JP2617187B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a high-sensitivity silver halide photographic light-sensitive material having a spectral sensitivity in the near infrared region. The present invention relates to a technique for improving color sensitization and preservability.

(B) Prior Art and its Problems In recent years, scanning and exposure of silver halide photographic materials with a laser beam to record images has been actively performed. Typical examples of such devices are a scanner that separates continuous tone photographs into a net, a facsimile that outputs a transmitted image, and an output device that uses a computer to type in the field of printing. .

As the laser light source used for these output machines,
There are ion lasers such as Ar and Kr, and gas lasers such as He-Ne and He-Cd.
The device has disadvantages such as large scale and short life. on the other hand,
With the development and commercialization of new materials in the electronics field, semiconductor lasers have recently attracted attention as new laser light sources. And the oscillation wavelength is 730
It has been reduced to near-infrared light of up to 780 nm, and is considered to become the mainstream of laser light sources for image output in the future, in addition to the advantages of low cost and compact size of the device. However, photosensitive materials used in this application are required to have high sensitivity characteristics having a spectral sensitivity in the near infrared region and storage stability, and require extremely high technology for photosensitive material manufacturers.

Spectral sensitization techniques from the red light to the near-infrared light region have been studied for many years, and many suitable polymethine cyanine dyes and merocyanine dyes have been reported. In addition, to improve the stability of the polymethine dye,
Improvements have been made such as introducing a substituent into the methine chain. For example, USP 2,839,403, 2,839,404, 2,872
5,058, 2,882,158, 3,148,065, 3,253,925
Nos. 3,357,833 and 3,623,881.

In addition, a number of supersensitizing techniques for improving spectral sensitivity by using two or more sensitizing dyes in combination or using a sensitizing dye and a certain compound in combination have been studied and reported. For example, USP 3,592,657 and 3,635,721
No. 3,649,288, No. 3,669,672, No. 3,674,499,
Nos. 3,695,888 and 3,994,733 are examples.

Despite these many techniques, they are not yet satisfactory, and new techniques for obtaining high-sensitivity photographic emulsions for near infrared are required.

Further, in addition to this supersensitizing technique, in a photosensitive material having a spectral sensitivity in the infrared region, the spectral sensitivity tends to change with time, and storage stability is an important issue.

As stabilizers for improving the storage stability, for example, amidimide benzol and benzimidazole have been known for a long time, but sufficient ones have not been found, and new techniques for improving the stability have been developed. Has been requested.

(C) Object of the Invention It is an object of the present invention to provide a high-sensitivity silver halide photographic material having a spectral sensitivity in the near infrared region. Another object of the present invention is to provide a silver halide photographic material having high storage stability.

(D) Structure of the Invention The object of the present invention is to provide at least one silver halide photographic emulsion layer spectrally sensitized by at least one sensitizing dye having a maximum spectral sensitivity in a wavelength region longer than 700 nm, and And a silver halide photographic light-sensitive material characterized in that at least one of the silver halide photographic emulsion layers contains a compound represented by formula (I) or (II). .

General formula (I) General formula (II) Here, n ₁₁ , n ₁₂ , n ₂₁ , n ₂₂ , and n ₂₃ are positive integers, and generally 1 to 20, preferably 4 to 10. n ₁₁ and n ₁₂ may be different even in the same.
Similarly, n ₂₁ , n ₂₂ and n ₂₃ may be equal or different. X represents hydrogen or a monovalent metal atom. Among them, an alkali metal such as sodium is preferable. X _11, X _12, X
_21, X _22, X ₂₃ represents an alkyl group, or an aryl group. The alkyl group is preferably a straight-chain alkyl group having 5 to 20 carbon atoms. In addition, it may have an unsaturated bond. Also,
The aryl group may have a substituent such as a sulfone group. X ₁₁ and X ₁₂ may be different even in the same.
Similarly, X ₂₁ , X ₂₂ , and X ₂₃ may be the same or different.

Sensitizing dyes having a maximum spectral sensitivity in the wavelength region longer than 700 nm used in the present invention, for example, USP 2,095,854,
095,856, 2,955,939, 3,482,978, 3,552,9
No. 74, 3,573,921, 3,582,344, 3,623,881 and the like.

Preferably, for example, dyes represented by the following general formulas (I) to (IV) are used.

General formula (I) General formula (II) General formula (III) General formula (IV) In the general formulas (I) to (IV), Z ₁ and Z ₂ may be the same or different and each represents an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. . R ₁ and
R ₂ may be the same or different and each represents an alkyl group or an alkenyl group. R ₃ represents an alkyl group, an alkenyl group, or an aryl group. R _{4 to} R ₁₀ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an alkoxy group. However, R ₆ and R ₇ or R ₈ and R ₉ can be linked to each other to form a 5- or 6-membered ring. R ₁₁ and R ₁₂ may be the same or different, and each is an alkyl group,
Represents an aryl group, and R ₁₁ and R ₁₂ may be linked to each other to form a 5- or 6-membered ring. Y is a sulfur atom, an oxygen atom, N-R ₁₃ (R ₁₃ is an alkyl group). X represents an acid anion. l, m, n, p and q each represent 1 or 2.

Specific examples of Z ₁ and Z ₂ include thiazole, benzothiazole, naphtho [1,2-d] thiazole, naphtho [2,1-
d) thiazole, naphtho [2,3-d] thiazole, selenazole, benzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole, oxazole, benzoxazole, naphtho [1,2 -D) oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, 2-quinoline, 4-quinoline, 3,3-dialkylindolenin, imidazole, benzimidazole, naphtho [1, 2-d) imidazole,
Examples include a nitrogen-containing heterocyclic ring such as pyridine. These heterocycles are alkyl groups (eg, methyl, ethyl,
Butyl, trifluoromethyl, etc.), an aryl group (eg, phenyl, tolyl, etc.), a hydroxy group, an alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), a carboxy group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.) ), A halogen atom (eg, fluorine, chlorine, bromine, iodine), an aralkyl group (eg, benzyl, phenethyl, etc.), a cyano group, an alkenyl group (eg, allyl, etc.) with 1 or 2
It may have the above.

In R ₁ and R ₂ , the alkyl group is methyl, ethyl,
Propyl, lower alkyl groups such as butyl, β-hydroxyethyl, hydroxyalkyl groups such as γ-hydroxypropyl, β-methoxyethyl, alkoxyalkyl groups such as γ-methoxypropyl, β-acetoxyethyl, γ-acetoxypropyl, β Acyloxyalkyl groups such as -benzoyloxyethyl, carboxymethyl groups such as carboxymethyl and β-carboxyethyl, alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl and β-ethoxycarbonylethyl, β-sulfoethyl, γ-sulfoethyl Sulfoalkyl groups such as propyl and δ-sulfobutyl; aralkyl groups such as benzyl, phenethyl and sulfobenzyl; and alkenyl groups include allyl.

As R ₃ , an alkyl group as described above for R ₁ and R ₂ ,
Examples include alkenyl groups and aryl groups such as phenyl, tolyl, methoxyphenyl, chlorophenyl, and naphthyl.

R _{4 to} R ₁₀ represent a hydrogen atom, a halogen atom (eg, chlorine,
Bromine, iodine, fluorine), alkyl groups as described in R _1, R _2, an aryl group, or R _1, an alkoxy group having alkyl as mentioned in R ₂ (i.e. group OR _1), and R ₆ R ₇
Alternatively, the 5- or 6-membered ring formed by R ₈ and R ₉ may be substituted with a lower alkyl group or the like. R ₁₁ and R
₁₂ represents an alkyl group or an aryl group as described for R ₁ and R ₂ , and R ₁₁ and R ₁₂ may be mutually linked to form a 5- or 6-membered ring. R ₁₃ is an alkyl group as described for R ₁ and R ₂ .

Examples of the acid anion of X include alkyl sulfate ions such as methyl sulfate and ethyl sulfate, thiocyanate ions, toluene sulfonate ions, halogen ions such as chlorine, bromine and iodine, and perchlorate ions. It does not exist when taking.

Next, specific examples of the compounds represented by formulas (I) and (II) used in the present invention will be illustrated below.

Specific examples of the sensitizing dye used in this study are shown below.

The sensitizing dye and the compounds represented by the general formulas (I) and (II) can be added at any time during the preparation of the silver halide photographic emulsion until the emulsion is coated. After chemical ripening, it is preferable to wait until coating. In addition, the addition amount of the sensitizing dye is 1 × 10 ⁻⁷ to 1 × 10
^-3 mol / mol Ag, preferably 1 × 10 ^-6 to 1 × 10 ^-4 mol / mol
Molar Ag, and 1 × 10 ⁻⁶ or more for compound (I) or (II).
1 × 10 ^-1 mol / mol Ag, preferably 1 × 10 ^-4 to 1 × 10 ^-2
Mol / mol Ag.

The silver halide emulsion used in the present invention can be prepared by various known methods.

The silver halide emulsion used in the present invention may be prepared by using any of the so-called single jet method or double jet method, but preferably a monodisperse emulsion prepared by using the latter method. Is good. Further, the crystal habit of the silver halide crystal used in the present invention may be any of cubic, octahedral, tetradecahedral, and tabular crystals, and the grain size is not particularly limited, but is preferably 0.1%.
Those having an average particle size of from μm to 2.0 μm are preferred.

The silver halide emulsion used in the present invention can be chemically sensitized by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine, rhodanine, and U.S. Pat.
No. 2,278,947, 2,410,689, 2,440,206,
No. 3,187,458, 3,415,649, 3,501,313 and the like can be used. Also, with sulfur sensitization, U.S. Pat.
A sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium or ruthenium described in JP-A Nos. 40,086, 2,556,245 and 2,566,263 can be used in combination. Also, potassium chloroaurate,
A sensitization method using various gold compounds such as auric trichloride or palladium compounds such as palladium chloride can be used in combination.

In the present invention, for example, known development stabilizers such as mercaptotetrazole, mercaptotriazole, benzotriazole, and benzimidazole, and various development accelerators such as antifoggants, polyalkylene oxides, thioether compounds, and quaternary ammonium salt compounds are used. Can be.

As the hydrophilic colloid used in the present invention, gelatin, colloidal albumin, protein derivatives such as carboxymethyl cellulose, such as casein, agar,
Sugar derivatives such as sodium alginate and starch, and synthetic polymers such as polyvinyl alcohol and polyacrylamide can be used alone or in a mixture at an appropriate ratio.

As the support used in the present invention, cellulose acetate film, films such as polyethylene terephthalate film or baryta or polyethylene, any material which is usually used for photographic light-sensitive materials such as paper coated or laminated with polypropylene or the like can be used. But it is good.

Various compounds such as a hardener, a surfactant, an antistatic agent, a plasticizer, and a matting agent in addition to the above,
Can be included to control the properties of the material.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the description.

(E) Example A cubic monodispersed silver iodobromide emulsion having an average particle size of 0.25 μm was prepared by the pAg controlled double jet method. The content of silver iodide was 1.5 mol%, and the average was distributed throughout the grains.

This emulsion was subjected to sulfur-gold sensitization by a conventional method, and 1-phenyl-5-mercaptotetrazole was added. The emulsion was divided and the sensitizing dye shown in Table 1 and the compound (I) or (I)
I) was added. After that, silver was added on a polyethylene terephthalate film base obtained by subbing an emulsion containing betaine-type fluorinated surfactant and formalin as a hardener.
It was applied so as to be 8 g / m ² .

Each sample thus obtained was exposed and developed, and the sensitivity value was measured.

The exposure was performed using a xenon lamp through an interference filter having a transmitted light peak at 782 nm for ^10-4 seconds.
The sensitivity value was determined as the reciprocal of the exposure required to obtain a transmission density of 3.2.

(Example 1) Table 1 shows the exemplified sensitizing dye (Dye-1) and the general formula (I).
Alternatively, the sensitivity values in combination with the compound represented by (II) are summarized for the case of Fresh and the case of forced aging for 72 hours at 50 ° C. and 80% relative humidity. Sensitivity value of comparative example
It is shown as a relative value when the value at the time of Fresh is set to 100.

(Example 2) Table 2 shows some sensitizing dyes and an example compound (I-
The sensitivity values obtained by the combination of 1) are summarized in the case of Fresh and the case where forced aging is performed for 72 hours under the condition of 50 ° C. and a relative humidity of 80%. The sensitivity value was 100% of the fresh value of each comparative example.
The relative values are shown as

(Example 3) Table 3 shows some sensitizing dyes and exemplary compounds (II-
The sensitivity values obtained by the combination of 1) are summarized in the case of Fresh and the case where forced aging is performed for 72 hours under the condition of 50 ° C. and a relative humidity of 80%. The sensitivity value was 100% of the fresh value of each comparative example.
The relative values are shown as

The examples show that the presence of compound (I) or (II) improves the sensitivity and at the same time stabilizes over time.

In addition, in the combination of the exemplified dye (Dye-1) and the following compound (III) having only one polyethylene oxide chain, the sensitivity value is 86 at the time of Fresh, and 36 after the elapse of time,
It does not exhibit the effects of compounds (I) and (II).

Compound (III) (F) Effects of the Invention According to the present invention, a silver halide photographic material having high sensitivity having a spectral sensitivity in the near infrared region and high storage stability can be obtained.

Continuation of the front page (56) References JP-A-62-108241 (JP, A) JP-A-62-145238 (JP, A) JP-A-60-134232 (JP, A) JP-A-58-190944 (JP) JP-A-60-80847 (JP, A) JP-A-60-200251 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic emulsion layer spectrally sensitized by at least one sensitizing dye having a maximum spectral sensitivity in a wavelength region longer than 700 nm, and
A silver halide photographic light-sensitive material characterized in that at least one of the silver halide photographic emulsion layers contains a compound represented by the formula (I) or (II). General formula (I) General formula (II) (Here, n ₁₁ , n ₁₂ , n ₂₁ , n ₂₂ , and n ₂₃ are positive integers. N ₁₁ and n ₁₂ may be the same or different. Similarly, n ₂₁ , n ₂₂ , n ₂₃ may be the same or different, X represents hydrogen or a metal atom, X ₁₁ ,
X ₁₂ , X ₂₁ , X ₂₂ and X ₂₃ represent an alkyl group or an aryl group. X ₁₁ and X ₁₂ may be different even in the same.
X ₂₁ , X ₂₂ and X ₂₃ may be the same or different. )