JPH0621934B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a silver halide photographic light-sensitive material. In particular, it is a photographic light-sensitive material that has been protected from irradiation and halation by a dye that is easily decolorized during photographic processing and has improved safelight safety, and silver halide that does not deteriorate the decolorization after dye processing due to aging. The present invention relates to a photographic light-sensitive material.

(B) Prior art and its problems In a silver halide photographic light-sensitive material, it absorbs harmful reflection, scattering, diffused light, etc. in the light-sensitive emulsion layer, or the emulsion layer and the support base boundary surface and the support. It is well known to include dyes that absorb unwanted reflected light from the back of the body base to prevent irradiation and halation and improve the sharpness of the finished photographic image. It is also well known to incorporate a dye in order to improve safety of safelight.

The dye used for this purpose needs to satisfy the following conditions.

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

2) Do not adversely affect the photographic characteristics, that is, do not give rise to fog or desensitization.

3) It is stable in an aqueous solution and in a light-sensitive material without any decrease in density or discoloration with time.

4) In the course of photographic processing, it must be completely and quickly decolorized or dissolved and removed so that no harmful coloring is left on the photographic light-sensitive material after processing. Also, do not leave stains on the processing liquid due to coloring.

Oxonol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes and the like are known as dyes satisfying these conditions, and are widely used in silver halide photographic light-sensitive materials.

On the other hand, in recent years, a polyolefin-coated paper support has been widely used as a support for silver halide photographic light-sensitive materials. Compared with conventional baryta paper, the processing liquid is hardly absorbed by the base paper, washing and drying can be done in a short time like a film, the processing time can be shortened, and the washing can be completed completely. Therefore, this is because of advantages such as improved storage of images. However, among the above dyes, a dye that is dissolved and removed in the photographic processing process does not pose a problem, but in a silver halide photographic light-sensitive material containing a dye excellent in decolorization in the photographic processing process, these polyolefin-coated papers are supported. When used as a body, this decolorizing property is impaired when it is stored for a long period of time, and coloring often remains after the treatment. There is no satisfactory silver halide photographic light-sensitive material that cannot be overlooked.

(C) Purpose of the invention The purpose of the present invention is to prevent irradiation and halation, halogenation without degrading the bleaching property of the dye contained in the photographic processing process for the purpose of improving safelight safety with the passage of time. It is to provide a silver photographic light-sensitive material.

(D) Structure of the Invention The above object is to provide a polymer-containing undercoat layer on a polyolefin-coated paper support, and the following general formula (1), (2) on the side farther from the support than the undercoat layer. ), (3), (4), (5)) is effectively achieved by providing at least one layer containing at least one of the dyes represented by

General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) In the formula, Z represents a nonmetallic atom group necessary for forming a heterocyclic nucleus of benzthiozole, naphthothiazole or benzoxazole.

Q is pyrazolone, barbituric acid, thiobarbituric acid, isoxazolone, 3-oxythionaphthene or
Represents the atomic group necessary to form 1,3-indandione.

R represents a substituted or unsubstituted alkyl group.

R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkoxy group,
Dialkylamino group or sulfone group, R ₅ is hydrogen atom or halogen atom, M is hydrogen atom, sodium atom or potassium atom, X is anion, m, n and n2 are 1
Or represents 2. However, when m is 1, an intramolecular 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 ₁₀ , R ₁₁ and R ₁₂ represent a substituted or unsubstituted lower alkyl group, an alkoxy group, an alkenyl group, a halogen atom, a nitro group, a cyano group, — (X) _n6 —SO ₃ M, and n3, n
4, n5 is 0, 1, or 2.

X ₁ is a divalent organic group, and n6 is 0 or 1.

M represents a hydrogen atom or a cation.

Specific examples are shown below, but the dyes used in the present invention are not limited thereby.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) The addition amount of these dyes required to obtain proper spectral absorption characteristics depends on the type of silver halide photographic emulsion, presence / absence of spectral sensitization, degree, purpose of use of silver halide photographic light-sensitive material, etc. m ² can be widely used in ~ 1 g / m ^2, but usually in the range of 1 mg / m ² to 0.5 g / m ² 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., which are produced by a conventional method. Sulfur sensitization, reduction sensitization, sensitization combining them, 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 by using a sensitizing dye such as cyanine or merocyanine if necessary, and further, a stabilizer, a surfactant or a hardener by a known method. Additives such as

When the silver halide photographic emulsion of the present invention is used in a color photographic light-sensitive material, it can contain a color coupler or a dispersant thereof. Further, as a protective colloid for silver halide photographic emulsions, in addition to gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, water-soluble polymers and the like, and plasticity for dimensional stability, for example, , A latex polymer, etc. can be added.

Examples of the base paper used for the polyolefin-coated paper of the present invention include natural pulp paper, synthetic pulp paper, mixed paper of natural pulp and synthetic pulp, which are generally used for photographic printing paper. it can. The base paper is usually 50-300
It is used with a thickness of micron.

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 density polyethylene and mixtures thereof are often used in particular.

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

It is common to add various additives such as a white pigment, a coloring pigment, a fluorescent whitening agent, and an antioxidant to a polyolefin resin.

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

As gelatin, any of those commonly used in the art such as lime-processed gelatin, acid-processed gelatin and oxygen-processed gelatin can be used.

The thickness of the undercoat layer is not particularly limited, but preferably,
The coating amount after drying is 0.3 to 1.0 g / m ² .

The polymer-containing aqueous solution may contain various additives such as stabilizers, surfactants and hardeners. Further, if desired, a small amount of an antihalation agent, a coloring dye, a pigment or the like may be contained.

The subbing liquid can be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, an extrusion-coating method, etc. Alternatively, the subbing layer alone may be applied and then another coating layer may be applied.

(E) Examples Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these, and various applications can be made within the scope of the claims.

Example 1. A silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion was subjected to a second ripening by a sulfur sensitization method, and a stabilizer, a coating aid and a hardener were added to prepare a coated emulsion.

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

On the other hand, 5% for 100 μm thick polyethylene coated paper for photography
A solution prepared by adding a surfactant to an aqueous gelatin solution is applied by a wire bar code method so that the amount of gelatin applied after drying is 0.6 g / m ^2, and dried at 80 ° C. for 2 minutes to prepare a gelatin-undercoated base paper.

Using such gelatin subbed base paper and the above-mentioned photographic polyethylene coated paper not subjected to gelatin subbing as a support, the dye (1) shown in Table 1 was added to the above coating emulsion and overcoat solution to prepare an emulsion. Layer coated silver amount 1.8g / m ² ,
A sample was obtained by coating so that the coating amount of gelatin on the over layer after drying was 1.5 g / m ² , and drying.

This sample was developed with D-72 developer at 20 ° C. for 90 seconds, stopped, and fixed with F-5 fixing solution at 20 ° C. for 90 seconds and further washed with water.

The hue of this sample was measured with a Minolta CR-121 color difference meter to obtain L ^* , a ^* , b ^* , color system [CIE1976 (L ^* , a ^* , b ^* )-Co.
Lor Space] a ^* value and b ^* value.

A higher a ^* indicates a red hue, a lower a ^* indicates a green hue, a higher b ^* value indicates a yellow hue, and a lower a ^* value indicates a blue hue.

In addition, in order to check the preservability of each sample, 50 ℃ 80% RH
After performing forced heating for 6 days, the same treatment was performed and evaluated.

The results are shown in Table 1.

As described above, in Nos. 4 and 5, the a ^* of the sample after the forced heating was higher than that immediately after coating, and the decolorization by the photographic process of Exemplified Dye (1) was poor and the reddishness remained. Invention No.
In Nos. 1 and 2, the a ^* value after forced heating was the same as that immediately after coating, and it was found that the decolorizing property did not deteriorate due to storage.

Example 2. The same coating emulsion as in Example 1 was prepared with the exemplified dyes (1), (2), (5), (7),
(8), (11), (12) and (16) were added as a 20 mg aqueous solution per 1 g of silver, and a hardener and a coating aid were added.

This emulsion was coated by the wire bar code method so that the coated silver amount was 2.0 g / m ^{2 using} the same gelatin-undercoated base paper as in Example 1 and photographic polyethylene-coated paper without gelatin sub-treatment as a support. Then, it was dried to obtain a sample.

This sample was developed with D-72 developer at 20 ° C. for 90 seconds, stopped, fixed with F-5 fixing solution at 20 ° C. for 90 seconds, and further washed with water.

This sample is a MACBETH TD manufactured by Macbeth Corporation in the United States.
The concentration was measured using a -504 densitometer.

In addition, in order to check the preservability of each sample, 50 ℃ 80% RH
After performing forced heating for 6 days, the same treatment was performed and evaluated.

The results are shown in Table 2.

Thus, in the sample treated immediately after coating, there is no difference in the concentration with or without subbing, but after forced heating, the concentration is high without subbing, and the decolorizing property of the dye is deteriorated. It can be seen that when the value is "Yes", the concentration is almost the same as that when the treatment is performed immediately after coating, and the decolorizing property is not deteriorated by the storage, and the storage property is excellent.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a polyolefin-coated paper support, and a polymer-containing undercoat layer is provided on the polyolefin-coated paper support. , And the following general formula (1), (2) on the side farther from the support than the undercoat layer,
A silver halide photographic light-sensitive material, comprising at least one layer containing at least one dye represented by (3), (4) or (5). General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) (In the formula, Z represents a group of non-metal atoms necessary for forming a heterocyclic nucleus of benzthiazole, naphthothiazole or benzoxazole. Q represents pyrazolone, barbituric acid,
Represents the atomic group necessary to form thiobarbituric acid, isoxazolone, 3-oxythionaphthene or 1,3-indandione. 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, a sodium atom or a potassium atom X is an anion, m, n ¹ and n ² represent 1 or 2. However, when m is 1, an intramolecular 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 ₁₀ , R ₁₁ and R ₁₂ represent a substituted or unsubstituted lower alkyl group, an alkoxy group, an alkenyl group, a halogen atom, a nitro group, a cyano group,-(X ₁ ) _{n 6} -SO ₃ M, and 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. )