JPH0264630A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the subject material which does not deteriorate whiteness and photographic gradation and has improved sharpness by incorporating a yellow, a magenta and a cyan water-soluble dyestuff in the photographic constituting layer of the material, and by specifying the reflected density of the material at each of wavelengths of 450nm, 550nm and 700nm before developing the material to >=0.8, respectively. CONSTITUTION:The photographic constituting layer contains the yellow, the magenta and the cyan water-soluble dyestuff, and the water-soluble dyestuff is exemplified by an oxonol dye, a cyanine dye, a merocyanine dye, an azo dye, an anthraquinone dye and an allylidene dye, etc. The reflected density of the material at each of the wavelength of 450nm, 550nm and 700nm before developing the material is specified to >=0.8, respectively. Thus, the obtd. color photosensitive material does not deteriorate the whiteness and the photographic gradation and has the improved sharpness.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a reflective silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material) with improved sharpness. The present invention relates to a color sensitive material for creating a color proof from a color-separated transmission black-and-white dot image.

[Background of the invention]

Recently, color sensitive materials have been diversified. For example, it is a color sensitive material for imprinting characters on business cards, postcards, etc., or a color sensitive material for color proofing.

The characteristics of color photosensitive materials used in these applications are high sharpness, no blurring of characters, and faithful reproduction of halftone dots for color proofs.

It goes without saying that high sharpness is one of the conditions for high quality in general color printing.

Color proofing is an alternative process in the printing industry to omit the trial printing process in the process of converting color original documents into printed matter. Various methods are known for color proofing, including silver salt photosensitive material method, photopolymer transfer method, toner transfer method, etc. Specifically, Consensus (Konica), Color Art (Fuji Photo Film), It is commercially available under trade names such as Color Key (3M Company) and Cromarin (Dupont Company).

In the photopolymer transfer method, the transfer process is complicated and images cannot be obtained quickly, and the cost is also high. The L. toner transfer method causes toner leakage, which is unfavorable in terms of environmental hygiene. The silver halide method does not have these drawbacks, is low cost, has good workability, and can quickly produce color proofs.

However, generally commercially available color photosensitive materials have insufficient sharpness and cannot provide faithful halftone dot reproducibility. In addition, high-sharp color sensitive materials with an antihalation layer containing a colloidal silver layer are commercially available, but they have problems such as deterioration of the white background and softening of photographic gradation. There is a demand for colored photosensitive materials.

The following method is known as a method for improving the sharpness of color sensitive materials.

(1) Preventing irradiation with water-soluble dyes.

(2) An antihalation layer containing colloidal silver or colloidal manganese is provided.

(3) Increasing the packing density of the white pigment in the polyolefin layer of a reflective support in which a base paper is laminated with polyolefins.

(4) Thinning the photographic constituent layer containing hydrophilic colloid.

(5) A photographic constituent layer contains a compound that releases a development inhibiting compound during development.

Method (1) is generally used for commercially available color photosensitive materials for printing, but the content of water-soluble dyes is low, and each wavelength of 450 nm is used before the color photosensitive material is developed.
, 550 nm, and 700 nm reflection density is less than 0.5. For this reason, sufficient sharpness and faithful color proof cannot be obtained.

With method (2), staining occurs due to poor bleach-fixing of colloidal silver and deterioration of the white background due to fogging of silver halide, and the photographic gradation is significantly softened, resulting in images with poor color balance as color proofs. can't get it. For this problem, Japanese Patent Application Laid-Open No. 63-63034
In JP-A-63-63040, it was proposed to specify the ratio of gelatin to colloidal silver in the antilation layer and the adjacent auxiliary layer, and in JP-A-63-63040, it was proposed to specify the thickness of the antilation layer, but no satisfactory effect could be obtained.

Regarding (3), please refer to JP-A No. 61-284763 and JP-A-61-284763.
No. 1-270749, No. 61-270750, etc., but an image satisfactory as a color proof cannot be obtained.

Regarding (4), there is a limit to how thin the photographic constituent layer can be made, and the effect is small.

Regarding (5), the edge effect is emphasized at low spatial frequencies, but an image that is satisfactory as a color proof cannot be obtained.

[Purpose of the invention]

Therefore, the object of the present invention is to eliminate deterioration of white background and photographic gradation,
An object of the present invention is to provide a color photosensitive material with greatly improved sharpness. The object of the present invention is to provide a color photosensitive material that can provide faithful halftone dot reproduction images particularly suitable for color proofing.

[Structure of the invention]

An object of the present invention is to provide a silver halide color photographic material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. The Maekita photographic constituent layer contains yellow magenta and cyan water-soluble dyes, and has a reflection density of 0.8 or more at each wavelength of 450 nm, 550 nm, and 700 nm before development of the silver halide color photographic light-sensitive material. This can be achieved with certain silver halide color photographic materials. Note that the reflection density in the present invention is a value measured using a color analyzer model 607 manufactured by Hitachi, Ltd.

The present invention will be explained in more detail below.

Examples of yellow magenta and cyan water-soluble dyes included in the photographic constituent layer of the present invention include oxonol dyes, cyanine dyes, merocyanine dyes, azo dyes, anthraquinone dyes, and arylidene dyes. Particularly preferred dyes are oxonol dyes and merocyanine dyes from the viewpoint of degradability and non-color sensitization of silver halide emulsions.

As an oxonol dye, US Pat. No. 4,187,22
No. 5, JP-A No. 48-42826, No. 49-5125, No. 49-99620, No. 50-91627, No. 5
No. 1-77327, No. 55-120660, No. 58-
No. 24139, No. 58443342, No. 59-387
No. 42, No. 59-111640, No. 59-11164
No. 1, No. 59-168438, No. 60-218641
No. 62-31916, No. 62-66275, No. 62-66276, No. 62-185755, No. 62
-273527, Sono No. 63-139949, etc. As a merocyanine dye, JP-A-50-1
No. 45124, No. 58-120245, No. 63-35
No. 437, No. 63-35438, No. 63-34539
No. 63-58437, etc.

Typical specific examples of oxonol dyes and merocyanine dyes are shown below, but are not limited thereto.

(Water-soluble yellow dye) IY-3 IY IY-5 S[33K 03K IY-6 IY-9 IY-7 IY IY-3 IY-11 to S03 AIY-12 AIY-13 AIY-14 IM-4 IM-5 IM-6 Usb (Water-soluble magenta dye) IM-1 IM-2 IM S○3K S.I.J., K. IM-7 IM-8 IM-9 AIM-10 A.I.M. AIM-12 A I C-2 IC IC-4 AIM-13 AIM-14 (Water-soluble cyan dye) IC-1 Kiri 3K IC-5 IC-6 IC-7 So, to AlC-8 AIC-9 IC-10 ,1C-14 then oxo Nol dyes and metals Russianine dye Typical examples of other water-soluble dyes are shown below. The light is not limited to these.

IY-15 IY Shikun (JH IC-11 Ic-12 IC-13 IY-17 IY IM-15 IM-16 So, AIM-17 AIC-17 AIM-18 IC-18 IC-15 Water-soluble in the present invention The amount of dye used is 450 nm, 550 nm, and 700 nm for each wavelength before the color photosensitive material is developed.
It is added in such an amount that the reflection density in nm is 0.8 or more.

The reflection densities preferably range from 0.9 to 1.2 in each case.

The water-soluble dye in the present invention is contained in a photosensitive silver halide emulsion layer and/or a non-photosensitive layer.

The water-soluble dye of the present invention is used in combination of yellow, magenta, and cyan water-soluble dyes, and each of the yellow-magenta and cyan water-soluble dyes can be used alone or in combination of two or more.

In the silver halide emulsion used in the present invention, any silver halide can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. can.

The silver halide grains may be formed by any of the acid method, neutral method, and ammonia method, and methods known in the photographic field such as simultaneous mixing method, forward mixing method, back mixing method, and conversion method are used.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions can be used either with a wide grain size distribution (polydisperse emulsion) or with a narrow grain size distribution (monodisperse emulsion), but preferably a monodisperse emulsion (with a standard grain size distribution). deviation/average particle size - coefficient of variation 0.20 or less)
It is. The particle size is preferably 0.1 to 1.0 μm.

Silver halide emulsions can be chemically sensitized (for example, sulfur sensitization, gold sensitization, selenium sensitization, reduction sensitization) and spectral sensitization (for example, cyanine dyes, merocyanine dyes, hemicyanine dyes, styryl dyes, Spectral sensitization using hemioxonol dyes) is possible. Additionally, antifoggants or stabilizers known in the art (eg, azaindenes, mercapto heterocycles) can be added.

The emulsion layer of the light-sensitive material contains a diffusion-resistant material that couples with an oxidized form of an aromatic primary amine compound (e.g., p-7 22-diamine derivative or aminophenol derivative) to form a dye during color development. sexual couplers are used.

As the yellow dye-forming coupler, acylacetanilide couplers can be used, and among these, benzoylacetanilide and pivaloylacetanilide compounds are preferred. Specific examples of yellow couplers include, for example, U.S. Pat.
5, No. 506, No. 3,408,194, No. 3゜55
No. 1.155, No. 3,891,445, Japanese Unexamined Patent Publication No. 1973-
No. 73147, No. 50-6341, No. 52-2182
Examples include couplers described in No. 7, No. 52-115219, and No. 58-95346.

As the magenta dye-forming coupler, 5-pyrazolone type, pyrazoloazole type, pyrazolinobenzimidazole type, indasilone type, open chain acylacetonitrile type coupler, etc. can be used, and these are described, for example, in US Pat. No. 2,600.788. No. 3,062゜653, No. 3
, No. 152.896, No. 3,558.318, No. 3,
930゜866, JP-A-49-29639, JP-A No. 50
-13041 etc.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. These cyan couplers are disclosed in, for example, U.S. Pat.
No. 3,034,892, No. 3,839.044, JP-A-47-3742, No. 50-112038, No. 5
0-130441 etc.

A benzophenone-based or benzotriazole-based ultraviolet absorber may be added to the photosensitive material.

Particularly preferred are benzotriazole compounds, such as U.S. Patent No. 3,754,919, U.S. Pat.
Those described in No. 41572 and the like can be used.

Hydrophobic compounds, such as the dye-forming couplers and UV absorbers described above, are typically combined with high boiling organic solvents (e.g. phthalates, phosphates, phenol derivatives, alkylamides, cycloalkanes), optionally with low boiling points, and/or Alternatively, it is used by dissolving it in combination with a water-soluble organic solvent and emulsifying and dispersing it in a binder using a surfactant.

The binder used in the photographic constituent layer of the present invention includes:
Gelatin, albumin, agar, gum arabic, partially hydrolyzed, polyvinyl acetate, polyacrylamide, etc. can be used, and gelatin is particularly preferred.

The emulsion layer and auxiliary layer on the emulsion side may contain various photographic additives. For example, as described in Research Disclosure No. 17643, color image stabilizing agents, color stain prevention agents, optical brighteners, antistatic agents, hardening agents,
Surfactants, plasticizers, wetting agents, etc. can be used as appropriate.

As a coating method for the emulsion layer and the constituent layers, slide hopper coating, curtain coating, air doctor coating, etc. are useful, but simultaneous multilayer coating using a slide dropper is particularly preferred.

The reflective support of the present invention contains white pigments on both sides of the base paper! ; Laminated thermoplastic resin such as polyolefin (e.g. polyethylene, polypropylene) (r
Rc* paper), baryta paper, plastic film containing white pigment, etc., especially those with a thickness of 100-1
50. um RCIJf [Paper, Ah] - Preferred for color proofing because it has a texture similar to paper.

The photographic gradation in the present invention is not particularly limited, but preferably the leg photographic gradation is 1.7 or more. By setting the leg photo gradation to 1.7 or higher, a color proof with even more faithful halftone dot reproducibility can be obtained. Further, in order to stabilize the exposure latitude, the photographic gradation with a reflection density of about 1.7 is preferably 1.8 to 2.5.

The leg photo gradation referred to here means that the characteristic curve is fog + 0.
The exposure methods used in the present invention obtained by connecting the point that intersects 25 (A in Fig. 1) and the point that intersects fog +0.75 (B in Fig. 1) include contact exposure method, photographic exposure method. There are two methods: an enlargement exposure method, and a scanning exposure method, and the contact exposure method is particularly preferable from the viewpoint of halftone dot reproducibility of color proofs and dimensional reproducibility with respect to originals.

Light sources used in the exposure of the present invention include natural light, tungsten electric lamps, fluorescent lamps, mercury lamps, halogen lamps, etc. Fluorescent lamps are particularly preferred because they generate less heat and can achieve miniaturization of exposure equipment in scanning exposure.

The color development process in the present invention is usually carried out in the order of a color development step, a bleach-fixing step, a water washing step, or a stabilization step known in the photographic industry.

In addition, for direct positive color photosensitive materials, in addition to the above methods, there are also reversal processing methods such as fogging processing, and for reversal color photosensitive materials, a positive image can be obtained by combining with the first monochrome development processing.

Aromatic primary amines are typical color developing agents for the color sensitive material of the present invention, and known alkaline agents, preservatives, antifoggants, optical brighteners, etc. are used in the color developing solution. be able to. Known bleaching agents and fixing agents can be used in the bleach-fixing solution.

〔Example〕

EXAMPLES The present invention will be explained in detail by examples below, but the present invention is not limited to the examples.

Example 1 A color photosensitive material for color proofing was prepared by coating a photographic constituent layer as described below on a 135 μm thick RC base paper as a reflective support. In addition, unless otherwise specified, the amount added is for photosensitive material 1.
The amount applied per m2 is shown.

(Photographic constituent layers) Layer 1: Blue-sensitive emulsion layer A monodisperse (coefficient of variation 0.18) silver chlorobromide emulsion (silver chloride) spectrally sensitized with sensitizing dye (D-1) and sulfur-sensitized. 5 mol%) converted to silver 0.34g yellow coupler 0.9g gelatin
1.6g layer 2: First intermediate layer 2.5-di-t-octylhydroquinone 0.05g gelatin 1.06g layer 3: Green-sensitive emulsion layer Spectral sensitization with sensitizing dye (D-2) and sulfur Sensitized monodisperse (coefficient of variation 0.18) silver chlorobromide emulsion (containing 15 mol% silver chloride) converted to silver: 0.29g magenta coupler (M -1) 0.36g gelatin
1.4g layer 4: second intermediate layer ultraviolet absorber (UV-1) 0.3g2
．． 5-sheet t-octylhydroquinone 0.05g Gelatin 1.4g Layer 5: Red-sensitive layer Emulsion layer Spectral sensitization with sensitizing dye (D-3), sulfur-sensitized monodispersity (coefficient of variation 0.18 ) silver chlorobromide emulsion (containing 15 mol% silver chloride) is converted into silver: 0.22g cyan coupler (C-1) 0.14g cyan coupler (C
-2) 0.28g gelatin
1.5 g Layer 6: First protective layer Ultraviolet absorber (UV-1) 0.7 g Gelatin 0.6 g Layer 7: Second protective layer Gelatin 0.9 g Surfactant S-15- (Additives used) a Q Cα D-2 C,H.

For sample Nos. 1 to 4 obtained as above, adding the water-soluble dyes shown in Table 1 to the above photographic constituent layer,
The following treatments were performed.

(Exposure method) There are 175 dots per inch as a transmission black and white halftone image,
The samples with varying area ratios were vacuum-adhered to a color photosensitive material and exposed.

Fluorescent lamps are used as light sources, and blue and blue color separation filters are used.
Kodak Wratten gelatin filters No. 47BX No. 61, No. 29 were used for green and red, respectively.

(Development processing method) Color development 2 minutes 38°C bleach fixing
45 seconds 33°C stabilization 1 minute 30 seconds 3
3°C dry 1 minute 70°C
Color developer composition N-ethyl-N-β-methanesulfonamidoethyl = 3
-Methyl-4-amino)aniline sulfate 4.5g Hydroxylamine sulfate 2.0g Potassium carbonate Sodium chloride Sodium bromide Anhydrous sodium sulfite Benzyl alcohol water was added to make 1Q, and the pH was adjusted to 10.15.

Bleach-fix solution composition Ethylenediami sodium salt ammonium thiosulfate sodium bisulfite Add water to make If, adjustment.

Stabilizing liquid iron (III) tetraacetate hydroxide 25.0g 0.1g o. 2g 2.0g 10.0mI2 60.0g using thorium 100.0g 20.0g 5-chloro-2-methyl-4-inthiazolin-3-one to pH 7.0 using sulfuric acid 1.0g Ethylene glycol 1. 0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Ammonium sulfite 3.0g Optical brightener (4
-4'-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to obtain IQ, and adjust to pH = 7.0 with sulfuric acid or potassium hydroxide.

The following evaluations were performed on the treated samples.

Evaluation Items (1) Leg photo gradation was measured for yellow images, magenta images, and cyan images.

(2) The white background density after the development process was measured.

(3) The image quality of the halftone image after the development process was evaluated as follows.

O...Color proof with halftone image quality matching the printed matter.

△・・・Color proof with out of color balance compared to printed matter.

X: Color proof with large dots crushed compared to printed matter.

XX...Color proof with large dots and small dots crushed against the printed matter.

The evaluation results are shown in Table-2.

In Sample No. 2, the photographic gradation of the yellow image was lowered due to the influence of the black colloidal silver, resulting in a halftone image in which red became vermilion and green became yellow-green as a color proof. In addition, black colloidal silver remained unbleached and fixed, resulting in deterioration of the white background.

In Samples No. 3 and 3, there was some deterioration of the white background because they were water-soluble dyes called azo dyes and anthraquinone dyes that were difficult to decompose in the developing solution.

Sample No. 094 was a water-soluble dye that easily decomposed in the developing solution, and there was no deterioration of the white background at all.

In sample No. 5, there was a slight shift in color balance.

Example-2 As sample No. 5, each emulsion layer of sample No. 094 of Example-1 was prepared as a polydisperse silver halide emulsion (coefficient of variation -0°40
) was prepared. The leg photo gradations are y = 1.56 M = 1.52 C = 1.55, respectively.
Met.

Further, as sample No. 7, sample No. 4 of Example-1 was exposed using a photographic exposure method. Samples No. 5 and No. 7 are the same as those shown in Example-1 except for the changes shown above. Example-1 for samples No. 6 and No. 7
The same process was performed.

The visual color proof finish is Example = 1
Sample No. 4 is Sample No. 6 Sample No.

This was a slightly better result than 7.

Example 3 An experiment similar to Example 1 was carried out using a direct positive silver halide emulsion in which latent image nuclei are generated inside by exposure and a positive image is directly formed by fogging treatment. The development processing method is shown below.

(Development processing method) Immersion in color developing solution 15 seconds 38°C light fog treatment l Color development with Qux for 10 seconds 2
Minutes 38°C Bleach-fixing 45 seconds 33°C Setting 1 minute 30 seconds
Dry at 33°C 1
minutes at 70°C. As a result, the same results as in Example-1 were obtained.

Furthermore, in terms of running fluctuations, when water-soluble dyes that are easily decomposed in the developing solution were used, the sensitivity fluctuations due to light fogging were small.

[Brief explanation of the drawing]

FIG. 1 illustrates a method for determining the leg photographic gradation of a photographic light-sensitive material. D represents the reflection density, and Ωo9E represents the exposure amount expressed logarithmically. F indicates fog value;
A is a point on the characteristic curve where D takes a value of F+0.25, and a represents the QogE value at that time. Similarly, B is the point at which D takes the value F + 0.75, and b represents the corresponding log E value.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support, the photographic constituent layer is yellow. , magenta and cyan water-soluble dyes, and each wavelength of 450 nm and 5 before the development process of the silver halide color photographic light-sensitive material.
A silver halide color photographic material characterized by having a reflection density of 0.8 or more at 50 nm and 700 nm.