JP2898115B2 - Silver halide photographic material - Google Patents

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 material having a reflective support for obtaining a color image having a gradation from soft information recorded on a magnetic medium or the like. The present invention relates to a silver halide photographic material capable of obtaining an image having excellent sharpness.

[0002]

BACKGROUND OF THE INVENTION Today in the field of electronics, C
2. Description of the Related Art The remarkable progress of image pickup devices such as CDs and magnetic recording media has made it possible to take pictures with the same ease as conventional pictures using silver halide, and immediately transfer them to a television to enjoy them. In the field of printing and plate making, thanks to advances in scanners and image processing equipment, after reading the original image with a scanner, you can easily edit, correct, change contrast, enlarge and reduce the size, etc. while looking at the color display. You can now do it. As described above, recording and processing of an image as an electric signal is permeating not only in the industrial field but also in the general society.

[0003] However, simply displaying an image on a television screen is still not satisfactory, and an image recorded on paper is required. Various methods such as a thermal transfer method, an ink jet method, and an electrophotographic method are practically used. Has been Even in such fields, the rich gradation of silver halide photographic materials is outstanding compared to other systems and has excellent descriptive power, but conventional silver halide photographic materials have , Blue, green and red photosensitive silver halide emulsion layers, it is difficult to obtain a light source suitable for recording on the silver halide emulsion layers.

For exposing a silver halide photographic light-sensitive material for the above purpose, gas lasers such as helium / neon, argon ion, and helium / cadmium have been widely used. However, these lasers have disadvantages such as being large, expensive, and short in life. On the other hand, a method using a semiconductor laser and a non-linear optical element is known, but the conversion efficiency is not sufficient, and when viewed from the side of the silver halide photographic material, an appropriate wavelength is used. Due to problems such as lack of light, they had not been put to practical use.

[0005] The use of a silver halide emulsion sensitive to infrared rays solves these problems, and makes it possible to supply an inexpensive and compact exposure apparatus using a semiconductor laser. Regarding a silver halide photosensitive material having a silver halide photographic emulsion layer sensitive to infrared light, for example, Japanese Patent Application Laid-Open No. S61-137149 discloses a plurality of silver halide photographic emulsions having sensitivity to different wavelength ranges of infrared rays. A basic structure to be satisfied by a silver halide photographic light-sensitive material having a layer is disclosed. Also, JP-A-2-216148
The sharpness is deteriorated in such an infrared-sensitive silver halide color photographic light-sensitive material, and in a silver halide color photographic light-sensitive material in which two or more layers are sensitized to longer wavelengths than 670 nm, It discloses that sharpness deterioration can be made less noticeable visually by combining a yellow coupler with a layer spectrally sensitized to the longest wavelength. However, this technique can only make the physical property less noticeable even if it deteriorates, and its effect has not been sufficient yet.

JP-A-1-280750 and 2-173
No. 630, No. 2-239135, No. 2-277744
No. 2-282244, No. 3-7931, No. 3-
No. 13937 discloses a dye which can be used in an infrared-sensitive silver halide photographic light-sensitive material and which can obtain a desired spectral absorption with less contamination. However, the use of these dyes alone does not provide sufficient effects, and many water-soluble dyes have the disadvantage that the sensitivity varies greatly depending on the temperature at which the silver halide photographic material is exposed. However, the density fluctuation is further increased in addition to the characteristics of the semiconductor laser used for infrared exposure. In addition, many solid dyes have a drawback that when added in an amount necessary to obtain a sufficient sharpness improving effect, unevenness due to uneven development is likely to occur during development processing. This has been a major problem as a silver halide photographic material using a reflective support.

[0007]

The present invention relates to a silver halide color photographic material for obtaining a color image having a gradation from soft information described on a magnetic medium or the like. The present invention relates to a silver halide photographic light-sensitive material capable of stably obtaining an image having excellent sharpness.

[0008]

The present inventors have developed a silver halide photographic light-sensitive material having an infrared-sensitive emulsion layer for forming an image by scanning and exposing with infrared rays having a wavelength longer than 720 nm and developing the same. During the intensive studies, an object of the present invention is to provide a silver halide photographic emulsion layer containing a yellow coupler, a magenta coupler, and a cyan coupler on a reflective support, and at least one of the silver halide photographic emulsion layers. Is a silver halide photographic light-sensitive material having a spectral sensitivity maximum on the longer wavelength side than 720 nm, wherein the cyan coupler has a cyan image density of 0.
4 (CIE 1976)
It has been found that the object of the present invention can be achieved by a silver halide photographic light-sensitive material having a L ^* a ^* b ^* color difference of 23 or more, and the present invention has been completed.

Further, the silver halide photographic material is 3
H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-Flopyrrole and 6H-Flopyrrole have a mother nucleus and have at least two acid groups in the molecule or a —CH ₂ CH ₂ OR group (R is a hydrogen atom or When at least one of cyanine dyes having at least two substituents having one or more alkyl groups (hereinafter referred to as dyes of the present invention) is contained, more excellent effects of the present invention can be obtained, and The present inventors have found that there is no contamination due to the residual material and that the density fluctuation in the continuous operation state of the exposure apparatus is small, and have completed the present invention.

The cyan coupler according to the present invention is characterized in that when the cyan image density is 0.4, the color difference between the cyan coloring portion and the minimum density portion is 23 or more. The color difference between the color-developed portion and the minimum density portion as referred to here means that after coating a photographic component layer including a silver halide emulsion layer containing a cyan coupler on a reflective support having a smooth surface, an appropriate spectral composition is obtained. By exposing this to light and developing it, cyan color patches and white backgrounds of various color densities are obtained, and these can be obtained by measuring their spectral absorption. Spectral absorption is measured according to the geometrical conditions of illumination and light reception c in JIS Z-8722 (1982).
The tristimulus values X, Y, and Z were determined by the method described in SZ-8722 (1982), and the values were determined according to JIS Z-8729 (198).
0), the value of each L ^* a ^* b ^* is obtained, and the color difference is obtained according to the method described in JIS Z-8730 (1980). As a method of measuring cyan image density, JI
Status A defined in SK 7653-1988
The density of the cyan color patch may be measured using a densitometer that has the following spectral conditions and satisfies the geometric conditions defined in JIS K 7654-1990.

With respect to the above conditions required for the cyan image obtained from the silver halide photographic light-sensitive material according to the present invention, the structures of the cyan coupler and the color developing agent which determine the structure of the cyan image dye are as follows. Has the greatest impact. The effects of other components are relatively small, but additives having the ability to shift the spectral absorption of image dyes to longer or shorter wavelengths due to the formation of intermolecular hydrogen bonds, etc., and high boiling organics used for dispersion of couplers The type and amount of the solvent or the polymer, the ratio of the amount of the coupler to the high-boiling organic solvent, the amount of the dispersion of the coupler, and the like are affected.

As the cyan coupler which can be used in the silver halide photographic light-sensitive material of the present invention, a compound which can be used alone and which satisfies the above conditions is preferable. However, when a plurality of couplers are mixed and used, Even so,
If the above conditions are satisfied, the effects of the present invention can be obtained and can be preferably used.

Examples of the cyan coupler used in combination include cyan couplers represented by the following formulas [CI] and [C-II]. General formula [C-I]

[0014]

Embedded image In the formula, R _C1 represents an alkyl group having 2 to 6 carbon atoms. R
_C2 represents a ballast group. Z _C represents an atom or group which can be eliminated by a reaction with an oxidized form of the color developing agent. General formula [C-II]

[0015]

Embedded image In the formula, R ^C1 represents an alkyl group or an aryl group. R ^C2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. , R ^C3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ^C3 may form a ring together with R ^C1 . Z ^C represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

Cyan couplers which can be used in combination include the following CC-1 to CC-11.

Compounds which can be used alone in the silver halide color photographic light-sensitive material of the present invention to exhibit the effects thereof include the following CC-12 to CC-14, but are not limited thereto. It is not something to be done.

[0018]

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[0019]

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[0020]

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When an oil-in-water emulsion dispersion method is used to add the coupler according to the present invention to a silver halide photographic light-sensitive material, it is usually necessary to use a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination and dissolved, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of the high boiling point organic solvent which can be used for dissolving and dispersing the coupler include (1) dioctyl phthalate (2) dinonyl phthalate (3) diisododecyl phthalate (4) dicyclohexyl phthalate (5) tricresyl phosphate (6) trihexyl phosphate (7) tri (2-ethylhexyl) phosphate (8) diethyl lauramide (9) dinonylphenol (10) decalin (11) 1,4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane, etc. Can be raised.

The weight ratio of the coupler to the high-boiling organic solvent is such that the amount of the high-boiling organic solvent is 0.1 to 2 parts per coupler.
Is preferably used, and more preferably 0.2 to 1. A higher ratio of the high boiling point organic solvent makes it easier to obtain preferable spectral absorption, but is disadvantageous in terms of stability of the silver halide light-sensitive material and resistance to physical damage, and should be determined in consideration of both. It is.

In place of the method using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound may be dissolved in a low-boiling and / or water-soluble organic solvent, if necessary, and a gelatin aqueous solution or the like may be used. A method of emulsifying and dispersing by using various kinds of dispersing means using a surfactant in a hydrophilic binder can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include [PO-1] poly (Nt-butylacrylamide) and [PO-2] Nt-butylacrylamide-methyl methacrylate copolymer (60:40). [PO-3] Polybutyl methacrylate [PO-4] Methyl methacrylate-styrene copolymer (90:10) [PO-5] Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) ) [PO-6] ω-methoxypolyethylene glycol acrylate (additional mole number n = 9) -Nt-butylacrylamide copolymer (25:75) [PO-7] 1,4-butanediol-adipate polyester [PO-8] polypropiolactam and the like. The numerical value in parentheses of the copolymer indicates the weight ratio of the monomer.

The following compounds can be used for shifting the absorption wavelength of the coloring dye.

[0025]

Embedded image In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 ^{−3 to} 5 mol, more preferably 1 × 10 ⁻³ mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.
The larger the coating amount of the coupler, the larger the color difference at the same density can be.

As the yellow coupler and the magenta coupler used in the silver halide photographic light-sensitive material according to the present invention, various conventionally known couplers can be used, but the detail can be described by appropriately selecting the magenta coupler. It is possible to obtain an excellent photographic image, which is preferable. As a magenta coupler useful for the silver halide color photographic light-sensitive material according to the present invention, a coupler having a maximum color difference of 90 or more between a magenta coloring portion and a minimum density portion is preferable.

The yellow coupler for use in the silver halide photographic light-sensitive material according to the present invention includes the following general formula [Y
-I] is preferred. General formula [Y-I]

[0029]

Embedded image In the formula, R _Y1 represents a halogen atom or an alkoxy group;
_Y2 is -NHCOR _Y3 SO ₂ R _Y4 , -COOR _Y4 , -NH
COR _Y4 , -COOR _Y3 COOR _Y4 , -N (R _Y5 ) SO
₂ represents the R _Y4 or _{-SO 2 N (R Y5) R} Y4. R _Y3 represents an alkylene group, R _Y4 represents a diffusion-resistant group, R _Y5 represents a hydrogen atom, an alkyl group or an aralkyl group, and Z _Y represents a coupling-off group.

Specific examples of the yellow coupler preferably used in the present invention are shown below, but are not limited thereto.

[0031]

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[0032]

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[0033]

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The magenta coupler preferably used in the silver halide photographic light-sensitive material according to the present invention includes magenta couplers represented by the following formulas [MI] and [M-II]. General formula [MI]

[0035]

Embedded image In the formula, Z _M represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z _M may have a substituent. X _M represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R _M represents a hydrogen atom or a substituent. General formula [M-II]

[0036]

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In the formula, Ar _M represents an aryl group, X represents a halogen atom, an alkoxy group or an alkyl group, and R represents a group that can be substituted on a benzene ring. n represents 1 or 2. When n is 2, R may be the same group or different groups. Y represents a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

Specific examples of the magenta coupler preferably used in the present invention are shown below, but are not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodobromide, silver iodobromide, and salt. Any of silver iodobromide may be used.

The silver halide emulsion used in the present invention can be sensitized by a sensitization method using a reducing substance, a sensitization method using a chalcogen sensitizer, a sensitization method using a noble metal compound, or the like. The sensitization method can be used in combination. Sulfur sensitization, gold sensitization, and gold sulfur sensitization, which is a combination thereof, are preferred.

As a chalcogen sensitizer applied to the silver halide emulsion used in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned.

The noble metal sensitizer applied to the silver halide emulsion used in the present invention is preferably a gold sensitizer. The gold sensitizer may have a monovalent or trivalent gold oxidation number, and may be chloroauric acid, potassium chloroaurate, or the like.

The silver halide emulsion used in the present invention and the silver halide photographic material according to the present invention are spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. Having a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes. In the silver halide photographic light-sensitive material according to the present invention, the combination of each silver halide emulsion and coupler is not particularly limited, but the coupler used in combination with the silver halide emulsion having the longest wavelength photosensitive area is a yellow coupler. Certain cases are preferred.

Preferred specific compounds of the infrared sensitizing dye used in the present invention are shown below.

[0049]

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[0050]

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[0051]

Embedded image The red-sensitive sensitizing dye and the infrared-sensitive sensitizing dye can be used in combination with the following compounds as a supersensitizer.

[0052]

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[0053]

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The apparatus for exposing the silver halide photographic light-sensitive material of the present invention has three light sources corresponding to the photosensitive areas of three emulsions combined with a yellow coupler, a magenta coupler, and a cyan coupler. This light source can be selected according to its wavelength, and a gas laser such as helium / cadmium, argon ion, helium / neon, or a semiconductor laser can be used in combination.

In particular, it is preferable to use a semiconductor laser in consideration of miniaturization and cost reduction of the device. Any semiconductor laser may be used as long as it has a sufficient intensity at a wavelength of 720 nm or more.
Arsenic / phosphorus, aluminum / gallium / arsenic, indium / gallium / arsenic / phosphorus, aluminum / gallium /
Arsenic, antimony and the like can be given. Among them, 7
Semiconductor lasers having a wavelength of 50, 780, 810, 830, and 880 nm are advantageously used in view of light intensity, handling of silver halide photosensitive materials, and the like.

As a laser printer device considered to be applicable to such a system, for example, Japanese Patent Application Laid-Open
-4071, JP-A-59-11062, JP-A-63
-197947, JP-A-2-74942, JP-A-2-74942
No.-236538, JP-B-56-14963, JP-B-56-40822, European Wide-Area Patent 77410, Electronics and Telecommunications Department Technical Research Report Vol. 80, No. 244, and Movie Television Technical Journal 1984/6 (382) 34-36. Some are described on pages.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used, and in particular, a sharp image can be obtained visually regardless of the scene by using the dye of the present invention,
Furthermore, it is preferable without residual color contamination. Further, it is preferable that the density fluctuation in the continuous operation state of the exposure apparatus as seen with other dyes is small. Examples of the dye of the present invention include compounds represented by the following general formulas (I), (II) and (III).

[0058]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent an alkyl group, and Z ₁ and Z ₂ are each required to form a pyrrolopyridine, thienopyrrole or flopyrrole ring. Represents a group of non-metallic atoms.

Y ₁ and Y ₂ each represent a group of non-metallic atoms necessary for forming a pyrrolopyridine ring, and ＮN ⁺ in the ring of Y ₁
(R ₁ ) -bond; and ＝ N (R ₄ ) -bond in Y ₂ ring.

In the general formula (I), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , Z ₁ , Z ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Y ₁ , Y _{2 in the} general formula (II) and the general formula (III) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Y
_1, Z ₂ are each, group or -CH ₂ CH ₂ allows the dye molecule has a substituent having at least two acid groups
Represents a group capable of having at least two substituents having one or more OR groups. R represents a hydrogen atom or an alkyl group.

L represents a methine group, which may have a substituent. Further, the substituents may be bonded to each other to form a ring. X ^- represents an anion. m represents an integer of 4 or 5, and n represents an integer of 1 or 2. N is 1 when the dye forms an inner salt.

The acid groups in the general formulas (I), (II) and (III) include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups and the like, and these acid groups each include their salts. I do. Examples of the salt include alkali metal salts such as sodium and potassium, and organic ammonium salts such as ammonium, triethylamine and pyridine. Moreover _{R 1 ~R 6, Z 1,} Z 2, Y 1, Y 2, L, X - Details of,
R _{1 to} R ₆ described in JP-A-1-280750, pages 7-8,
These are synonymous with Z ₁ , Z ₂ , Y ₁ , Y ₂ , L, and X ⁻ .

Specific examples of the dye of the present invention are shown below, but the present invention is not limited to these.

[0065]

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[0066]

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[0067]

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[0068]

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Other dyes of the present invention include those described in
(4), (5), pp. 9-16 of 280750
(8), (10), (13), (15) to (20),
(22), (28)-(31), (33), (37),
The compound of (38) can be used equally.

These dyes are available from Journal of the
Chemical Society (J. Chem. Soc.) 1
89 (1933), U.S. Pat. No. 2,895,955 and JP-A-62-123454.

The dye of the present invention can be contained in a silver halide emulsion and used as an anti-irradiation dye, or can be contained in a non-photosensitive hydrophilic colloid layer to form a filter dye or And an antihalation dye. Further, two or more dyes may be used in combination depending on the purpose of use, or may be used in combination with another dye. The dye of the present invention can be easily contained in a silver halide emulsion layer or another hydrophilic colloid layer by an ordinary method. In general, a dye or an organic / inorganic alkali salt of a dye is dissolved in water to form an aqueous solution of a dye having an appropriate concentration, added to a coating solution, and coated by a known method to be contained in a photosensitive material. . The content of these dyes may vary depending on the intended use, generally used by applying so as to photosensitive material 1 m ² per 1～800Mg.

As the reflective support according to the present invention, any material may be used, and examples thereof include polyethylene-coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment, and polyethylene terephthalate support. Can be used. Among them, a support having on its surface a polyolefin resin layer containing a white pigment is preferable.

As the white pigment used for the reflective support according to the present invention, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably at least 10% by weight, more preferably at least 13% by weight. More preferably, it is 15% by weight or more. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured in this way,
The degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less, as the variation coefficient described in the above publication.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention are aminophenol and p-phenylenediamine widely used in various color photographic processes. A system compound is used. In particular, aromatic primary amine color developing agents are preferably used. A known developer component compound can be added to the color developing solution in addition to the above-described color developing agent.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both the water washing and the stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank. An endless belt system in which the material is fixed and conveyed may be used. In particular, a system in which a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank, and the photosensitive material is conveyed may be used.

[0079]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support.
However, on the side to be coated with the emulsion layer, a molten polyethylene in which 13% by weight of surface-treated anatase-type titanium oxide was dispersed was laminated to produce a reflective support. The degree of dispersion of titanium oxide was 0.19 as measured by the method described in JP-A-2-28640. Each layer having the following constitution was coated on this reflective support to prepare a multilayer silver halide photographic material, Sample 101. The coating solution was adjusted as described below.

Yellow coupler (YC-8) 26.7
g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-
1) 0.67 g and high boiling organic solvent (DNP) 6.6
Ethyl acetate (60 ml) was added to 7 g and dissolved.
10% containing 9.5 ml of surfactant (SU-1)
The emulsion was dispersed in 220 ml of an aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion.
This dispersion was mixed with a blue-sensitive silver halide emulsion (Em-B) (containing 8.68 g of silver) prepared under the following conditions, and a 5% aqueous solution of an anti-irradiation dye AI-35 was added.
7 ml was added to prepare a first layer coating solution. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. (H-1) was added to the second and fourth layers as a hardener, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

The layer structure is as shown in Tables 1 and 2.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

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[0085]

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[0086]

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[0087]

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(Method for preparing blue-sensitive silver halide emulsion Em-B) 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C
The following (Solution A) and (Solution B) were added with pAg 6.5, pH 3.0.
Over 30 minutes while controlling at the same time.
Solution) and (Solution D) were simultaneously added over 180 minutes while controlling to pAg 7.3 and pH 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 10 g of potassium bromide 1.0 g of water To 600 ml (Solution D) 300 g of silver nitrate Add water to 600 ml

After completion of the addition, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (S / R) = 0.07, and a silver chloride content. 99.5 mol% monodisperse cubic emulsion (EMP-
1) was obtained. Here, S represents the standard deviation of the particle diameter, and R represents the average particle diameter.

The emulsion (EMP-1) was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

(Preparation of Green-Sensitive Silver Halide Emulsion Em-G) Except for changing the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D), (EMP- In the same manner as in 1), the average particle diameter is 0.43 μm, and the variation coefficient (S /
R) = 0.08, a monodisperse cubic emulsion (EMP-2) having a silver chloride content of 99.5 mol% was obtained. (EMP-2) with green sensitive sensitizing dye (GS-1) at 55 ° C.
After 0-minute chemical ripening, a green-sensitive silver halide emulsion (Em-
G) was obtained.

(Method of adjusting red-sensitive silver halide emulsion Em-R) Except for changing the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D), (EMP-R) In the same manner as in 1), the average particle size is 0.50 μm, and the variation coefficient (S /
R) = 0.08, a monodisperse cubic emulsion (EMP-3) having a silver chloride content of 99.5 mol% was obtained. (EMP-3) using a red-sensitive sensitizing dye (RS-1) at 60 ° C.
After performing chemical ripening, a red-sensitive silver halide emulsion (Em-
R) was obtained.

In the preparation of Sample 101, the blue-sensitive emulsion was replaced with the following infrared-sensitive emulsion (Em-IR1), and the green-sensitive emulsion was replaced with the following infrared-sensitive emulsion (Em-IR2).
Sample 102 was prepared in the same manner except that the anti-irradiation dye AI-3 was replaced with an equimolar anti-irradiation dye AI-4 and the anti-irradiation dye AI-1 was replaced with an equimolar anti-irradiation dye AI-5. Produced. Next, Sample 103 was prepared in the same manner as Sample 102 except that the cyan coupler CC-1 was replaced with CC-12.

(Preparation of infrared-sensitive emulsion)
2) was subjected to chemical ripening at 55 ° C. using the following compounds.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer (STAB-1) 0.6 × 10 ⁻⁴ mol / mol AgX At the time when the optimum sensitometric performance is obtained. (STA
B-1) was added and the temperature was lowered to stop the chemical ripening, but the emulsion was divided 3 minutes before the addition of (STAB-1), and one of the emulsions was coated with an infrared sensitizing dye (IRS-11). The resulting mixture was subjected to spectral sensitization to obtain an infrared-sensitive emulsion (Em-IR1), and an infrared sensitizing dye (IRS-7) was added to the other, followed by spectral sensitization to obtain an infrared-sensitive emulsion (Em-IR1). Em-IR2) was obtained.

[0098]

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[0099]

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[0100]

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Samples 101, 102, and 103 were subjected to decomposition exposure at various exposure amounts using an interference filter KL-69 (manufactured by Toshiba Glass) and a color glass filter R-67 (manufactured by Toshiba Glass). Processing was performed according to the processing steps. The unexposed sample was processed in the same manner to produce a white patch.

[Color developing solution] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1. 0 g Ethylenediaminetetraacetic acid 1.0 g Disodium catechol-3,5-disulfonate 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 10 g Potassium carbonate 27 g Water is added to make the total volume 1 liter, and the pH is adjusted to 10.10.

[Bleaching-fixing solution] Ethylenediaminetetraacetate ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total volume to 1 liter. PH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing Solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7 with sulfuric acid or potassium hydroxide. Adjust to .0.

For the samples 102 and 103, the spectral absorption of each patch was measured by a 607 type color analyzer (manufactured by Hitachi, Ltd.), and based on the measured values, JIS Z-8729-
L ^* a ^* b ^* is calculated by the method of 1980, and then J
The color difference (ΔE) from the white patch was calculated according to the method of IS Z-8730-1980. The same sample was used for TR-811.
ΔE at a cyan image density of 0.4 was determined using a densitometer (manufactured by X-Rite). As a result, in the sample using the cyan coupler CC-12, ΔE = 23.
ΔE = 19.3 in the sample using 2, CC-1.

As an apparatus for exposing a photosensitive material, a helium-cadmium laser (about 442 nm) is used as a blue light source.
m), a helium-neon laser (about 544 nm) as a green light source, a helium-neon laser (about 633 nm) as a red light source, and an aluminum-gallium-indium-phosphorus semiconductor laser (about 6 nm) as an infrared light source.
70 nm), a gallium aluminum arsenide semiconductor laser (about 780 nm), and a gallium aluminum arsenide semiconductor laser (about 830 nm) were prepared, and an optical system was assembled according to the photosensitivity of the photosensitive material. The light emitted from the three lasers is modulated according to the image data, then focused into one beam, and applied to a silver halide photographic material conveyed at a speed of 20 mm / sec. 16
Scanning exposure was performed at a main scanning speed of m / sec. The beam diameter at this time was about 80 μm.

An image of a 4 × 5 inch color slide was digitally digitized by a scanner at a size of 50 × 50 μm per pixel. Images were output to the samples 101, 102, and 103 using the data. The output image was presented to 10 subjects and evaluated in terms of the sharpness of the image. One point was assigned to the inferior one, three points to the ordinary one, and five points to the excellent one. A five-point evaluation was performed. The average value of the scores was obtained, and the print image was evaluated. Table 3 shows the results.

For the evaluation, the following four scenes were used. (1) Portrait of a woman (2) Group photo (3) Mountain landscape photo (4) Amusement park landscape photo

[0109]

[Table 3]

As can be seen from the above results, when the silver halide photographic light-sensitive material having the infrared-sensitive emulsion layer was used, the visual sharpness was higher than that of the sample 101 in which an image was formed using visible light. It can be seen that the deterioration of the hardness is remarkable. On the other hand, when the silver halide photographic light-sensitive material according to the present invention is used, the improvement is remarkable especially in portraits such as scenes (1) and (2). Because of this, it is miniaturized,
It can be seen that the disadvantages encountered when using infrared light for exposure in search of an inexpensive image forming apparatus are better ameliorated by the present invention. (Example 2) Silver halide photographic light-sensitive materials 201 to 203 were prepared by changing the combination of the silver halide emulsion and the coupler in Sample 103 prepared in Example 1 as shown in Table 4.

[0111]

[Table 4]

Using this silver halide photographic light-sensitive material, the visual sharpness of the image was evaluated in the same manner as in Example 1. Table 5 shows the results.

[0113]

[Table 5]

When silver halide photographic materials prepared by variously changing the combinations of silver halide emulsions and couplers were prepared and evaluated, the effects of the present invention were obtained and a visually sharp image was obtained. It was confirmed that. It can be seen that silver halide photosensitive material samples 103 and 201 in which a long-wavelength photosensitive emulsion and a yellow coupler are combined have greater effects than other combinations. Example 3 A polyethylene-coated reflective support in which the degree of dispersion of titanium oxide in polyethylene shown in Table 6 was increased, and a reflective support in which a white pigment-containing reflective layer was formed by an electron beam-curable resin layer shown below. Sample 10 of Example 1 except used
Samples 301 and 302 were produced in the same manner as in No. 3.

(Preparation Method of Electron Beam Cured Resin Layer) The following composition was dispersed in a ball mill for 20 hours, and then the basis weight was adjusted to 18
0 g / m ² paper support on one side with a reverter to a film thickness of 25
μm. Epoxy acrylate 20 parts by weight (Sannobuco Photomer 3082) Aliphatic acrylate 10 parts by weight (Toagosei Aronix M233) Trimethylolpropane triacrylate 30 parts by weight Titanium oxide (rutile type average particle size 0.2 μm) 40 parts by weight Next, acceleration voltage Electron beam irradiation was performed at 150 kV and an absorbed dose of 1.5 Mrad to cure. An electron beam cured layer was similarly provided on the back side of the paper support to obtain a white pigment-containing reflective support. The degree of dispersion of the white pigment in the reflective support was 0.08.

[0116]

[Table 6]

Using this silver halide photographic material, the visual sharpness of the image was evaluated in the same manner as in Example 1. The results are shown in Table 7.

[0118]

[Table 7]

An image produced using an infrared-sensitive silver halide photographic material produced using a support in which the content and dispersity of titanium oxide in the resin layer forming the reflective layer of the support were changed was used. As a result of the evaluation, it was confirmed that the silver halide photographic light-sensitive material according to the present invention can provide an effect that a visually sharp image can be obtained. In particular, in a sample in which the degree of dispersion of titanium oxide is increased, the effect of the present invention can be enhanced even in scenes in which the effects of the present invention are not so strong in Examples 1 and 2, and such a support is used. Has been found to be a preferred embodiment of the present invention. (Example 4) Sample 401 was prepared in the same manner as in preparation of sample 103 of Example 1 except that the irrigation-preventing dyes of the second and fourth layers were replaced by the equimolar dyes of the present invention shown in Table 8. To 404 were produced.

[0120]

[Table 8]

Using this silver halide photographic light-sensitive material, visual sharpness of an image was evaluated in the same manner as in Example 1. The results are shown in Table 9.

[0122]

[Table 9]

Using this silver halide photographic light-sensitive material, the same image was continuously printed 100 times, and the range of density fluctuation at a color balance close to gray was determined. Table 10 shows the results.

[0124]

[Table 10]

It has been found that by using the dye of the present invention, not only an image excellent in visual sharpness can be obtained, but also density fluctuation in a continuous operation state of the exposure apparatus can be reduced. Example 5 In the preparation of the infrared-sensitive emulsion Em-IR2 of Example 1, the infrared sensitizing dyes IRS-2, IRS-3, IRS-6, and IRS were used instead of the infrared sensitizing dye IRS-7. −
9, using an infrared-sensitive silver halide emulsion Em-IR3;
Em-IR4, Em-IR5 and Em-IR6 were prepared. The Em-IR2 of Sample 103 was replaced with these Em-IR3,
Em-IR4, Em-IR5, and Em-IR6 were replaced with silver halide photographic materials 501, 502,
503 and 504 were produced. Example 1 using this sample
When the evaluation was performed in the same manner as in the above, the results in Table 11 were obtained, and it was confirmed that the effects of the present invention were obtained.

[0126]

[Table 11]

Example 6 In the preparation of Sample 103 of Example 1, the cyan coupler CC-12 was replaced with CC-3 and CC-3.
-8, CC-9, CC-13, CC-14 and CC-3
Silver halide photographic light-sensitive material samples 601, 602, 603, and 60 in place of an equimolar mixture of
4,605,606 were produced. A cyan color patch was created in the same manner as in Example 1, and the color difference from a white background at a density of 0.4 was determined. As a result, ΔE = 18.
9, ΔE = 21.0 for CC-8, ΔE =
17.7, ΔE = 25.1 for CC-13, CC-14
ΔE = 25.7, and ΔE = 23.9 in an equimolar mixture of CC-3 and CC-14. When this sample was evaluated in the same manner as in Example 1, the results shown in Table 12 were obtained.

[0128]

[Table 12]

When the cyan coupler used in the above table satisfies the conditions of the cyan coupler according to the present invention, the effect of the present invention is not affected whether two types of couplers are used in combination or a single coupler. Is obtained.

[0130]

The silver halide photographic light-sensitive material of the present invention comprises:
Using an inexpensive and small-sized exposure device having infrared light as an exposure light source, a visually sensible image can be stably obtained from information recorded on a magnetic recording medium or the like.

Continuation of front page (56) References JP-A-1-156747 (JP, A) JP-A-2-15749 (JP, A) JP-A-1-280750 (JP, A) JP-A-1-156748 (JP) JP-A-63-197947 (JP, A) JP-A-1-303433 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/38 G03C 1/83 G03C 7/00 520

Claims (2)

(57) [Claims] 1. A reflective support having a silver halide photographic emulsion layer containing a yellow coupler, a magenta coupler and a cyan coupler, respectively, wherein at least one of the silver halide photographic emulsion layers has a wavelength longer than 720 nm. In the silver halide photographic material having a maximum value of spectral sensitivity on the side, the color difference between the cyan coupler and the minimum density portion when the cyan image density becomes 0.4 (CIE 197)
6 L ^* a ^* b ^* color difference (color difference in a color space) of 23 or more. 2. A compound having 3H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-floppyrrole and 6H-floppyrrole as a mother nucleus and having at least 2
Number of or having an acid group or -CH ₂ CH ₂ OR group (R is a hydrogen atom or an alkyl group) at least one cyanine dye having at least two substituents having one or more
2. The silver halide photographic light-sensitive material according to claim 1, comprising a seed.