JPH01257843A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the decolorability of a specified dye contained to prevent irradiation and halation in a photographic processing stage from deteriorating with the lapse of time by forming a layer contg. the dye at a side farther from a support than a polymer-contg. underlayer. CONSTITUTION:A layer contg. at least one of dyes represented by formulae I-V is formed at a side farther from a support than a polymer-contg. underlayer formed on polyolefin coated paper as the support. In the formulae I-V, Z is benzothiazole, naphthothiazole, etc., Q is pyrazolone, barbituric acid, etc., R is optionally substd. alkyl, each of R1-R4 is H, alkoxy, etc., R5 is H, etc., M is H, Na, etc., X is an anion, each of (m), (n) and n<2> is 1 or 2, each of R6-R9 is H, lower alkyl, etc., each of n<3>-n<5> is 0, 1 or 2, X1 is a bivalent org. group and n<6> is 0 or 1. The decolorability of the dye to be dissolved and removed in a photographic processing stage is prevented from deteriorating with the lapse of time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a silver halide photographic material. In particular, in photographic materials that are treated with dyes that are easily decolorized during photographic processing to prevent irradiation and radiation, and to improve safelight safety, the decolorization properties of the dyes after photographic processing deteriorate due to changes over time. This relates to a silver halide photographic material that does not have a silver halide.

■) Prior art and its problems In silver halide photographic light-sensitive materials, harmful reflections, scattering, diffused light, etc. are absorbed in the light-sensitive emulsion layer, or the interface between the emulsion layer and the support base and the support It is well known to prevent irradiation and halation and improve the sharpness of the finished photographic image by incorporating dyes that absorb unwanted reflected light from the backside of the base. It is also well known that dyes can be added to improve safelight safety.

The dye used for this purpose must satisfy the following conditions.

1) It must have appropriate spectral absorption characteristics according to the purpose of use.

2) It should not have an adverse effect on photographic properties, ie, it should not cause fogging or desensitization, etc.7.

3) It must be stable in water bath liquids and photosensitive materials, with no decrease in concentration or discoloration over time.

4) In the photographic processing process, the color must be completely and quickly decolorized or removed by dissolution, so that no harmful coloration remains on the photographic material after processing. Also, do not leave any coloring contamination on the processing solution.

Oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, etc. are known as dyes that satisfy these conditions and are often used in silver halide photographic light-sensitive materials.

On the other hand, polyolefin-coated paper supports have recently been widely used as supports for silver halide photographic materials. Compared to conventional baryta paper, processing liquid is hardly absorbed into the base paper, and it can be washed and dried in as short a time as film, reducing processing time, and can be completely washed with water. This is because of the advantages such as improved storage stability of images. However, among the above-mentioned dyes, dyes that are dissolved and removed during the photographic processing process do not pose a problem, but silver halide photographic materials containing dyes with excellent decolorization properties during the photographic processing process do not have this problem.
When polyolefin-coated paper is used as a support, this decolorization property is often impaired when stored for a long period of time, and coloring often remains after processing. There has not been a fully satisfactory silver halide photographic light-sensitive material that does not impair its decolorizing properties.

(C) Purpose of the Invention The purpose of the present invention is to provide halogenated dyes that do not deteriorate over time the decolorization properties of the dyes contained in the photographic processing process in order to prevent irradiation and halide and to improve the safety of safelights. Our objective is to provide silver photographic materials.

(6) Structure of the Invention The above object is to provide a polymer-containing subbing layer on a polyolefin-coated paper support, and to form the following general formulas (1) and (2) on the side remote from the subbing layer from the support. ), (3)
This was effectively achieved by providing at least one layer containing at least one dye represented by (4) or (5).

General formula (3) General formula (4) General formula (5) In the formula, 2 represents a nonmetallic atomic group necessary for forming a complex nucleus of benzthiazole, naphthothiazole or penzoxazole.

Q is pyrazolone, barbylic acid, thiobarbylic acid, inoxacilone, 3-oxythionaphthene or 1
, 3-indandione.

R represents a substituted or unsubstituted alkyl group.

R,, R1, Ra and R4 are hydrogen atoms, alkoxy groups,
dialkylamino group or sulfone group, R3 is a hydrogen atom or a halogen atom, M is a hydrogen atom, a sodium atom or a potassium atom, x+,'z anion, m, n and R2 are 1 or 2 atoms.

However, when m is 1, an inner salt is formed.

R6, Ry, R8 and Ro are a hydrogen atom, a substituted or unsubstituted lower alkyl group, an alkoxy group, an alkenyl group, a halogen atom, a nitro group, a cyano group, -(X)-so
, Mv is represented, and R3, R4, and R5 are 0.1 or 2.

Xl is a divalent organic group, and R6 is O or 1.

M represents a hydrogen atom or a cation.

Specific examples thereof are shown below, but the dye used in the present invention is not limited by kneading.

If s O, K So, H ('13) Can these dye addition chambers necessary to obtain appropriate spectral absorption characteristics be used in a wide range of types of silver halide photographic emulsions? Normally X■/Go~0.51//r
A range of t is preferred.

The silver halide photographic emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. prepared by a conventional method (silver halide, silver Sensitization, sulfur sensitization, reduction sensitization, a combination thereof, or addition of a polyalkylene oxide compound or the like may be performed.

The silver halide photographic emulsion of the present invention may be spectrally sensitized using a sensitizing dye, such as cyanine, merocyanine, etc., if necessary, and further stabilizers, surfactants, hardeners, etc. by known methods. It may contain additives such as.

When the silver halide photographic emulsion of the present invention is used in a light-sensitive material for color photography, it can contain color couplers and dispersants thereof. In addition to gelatin, heptathallated gelatin,
Gelatin derivatives such as malonized gelatin, cellulose derivatives, soluble starches, water-disintegrable polymers, etc., and plasticizers for dimensional stability, such as latex polymers, etc. can be used.

Examples of the base paper used for the polyolefin-coated paper of the present invention include natural pulp paper, synthetic pulp paper, and mixed paper of natural pulp and synthetic pulp, which are commonly used for photographic paper. can.

The base paper is usually used with a thickness of 50 to 300 microns.

Examples of the polyolefin forming the polyolefin resin coating layer include polyethylene, polypropylene, copolymers thereof, and mixtures of these various polymers. High density polyethylene, low V! Particularly often used are polyethylenes and mixtures thereof.

The thickness of the polyolefin resin coating layer is not particularly limited, but is preferably selected from a range of 10 to 50 microns.

It is common to use various additives such as white pigments, colored pigments, fluorescent whitening agents, and antioxidants to polyolefin resins.

The undercoat layer used in the present invention is formed by applying a polymer-containing aqueous solution to the surface of the polyolefin layer.

As the polymer, film-forming polymers such as gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble polymers, and latex polymers can be used, but gelatin is preferably used.

As the gelatin, any gelatin commonly used in the art, such as lime-treated gelatin, acid-treated gelatin, acid-accumulated gelatin, etc., can be used.

There is no particular restriction on the thickness of the undercoat layer, but preferably,
The coating amount after drying is 0.3 to 1.01/i. The polymer-containing water bath solution may contain various additives such as stabilizers, surfactants, and hardening agents. If desired, a small amount of anti-halation staining agent, coloring dye, pigment, etc. may also be included.

The subbing liquid can be applied by commonly known coating methods, such as day lag coating, air knife coating, curtain coating, extrusion wear coating, etc., and can be applied simultaneously with other coating layers. Also, after coating the subbing J- alone, other coating layers may be applied.

(g) Examples Hereinafter, examples will be shown to further specifically explain the present invention, but the present invention is not limited to this, and can be applied in various ways within the scope of the claims.

Example 1 A silver chloride emulsion prepared by a conventional silver halide photographic emulsion manufacturing method was subjected to a second ripening process using a sulfur sensitization method, and various stabilizers, coating aids, hardeners, etc. were added to form a coated emulsion. .

Further, a 5% gelatin/water/water liquid coating aid and a hardening agent Z were added to prepare a coating over solution.

On the other hand, 5% on photographic polyethylene waxed paper with a thickness of 100μ
A solution prepared by adding a surfactant to an aqueous gelatin solution is applied using the wire bar code method so that the gelatin coating amount after drying is 0.611/I, and dried at 80°C for 2 minutes to prepare a gelatin-subbed base paper.

Using such gelatin-subbed base paper and the above-mentioned photographic polyethylene-coated paper without gelatin subbing treatment as supports, exemplified dye (1) was added to the above-mentioned coating emulsion and coating over solution as shown in Table 1 to form an emulsion. Coated silver layer i1.8
#/Go, the amount of gelatin applied after drying the over layer is 1.5
Sample 7 was obtained by coating and drying to obtain a coating of 11/G.

This sample was developed for 90 seconds at 20°C using D-72 developer, stopped, and fixed for 90 seconds at 20°C using F-5 fixer χ.
I washed it with water.

The hue of this sample was determined using a Minolta CR121 color difference meter using the LS"% b'1 color system (C
IE1976(L*a*b*)-Color 5pac
Evaluate using the a* value and b* value of e).

A higher a- value indicates a walking direction, a lower b8 value indicates an edge direction, a higher b8 value indicates a buy direction, and a lower b8 value indicates a forward direction.

In addition, in order to check the storage stability of each sample, it was
After 6 days of forced heating, the same treatment was performed and evaluated.

The results are shown in Table 1.

Table 1 In this way, at g;, 4.5, the *a value of the sample after strong flflJ7JO temperature was higher than that immediately after application, and the decolorization by photographic processing of the exemplary dye (υ) was poor, leaving a reddish tinge. However, in the case of Invention 1.2, the t value after forced heating is the same as that immediately after application, indicating that the decolorization property does not deteriorate due to storage.

Example 2゜Exemplary dyes (1), (2),
(5), (7'), (8), (11), (12), (
16) was added as a 2029+ water bath solution per silver I11,
A hardening agent and a coating aid were added. This emulsion was coated with the same gelatin-subbed base paper as in Example 1 and photographic polyethylene-coated paper without gelatin subbing treatment, and the coated silver amount was 2.0117 d. The sample was coated using the wire barcode method and dried to obtain a sample.

This sample was developed using D-72 developer for 90 seconds at 20°C, stopped, and fixed using F-5 fixer for 90 seconds at 20°C.
I washed it with water.

This sample was manufactured by MACBE manufactured by Mac Pesco Boreshire, USA.
Concentration measurements were performed using a THTD-504 densitometer.

In addition, to check the storage stability of each sample, the temperature was 50°C, 80% RH.
After 6 days of forced heating, the same treatment was performed 7 times and evaluated.

The results are shown in Table 2.

Table 2 In the sample treated immediately after application, there is no difference in density with or without subbing, but after forced heating, the density is high without subbing, and the decolorization of the dye deteriorates, whereas in the present invention It can be seen that the density of the undercoat cloth is almost the same as that when treated immediately after application, and the decolorization property does not deteriorate due to storage, indicating that it has excellent storage stability.

Claims (1)

[Claims] (1) In a silver halide photographic material in which at least one silver halide emulsion layer is provided on a polyolefin-coated paper support, a polymer-containing subbing layer is provided on the polyolefin-coated paper support, and The following general formulas (1), (2),
A silver halide photographic material comprising at least one layer containing at least one dye represented by (3), (4) or (5). General formula (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (5) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z is a nonmetal necessary to form the heterocyclic nucleus of benzthiazole, naphthothiazole, or benzoxazole. Represents an atomic group.Q is pyrazolone, barbituric acid,
Represents the atomic group necessary to form thiobarbituric acid, isoxazolone, 3-oxythionaphthene or 1,3-indanedione. R represents a substituted or unsubstituted alkyl group. R_1, R_2, R_3 and R_4 are a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfone group, R
_5 is a hydrogen atom or a halogen atom, M is a hydrogen atom, sodium atom or potassium atom X is an anion, m, n
and n_2 represents 1 or 2. However, when m is 1, an inner salt is formed. R_6, R_7, R_8 and R_9 represent a hydrogen atom, a substituted or unsubstituted lower alkyl group, or an alkenyl group. R_1_0, R_1_1 and R_1_2 are substituted or unsubstituted lower alkyl groups, alkoxy groups, alkenyl groups, halogen atoms, nitro groups, cyano groups, -(X_1)_
Represents n_^_6-SO_3M, n_3, n_4, n
_5 is 0, 1, or 2. X_1 is a divalent organic group, and n_6 is 0 or 1. M represents a hydrogen atom or a cation. )