JP3122412B2 - Color negative printed photographic element and method of forming an image thereon - Google Patents

Abstract

Dyes of the formula: <CHEM> where R1 is halogen, substituted or unsubstituted phenyl, or substituted or unsubstituted styryl, R2 and R3 are each independently substituted alkyl, substituted alkenyl, or substituted aryl that are substituted with an anionic solubilising group, Z represents the atoms necessary to complete a substituted or unsubstituted naphthyl ring, and X<+> is a cation, are disclosed as sensitizing dyes for photographic compositions containing silver halide that is high in silver chloride content, low in silver iodide content, or both.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic technology,
More particularly, it relates to a color negative print photographic element and a method of forming an image thereon.

[0002]

BACKGROUND OF THE INVENTION Light-sensitive silver halide emulsions containing mainly silver bromide, such as silver iodide or pure silver bromide, are widely used in photographic compositions. Emulsions having a high silver chloride content (eg, at least 80 mole% silver chloride) have been traditionally preferred because they can be processed faster than silver halide emulsions having a low silver chloride content. Although processing speeds are certain to be true, it is also known that the presence of significant amounts of iodide (eg, 1 mol% or more) in emulsions hinders development of exposed silver halide.

A problem in using an emulsion containing a high concentration of silver chloride is that the developing speed of a blue-sensitive emulsion is not sufficient. This is because high silver chloride emulsions are inherently less sensitive to blue light than low silver chloride emulsions. Blue sensitizing dyes can be used to spectrally sensitize silver chloride to blue light. Such dyes are described in EP 256,858 and U.S. Pat. No. 4,250,244.

[0004]

Many of the dyes known as dyes for sensitizing high silver chloride emulsions to blue are not sufficiently sensitized to blue light. Therefore, there is a strong demand for a blue sensitizing dye which gives silver halide emulsions having a high chloride content higher sensitivity to blue light.

[0005]

According to the present invention SUMMARY OF], will be arranged silver halide emulsion layer of the photosensitive yellow coupler against free Mikatsu blue light on a support, said silver halide emulsion Has the following structure (I):

[0006]

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[0007] The dyes having been spectrally sensitized comprises silver halide grains containing at least 80 mole% of silver and 1 mol% of silver iodide chloride, and the dye is silver halide grains The emulsion layer was sensitized by addition to the emulsion after precipitation, and the emulsion layer had the following structure (II):

Embedded image A color negative printed photographic element is provided which does not contain the compound of formula (I ). According to the present invention, there is also provided a method of exposing a color negative on a color negative printed photographic element using a tungsten light source to form an image on the photographic element, wherein the photographic element is halogenated by a dye having the above structure (I). halide grains are spectrally sensitized photosensitive silver halide emulsion comprising silver halide grains containing at least 80 mole% of silver and 1 mol% of silver iodide chloride respect containing Mikatsu blue light
Sexual least one light-sensitive silver halide, but comprising a support having emulsion layers said emulsion layer is the structure of (II)
An image forming method is provided that does not contain a compound .

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The use of a sensitizing dye having the above structure according to the present invention can significantly improve the sensitivity to blue light. The dye of formula (I) has the following two structures.

[0009]

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The amount of the sensitizing dye of the above-mentioned structure (I) useful in the present invention is preferably in the range of 0.1 to 1.0 mmol per mol of silver halide, more preferably 0.2 to 0.7 mmol per mol of silver halide. The optimum dye concentration can be determined by a known method.

The dye of the structure (I) is Hamer, Cyanine D
yes and Related Compounds (1964) and James. The T
It can be synthesized by a known technique described in heory of the Photographic Process 4th, 1977 and the like.

The silver halide predominantly sensitized by the dye of the structure (I) contains a large amount of chloride. High concentration of chloride means at least 80 mol%, preferably 95 mol%
It means the above-mentioned silver halide containing silver chloride. It is also desirable that the emulsion has a low iodine content. A low iodine content means a silver halide containing 1 mol% or less of silver iodide, preferably a silver halide containing no more than 0.5 mol% of silver iodide.

The silver halide grains used in the present invention do not have to be specific types of silver halide grains which can be used in the practice of the present invention. The grain size of the silver halide may be in any distribution useful for known photographic compositions, and may be polydisperse or monodisperse. The average particle size is desirably 0.05 μm to 1.5 μm.

The silver halide grains used in the present invention are:
Research Disclosure 17643, December 1978 (hereinafter Re
search Disclosure I) and Mees, The Theory
It can be prepared by a method described in ofthe Photographic Process or the like. These include the preparation of ammonia rubber emulsions, the preparation of neutral or acidic emulsions, and other known methods. These methods generally involve mixing a water-soluble silver salt and a water-soluble halide salt in the presence of a protective colloid, and adjusting the temperature, pAg, pH value, and the like to values suitable for silver halide precipitation. included.

The silver halide used in the present invention is preferentially subjected to chemical sensitization with a gold sensitizer (for example, gold sulfide) or another known compound. It is known for compounds and techniques useful for chemical sensitization of silver halide, resear
ch Disclosure I and the references cited therein.

The silver halide is sensitized with the dye of the structure (I) by any known method as described in Research Disclosure I. Dyes are added to the emulsion of silver halide grains and the hydrocolloid at the same time as or prior to coating the emulsion on the photographic element. The dye / silver halide emulsion is mixed with the dispersion of the color image-forming coupler immediately prior to coating or prior to coating (eg, 2 hours).
Two hours before, the dye of the structure (I) is silver halide /
It is desirable because the stability of the color image forming coupler in gelatin is improved.

The dye of the above-mentioned structure (I) is used for sensitizing silver halide by itself, and also shows a sensitizing effect on other silver halides in a wide wavelength range or a different wavelength range, Silver can also be used in combination with other sensitizing dyes that sensitize silver more strongly.

In a preferred embodiment of the invention, the dye of structure (I) is used for sensitizing silver halide in a photographic emulsion which can be coated as a layer on a photographic element. Essentially, such as any type of emulsion (such as surface-sensitive emulsions or latent image forming emulsions without head, negative-working emulsions, or such as surface head emulsions, direct-positive emulsions, other example Re
search Disclosure I).

Photographic emulsions generally include an excipient (vehicle) for coating the emulsion as a layer of a photographic element.
Useful excipients include proteins, protein derivatives, cellulose derivatives (eg, cellulose esters), gelatin (eg, alkali-treated bovine bone or skin gelatin, or acid-treated porcine skin gelatin).
Natural products such as gelatin derivatives (eg, acetylated gelatin, gelatin phthalate, etc.), and Research Discl
Others are listed in osure I. A hydrophilic water-permeable colloid is also a useful excipient or excipient developing agent. These include synthetic polymeric peptizers, carriers and / or poly (vinyl alcohol), poly (vinyl lactam), acrylamide polymers, polyvinyl acetal, polymers of alkyl and sulfoalkyl acrylates and methacrylic acid, hydrolysates of polyvinyl acetic acid, Research Discl such as polyamide, polyvinyl pyridine, methacrylamide copolymer and related compounds
osure I binders are included. Excipients may be in any amount that is considered useful in photographic emulsions.

Emulsions include any other useful photographic emulsion additives. These include active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium,
Chemical sensitizers such as rhenium, phosphorus or combinations thereof are included. Chemical sensitization pAg values 5 to 10, pH value 5 to 8, Research Disclosure can occur at a temperature 30 to 80 ° C.
I, June 1975, paragraph 13452 and U.S. Pat. No. 3,772,031.

Other additives include fogging agents, stabilizers, filter dyes, light absorbing or reflecting dyes, excipient hardeners such as gelatin hardeners, coating agents, dye-forming couplers, development inhibitor releasing couplers. Development modifiers, time-controlled development inhibitor releasing couplers, and bleach accelerators. These additives and the manner in which they are incorporated into emulsions and other photographic layers are known and are described in Research Disclosure I and the references cited therein.

The emulsion may also contain a stilbene brightener (bright
ener). Such brighteners are known and have been used to neutralize stains. Many of the dyes of the structure (I) (for example, those in which R ₁ is fluorine) have less dye stain than other dyes.

The emulsion layer containing silver halide sensitized by the dye of the above-mentioned structure (I) may contain various additions known as photographic elements such as other emulsion layers, undercoat layers, filter dye layers, intermediate layers or upper layers. It is coated simultaneously or sequentially with the layer containing the agent. These include antifog, oxidized developer scavengers, DIR couplers, antistatic agents, optical brighteners, light absorbing or light scattering dyes, and the like.

The photographic element layer can be coated on the support using known techniques. These techniques include dip or dip coating, roller coating, reverse roll coating, air knife coating,
Some include pharmaceutical scalpel coatings, stretch flow coatings and curtain coatings. The coated layer may be chill set, dried, or both. Drying is facilitated by known techniques, such as conduction, convection, radiant heating, or a combination thereof.

Photographic elements containing the compositions of this invention can be black and white or color. Color photographic elements generally include three silver emulsion layers or sets of layers. The blue photosensitive layer has a yellow coupler, the green photosensitive layer has a magenta coupler, and the red photosensitive layer has a cyan coupler. The photographic compositions of the present invention are advantageously utilized in blue sensitive layers of color photographic elements. These color imaging couplers are well known, along with an array of other elements, and are described, for example, in Research Disclosure I.

Photographic elements containing the compositions of this invention can be prepared by known means, such as Research Disclosure I or James, The Theor.
y of the Photographic Process 4th, 1977. Elements containing high chloride silver halide as a photographic component can be processed particularly advantageously by high speed processing with so-called high speed developers. Examples are described in Examples 1 to 3 below.

[0027]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 Preparation of Dye 1 27.8 g of anhydrous-2-hydroxyimino-methyl-1-
A mixed solution of (3-sulfopropyl) -β-naphthothiazolium hydroxide in acetonitrile: water volume ratio of 4: 1 1.
The slurry suspended in 93 l was heated to 70 ° C.
31 ml was added. Subsequently, this was mixed with 24.0 g of a mixture of anhydrous 5-chloro-2-methyl-3-sulfopropylthiazolium hydroxide in a 4: 1 volume ratio of acetonitrile: water.
The solution was dissolved in a solution obtained by adding 23.7 ml of triethylamine to 67 ml, and completely dissolved. The reaction was heated at reflux for 5 minutes and cooled. The supernatant was gently filtered. The obtained mud solid
When added to 450 ml of boiling acetonitrile, it solidified and was filtered while hot. The solid was washed with hot acetonitrile and dried by suction to give a yield of 43.9 g. The solid was extracted with 700 ml of boiling methanol, and the extract was cooled and filtered. The obtained solid was dried in a vacuum oven at 60 ° C. to give Dye 1: λma = 444 nm (in methanol),
ε = 7.98 × 10 ⁴ , 35.3 g were obtained.

Example 1 Dye 1 is compared with the formula for Dye A.

[0030]

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Each has the following coverage: 0.44
A gold sulfide sensitized silver chloride emulsion containing 0.7 mmol / mol of silver (particle size 0.7 μm) was coated on a polyester support.

Silver 344 mg / m ² Gelatin 1658 mg / m ² Fogging agent ^* 75 mg / mole silver coupler ^** 1076 mg / m ²

^* 1- (3-acetamidophenyl) -5
Mercaptotetrazole ^** Color coupler of the formula

[0034]

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The dispersing coupler was added to the dye / silver chloride emulsion just prior to coating. Its elements, and below the top of the emulsion layer, respectively, and the coated gel layer (1076mg / m ²⁾ and the lower layer (1076mg / m ^2).

The element may be white light (3000 ° K tungsten light source with ultraviolet and heat ray absorbing filters) or light source designed to simulate a color negative print exposure light source (3000 light source).
Exposure to a ° K tungsten light source (Wratten 65M and 140Y filter). This element was processed by a three-stage color development operation (45 seconds, 35 ° C), and bleach fixed (45 seconds, 35
° C), and washed under stability or with water (90 seconds, 35 ° C), and then dried (60 seconds, 60 ° C). The composition of the above solution is as follows.

1) Color developer Liquid lithium salt of sulfonated polystyrene 0.25 ml Triethanolamine 11.0 ml N, N-diethylhydroxylamine (85% by weight) 6.0 ml Potassium sulfite (45% by weight) 0.5 ml Color developer (4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methyl-phenylenediamine sesquisulfuric acid hydrochloride-hydrate 5.0 g Stilbene compound pollution reducing agent 2.3 g Lithium sulfate 2.7 g Potassium chloride 2.3 g Potassium bromide 0.025 g Sequestering agent 0.8 ml Potassium carbonate 25.0 g Water was added to 1 liter, and the pH was adjusted to 10.12.

2) Bleach fixing solution Ammonium sulfite 58 g Sodium thiosulfate 8.7 g Ferric ammonium salt of ethylenediaminetetraacetic acid 40 g Acetic acid 9.0 ml Add water to make 1 liter, and adjust the pH to 6.2.

3) Stabilizing solution 1 g of sodium citrate water was added to make 1 liter, and the pH was adjusted to 7.2. The .lambda.max and relative speed (relative to the control dye) of the sensitized emulsion are shown in Table I below.

[0040]

[Table 1]

The results in Table I show that the emulsion containing the dye of structure (I) was significantly faster than the control dye. This increase in speed cannot be obtained with silver halide emulsions other than the high chloride emulsion where the present invention is useful.

Example 2 For comparison, use Dye 1 of the present invention and Control Dye B in the same manner as in Example 1 except that the gelatin lower layer was 3076 mg / m ^2.
The element was prepared. Control Dye B is compound 1-1 of European Publication 256,858.

[0043]

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The element was exposed to a color negative print exposure source, developed according to the method of Example 1, and the relative photographic speed was measured. The results are shown in Table II below.

[0045]

[Table 2]

The results in Table II show that the dye of structure (I) was significantly faster than the control dye for the emulsions useful in this invention.

[0047]

The photographic composition wherein the dye of structure (I) comprises silver halide having a high silver chloride content increases the sensitivity to blue light.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Wayne Woodrow Weber The Second United States, New York 14472, Hornoy Falls, Partridge Hill 38 (72) Inventor Pamela Mac Ferguson United States, New York 14425, Farmington, Yarn Road 5955 (56 References JP-A-64-81946 (JP, A) JP-A-1-106603 (JP, A) JP-A-1-124845 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) G03C 1/16

Claims (2)

(57) [Claims] The method according to claim 1] Yellow couplers against free Mikatsu blue light
A light-sensitive silver halide emulsion layer is disposed on a support, and the silver halide emulsion has the following structure (I): At least spectrally sensitized by a dye having
Silver halide grains containing 80 mol% of silver chloride and 1 mol% or less of silver iodide, and the dye is a silver halide grain.
Although There are those sensitized by the addition to the emulsion after the precipitation,
It said emulsion layer is the following structure (II): ## STR2 ## Negative color photographic element containing no compound . 2. A method of exposing a color negative on a color negative print photographic element using a tungsten light source to form an image on the photographic element, wherein the photographic element has the following structure (I): The silver halide grains are spectrally sensitized with a dye having, including Mikatsu blue silver halide emulsion comprising silver halide grains containing at least 80 mole% of silver and 1 mol% of silver iodide chloride Although comprising a support having at least one photosensitive silver halide emulsion layer sensitive to light, the emulsion layer is the following structure (II): ## STR4 ## An image forming method which does not contain the compound of the above .