo group or a carboxyl group. The substituent has 1 to 5 carbon atoms.
Represents an alkyl group, a phenyl group or a naphthyl group. n,
m represents an integer of 0 to 2, respectively. Specific examples of the dyes represented by formulas [I] to [IV] are shown below, but are not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The dye represented by the general formula [I] belongs to compounds marketed under the trade name: Tartrazine (manufactured by Daiwa Kasei Co., Ltd.), and the dye represented by the general formula [II] is a special compound. The dyes represented by JP-A-51-10927 and the general formula [IV] can be synthesized with reference to German Patent No. 616,007, respectively.

When these dyes are used for the backing layer and the above-mentioned black colloidal silver is used for the antihalation layer of the emulsion layer, the effect of preventing light piping is improved despite the same total silver content. That is surprising.

In order to introduce the dye into the backing layer according to the present invention, the dye is prepared as an aqueous solution having a desired concentration, added to an aqueous solution of a hydrophilic colloid, and coated on a support by a known method (for example, dip coating, curtain coating, or the like). Wire bar coating, extrusion coating described in U.S. Pat. No. 2,681,294, and simultaneous multi-layer coating described in U.S. Pat. No. 2,761,418). Since the dye employed in the present invention has high solubility in water and compatibility with the hydrophilic colloid, the amount added is hardly restricted by the solubility or compatibility, but in order to obtain the effects of the present invention, The addition amount is preferably 0.01 to 1.0 g / m ² .

In the present invention, the silver halide emulsion is the same as Research Disclosure No. 308119 (hereinafter, referred to as
RD308119) can be used.

In the present invention, it is preferable to use a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization. As the chemical sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used. The photographic additive that can be used in the present invention is also RD308119 described above.
And RD17643, RD18716 and the like.

Various couplers can be used in the present invention, and specific examples are also described in the above-mentioned Research Disclosure.

The additive used in the present invention is RD3081
RD17643, p. 28, RD18.
The supports described in pages 716, 647-8 and RD308119, XIX can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the paragraph 19VII-K can be provided, and various layer configurations such as a normal layer, a reverse layer, and a unit configuration can be adopted.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions.

The color light-sensitive material of the present invention comprises the above-mentioned RD1
Pages 28 and 29 of 7643, page 647 of RD18716 and page 615 of RD18716 Left to right columns, and RD30
The development can be performed by the usual method described in XIX of No. 8119.

[0057]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A 0.2 μm vinyl acetate-maleic anhydride copolymer (50:50) was applied on both sides, and 0.2 μm was applied on the outside.
A 101 μm backing layer of a 100 μm triacetate cellulose support provided with an undercoat layer coated with a coating solution made of gelatin and a crosslinking agent was prepared to prepare Sample 101.

Backing layer First layer Gelatin 4.0 g / m ² Dye I-1 95 mg / m ² Dye II-1 40 mg / m ² Dye IV-1 60 mg / m ² Polyacrylic acid (weight average molecular weight = 100,000) 800 mg / m ² Second layer Gelatin 3.5 g / m ² Dye I-1 95 mg / m ² Dye II-1 40 mg / m ² Dye IV-1 60 mg / m ² Polyacrylic acid (weight average molecular weight = 100,000) 1200 mg / M ² third layer gelatin 1.5 g / m ² alkali-soluble matting agent (average particle size 2 μm) 60 mg / m ² polymethyl methacrylate particles (average particle size 3 μm) 24 mg / m ² SU-3 2 mg / m ² SU -4 mg / m ² Each layer contains gelatin hardeners H-1 and H- in addition to the above composition.
2. Coating aid SU-1, viscosity adjuster V-1, preservative DI
-1 was added.

[0060]

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Next, by changing the amount of dye added to the first and second layers, 450 nm, 550 nm,
Samples 102 to 11 were prepared in the same manner as Sample 101, except that the transmission spectral absorption concentration in nm was changed as shown in Table 1.
2 was produced.

Preparation of Black Colloidal Silver A Pure water 5 was placed in a 2 liter container capable of controlling the temperature with a stirrer.
Add 4 ml, stir at about 500 rpm, and dissolve 2.0 g of dextrin therein. Further, a solution prepared by dissolving 0.35 g of sodium hydroxide in 5.3 ml of pure water is added, and the temperature in the vessel is adjusted to 37 ° C. When the temperature reached 37 ° C., 0.58 mol / l silver nitrate aqueous solution was added to 1
Add 0.5 ml. After 10 minutes, cooling is started. When the temperature in the container reaches 23 ° C., 370 ml of a 3.5% gelatin aqueous solution is added.

One minute later, a solution prepared by dissolving 0.053 mol of hydrazine sulfate in 270 ml of pure water is added. After one minute, 153 ml of a 1.2 mol / liter aqueous silver nitrate solution is added. Twenty minutes after the addition of the aqueous silver nitrate solution, 41 ml of a 15% by mass aqueous ammonia solution is slowly added over two minutes. Thereafter, desalting was performed by decantation using Demol and magnesium sulfate, and an aqueous gelatin solution was added to finally obtain 970 g of black colloidal silver A containing 8% gelatin. Here, the gelatin in the aqueous gelatin solution has a maximum value of the average molecular weight of about 150,000. Colloidal silver molar extinction coefficient εAg of black colloidal silver A (950)
Was 340.

Preparation of Black Colloidal Silver B The same addition and temperature control pattern as that of black colloidal silver A was used, but the amounts of hydrazine sulfate and aqueous ammonia were increased by 15%. Further, the gelatin in the aqueous gelatin solution was changed to gelatin having a maximum average molecular weight of about 70,000. The colloidal silver molar extinction coefficient εAg of the obtained black colloidal silver B (95
0) was 362.

Preparation of Multilayer Color Photosensitive Material Sample On the opposite side of the backing layer of the support of Sample 101 prepared above, a multilayer color photographic image forming layer (photosensitive layer) composed of layers having the following compositions ) To prepare a silver halide photographic material sample 101. Next, except that the amount of the black colloidal silver A of the first layer (antihalation layer) was changed as shown in Table 1, on the opposite side of the backing layer of the support of Samples 102 to 112 prepared above. Similarly to the photosensitive side of 101, samples 102 to 11
The photosensitive side was applied to No. 2 to prepare Samples 102 to 112. The coating amount of each component is shown in g / m ² . However, with respect to silver halide, it is indicated by a coating amount converted to silver. First layer (antihalation layer) Black colloidal silver A 0.24 UV absorber U-1 0.14 Gelatin 2.20 Second layer (intermediate layer-1) Gelatin 0.55 Third layer (low-sensitivity red-sensitive Silver halide emulsion layer) AgBrI spectrally sensitized by red sensitizing dyes (S-1, S-2, S-3) (AgI 4.0 mol%, average particle size 0.22 μm) 0.30 Coupler C -1 0.15 High boiling point solvent O-1 0.225 Gelatin 0.70 4th layer (Medium-speed red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1, S-2, S-3) AgBrI (AgI 3.2 mol%, average particle size 0.38 μm) 0.25 Coupler C-1 0.15 High boiling solvent O-1 0.225 Gelatin 0.70 Fifth layer (high Red sensitive silver halide emulsion layer) Red sensitizing dye (S AgBrI (AgI 2.5 mol%, average particle size 0.60 μm) 0.76 Coupler C-1 0.80 High boiling point solvent O-1 spectrally sensitized by 1,1,2,3) 20 Gelatin 2.25 6th layer (Intermediate layer-2) Compound SC-1 0.10 High boiling point solvent O-1 0.20 Gelatin 1.28 7th layer (Low sensitivity green photosensitive silver halide emulsion layer) Green AgBrI (3.5 mol% AgI, average particle size 0.22 μm) spectrally sensitized by sensitizing dyes (S-4, S-5, S-6) 0.30 Coupler M-1 0.11 Coupler M -2 0.03 High boiling point solvent O-1 0.125 Gelatin 0.75 Eighth layer (Medium speed green light sensitive silver halide emulsion layer) Green sensitizing dye (S-4, S-5, S-6) AgBrI (AgI 3.0 mol%, average particle size 0.1%) spectrally sensitized by 8 μm) 0.25 Coupler M-1 0.11 Coupler M-2 0.03 High boiling point solvent O-1 0.125 Gelatin 0.75 9th layer (high-sensitivity green-sensitive silver halide emulsion layer) Green sensitization AgBrI (AgI 2.5 mol%, average particle size 0.60 μm) spectrally sensitized by the dyes (S-4, S-5, S-6) 0.80 Coupler M-1 0.75 Coupler M-2 0.16 High boiling solvent O-1 0.80 Gelatin 2.40 10th layer (intermediate layer-3) Compound SC-1 0.10 High boiling solvent O-1 0.20 Gelatin 1.00 11th layer (Yellow Filter layer) Yellow colloidal silver 0.15 Compound SC-1 0.10 High boiling point solvent O-1 0.20 Gelatin 1.00 12th layer (Low-sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S -7, S-8) AgBrI felt (AgI 2.5 mol%, average particle size 0.30 μm) 0.30 Coupler Y-1 0.45 High boiling solvent O-1 0.20 Gelatin 0.70 Layer 13 (Medium sensitivity blue light sensitive) Silver halide emulsion layer) AgBrI (AgI 2.5 mol%, average particle size 0.45 μm) spectrally sensitized by a blue sensitizing dye (S-7, S-8) 0.30 Coupler Y-10 .45 high boiling point solvent O-1 0.20 gelatin 0.70 14th layer (high-sensitivity blue-sensitive silver halide emulsion layer) AgBrI spectrally sensitized by a blue sensitizing dye (S-7, S-8) (AgI 2.5 mol%, average particle size 0.90 μm) 0.75 Coupler Y-1 2.30 High boiling point solvent O-1 1.00 Gelatin 2.25 15th layer (first protective layer) UV absorber U-1 0.30 UV absorber U-20 .40 2,5-di-t-octylhydroquinone 0.10 High boiling point solvent O-1 0.20 Gelatin 1.30 Sixteenth layer (second protective layer) Average grain size 0.08 μm, silver iodide 1 mol% Non-photosensitive fine grain silver halide emulsion composed of silver iodobromide containing 0.30 polymethyl methacrylate grains (diameter 3.0 μm) 0.03 gelatin 1.00 In addition to the above composition, a gelatin hardener is used in each layer. H-
1, H-2, preservative DI-I, ST-1, AF-1, A
F-2 and AF-3 were added. Su-2 was used as a dispersing aid for the coupler.

The silver halide emulsion used for each photosensitive layer was prepared by referring to the method of Example 1 in JP-A-59-178847. Each was a monodisperse emulsion having a distribution width of 20% or less.

Each of the emulsions was desalted and washed with water, and then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-methyl-1, 3,3a, 7-Tetrazaindene, 1-phenyl-5-mercaptotetrazole were added.

The structural formula of the composition used in the above sample is as follows.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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Sample 201 shown in Table 1 was prepared in the same manner as in Samples 101 to 112 except that the black colloidal silver A of the first layer (antihalation layer) was changed to black colloidal silver B.
To 212 were produced. The following measurements were performed on the above photosensitive materials.

Evaluation method Light piping The emulsion surface and the backing layer surface of each sample were devised so as to be completely shielded from light, and the illuminance of 7000 Lux and 1
20,000 Lux daylight was applied for 20 minutes. Thereafter, the following development reversal process was performed, and the length of a portion (fog) that did not develop color due to light irradiation from the cross section of the sample was measured. The shorter the fog length (mm), the better the light piping prevention effect.

Backing layer Decolorization of dye The sample was placed in an environment of 40 ° C. and 80% RH for 1 day, then 55%
C., 60% RH for 3 days, and after the following development processing, the silver halide emulsion coated on one side of the support was chemically removed to remove the dye coloring property of the backing layer itself ( Or contamination), and five sheets were visually evaluated.

○ None △ Weakly generated × Generated Processing solution contamination 5 m ² of each sample was immersed in the first developer for 6 minutes, and the sample was taken out. After the first developer was left at room temperature for 2 hours, turbidity and coloring of the first developer were visually observed.

The results are shown in Table 2 below. Developing process Step Processing time Processing temperature First development 6 minutes 38 ° C. Rinse 3 minutes 38 ° C. Inversion 3 minutes 38 ° C. Color development 6 minutes 38 ° C. Adjustment 3 minutes 38 ° C. Bleaching 6 minutes 38 ° C. Fixed 3 minutes 38 ° C water washing 6 minutes 38 ° C stable 3 minutes room temperature drying The composition of the processing solution used in the above processing step is as follows.

First developer solution Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to make up to 1000 ml (pH 9.60).

Inversion liquid Nitrilotrimethylene phosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to make up to 1000 ml (pH 5.5). 75).

Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl -N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 ml (pH 11.70).

Conditioner Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to adjust to 1000 ml (pH 6.15).

Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 ml (pH 5.56).

Fixer 80 g ammonium thiosulfate 5 g sodium sulfite 5 g sodium bisulfite 5 g Water was added to make up to 1000 ml (pH 6.60).

Stabilizer Liquid Formalin (37% by mass) 5 ml KONIDAX (manufactured by Konica Corporation) 5 ml Water was added to adjust to 1000 ml (pH 7.00).

[0086]

[Table 1]

[0087]

[Table 2]

From the above results, it is possible to prevent light piping by increasing the amount of the BC dye. However, in addition to the increase in the cost of the dye, problems such as contamination of the processing solution and coloring or remaining color of the BC layer have been raised. However, when the BC layer of the present invention adopts the spectral absorption mode, the problems of processing solution contamination and residual color can be avoided,
It can be seen that the essential prevention of light piping is not sufficient. However, when the black colloidal silver of the present invention was further combined with the BC layer absorption form of the present invention, all of these problems could be solved, and light piping could be efficiently prevented.

[0089]

According to the present invention, prevention of light piping of a brownie film can be achieved while solving all the problems of cost, residual color, and processing solution contamination.

Claims (7)

[Claims] 1. A transparent support having at least one photographic component layer comprising a red photosensitive layer, a green photosensitive layer, a blue photosensitive layer and a non-photosensitive layer, and a backing layer on the other side. D950 / D650, which is the ratio of the transmission spectral absorption density at 950 nm to the transmission spectral absorption density at 650 nm, of the silver halide photographic material before development of the photographic component layer is 0.65 or more. And the coating amount of black colloidal silver is 0.10 or more.
Less than 21 g / m ² , and the transmission spectral absorption density at 450 nm of the backing layer before development is 0.4 nm.
A silver halide having a transmission spectral absorption density at 5 to 1.0 and at 550 nm of 0.2 to 0.5 and a transmission spectral absorption density at 640 nm of 0.6 to 0.8. Photosensitive material. 2. A transparent support having, on a transparent support, at least one photographic component layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, and a backing layer on the other side. The silver halide photographic light-sensitive material has a D950 / D650 optical density ratio of 0.65 or more and a black colloidal silver coating amount of 0.10 to 0.21 g before development of the photographic component layer. / m is less than ^2, and transmission-type spectral absorption density and 0.15 to 0.25 550 the backing layer is at 450nm in a state before the development
The transmission spectral absorption density at 0.7 nm is 0.7 or more and 1.1 or less and the transmission spectral absorption density at 640 nm is 0.8
A silver halide photographic light-sensitive material having a ratio of at least 1.2. 3. A transparent support having at least one photographic component layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, and a backing layer on the other side. In the silver halide photographic light-sensitive material, the D950 / D650 optical density ratio is 0.65 or more before the development of the photographic component layer, and the coating amount of black colloidal silver is 0.15 to 0.27 g. / M ² , and when the backing layer is in a state before development, the transmission spectral absorption density at 450 nm is 0.13 or more and 0.2 or less, and the transmission spectral absorption density at 550 nm is 0.2 or more and 0.5 or less and 6
A silver halide photographic material having a transmission spectral absorption density at 40 nm of 0.11 or more and 0.15 or less. 4. A transparent support having at least one photographic component layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer, and a backing layer on the other side. In the silver halide photographic light-sensitive material, the D950 / D650 optical density ratio is 0.65 or more before the development of the photographic component layer, and the coating amount of black colloidal silver is 0.15 to 0.27 g. / M ² , and the backing layer has a transmission spectral absorption density at 450 nm of 0.2 to 0.3 and a transmission spectral absorption density at 550 nm of 0.3 to 0.6 at 550 nm before development. 64
Transmission spectral absorption concentration at 0 nm is 0.4 or more and 0.7
A silver halide photographic material characterized by the following. 5. The silver halide photographic material according to claim 1, wherein said D950 / D650 optical density ratio is 0.7 or more. 6. The silver halide photographic material according to claim 1, wherein said D950 / D650 optical density ratio is 0.8 or more. 7. The halogenation according to claim 1, wherein the black colloidal silver is a black colloidal silver having a molar extinction coefficient εAg (950) of 350 or more as defined by the following definition. Silver photographic photosensitive material. εAg (950) = D / f D: Spectral absorption concentration at 950 nm f: Silver coating amount per unit area (mol / m ² )