JP2831020B2 - Sensitizing fee for high chloride silver halide photographic compositions - 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

Description: FIELD OF THE INVENTION The present invention relates to photographic technology, and more particularly to spectral sensitization of silver halide emulsions having a high silver chloride concentration.

[Conventional technology]

Photosensitive silver halide emulsions containing primarily 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 the processing speed is fast,
It is also known that the presence of significant amounts of iodide (e.g., greater than 1 mole%) in an emulsion can hinder the development of exposed silver halide.

A problem with the use of emulsions containing high concentrations of silver chloride was that the development speed of blue-sensitive emulsions was 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.

[Problems to be solved by the invention]

Many dyes known as dyes that sensitize 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.

[Means for solving the problem]

 According to the present invention, a dye having the following structure (I)
At least 80 mol% silver chloride spectrally sensitized
And silver halide containing 1 mol% or less of silver iodide
True composition:(Where R₁Is halogen, substituted or unsubstituted phenyl
R or a substituted or unsubstituted styryl group; R_TwoAnd R_ThreeAre each independently a substituted alkyl group,
An alkenyl group or a substituted aryl group,
Z is substituted with a solubilizing group to complete a substituted or unsubstituted naphthyl ring.
Indicates the required atom, and X⁺Is a cation, and the structure (I) has the following structure (I
I):(Where R is (CH_Two)_ThreeSO_ThreeH or (CH_Two)_ThreeSO _Three NH (C_TwoH_Five)_ThreeTo
) Is provided.

(Embodiment)

According to formula (I), R ₁ is a halogen (eg, C1, F or I), a substituted or unsubstituted phenyl group (eg, phenyl, 4-chlorophenyl, 3-methylphenyl), or a substituted or unsubstituted styryl group (eg, For example, -CR = CR-
φ, wherein each R is independently H or a substituent such as a lower alkyl group, and the phenyl group may be substituted with a substituent such as an alkyl group, a halogen or an alkoxy group). In a preferred embodiment, R ₁ is halogen,
In a more preferred embodiment, R ₁ is fluoro or chloro.

Preferably, R ₂ and R ₃ are each independently a C 1-6 having an anionic solubilizing group substituent (eg, sulfoethyl, carboxypropyl, sulfatopropyl).
Having a substituted alkyl group having an anionic solubilizing group substituent (for example, p-sulfobenzyl),
It is a substituted alkenyl group having 3 to 10 carbon atoms having 12 aryl groups or an anionic solubilizing group substituent (for example, 2-carboxyaryl). As a more desirable specific example, R ₂ and R ₃ are each independently a substituted alkyl group having 1 to 6 carbon atoms having an anionic solubilizing group substituent. Anionic solubilizing groups as substituents on nitrogen substituents of cyanine dyes are well known in the art and include, for example, sulfo, carboxy and sulfato (preferably sulfo)
Is raised.

Z represents an atom necessary to complete a substituted or unsubstituted naphthyl ring.

X ⁺ is a cation such as sodium or triethylammonium.

R ₁ , R ₂ , R ₃ and Z are each one of the following substituents, an alkyl group (eg, methyl, ethyl, propyl, isobutyl, pentyl), an alkenyl group (eg, allyl, carboxyethyl), an aryl group ( For example, phenyl, benzyl), an alkoxy group (eg, methoxy, ethoxy), an allyloxy group (eg, phenyloxy), a halogen (eg, fluoro, chloro), a hydroxy group, a cyano group, and the like may be substituted.

Examples of dyes of formula (I) include: The amount of sensitizing dye of formula (I) useful in the present invention is preferably in the range of 0.1 to 1.0 mmol per mole of silver halide, more preferably 0.2 to 0.7 mmol per mole of silver halide. The optimum dye concentration can be determined by a known method.

The dyes of formula (I) are available from Hamer, Cyanine Dyes and Related
Compounds (1964) and James. The Theory of the Phot
It is synthesized by known techniques as described in, ographic Process 4th, 1977. Examples of the synthesis of representative dyes of formula (I) are shown below.

The silver halide predominantly sensitized by the dye of formula (I) is rich in chloride. By high concentration of chloride is meant silver halide containing at least 80 mol%, preferably 95 mol% or more of 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 are 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 described in Research D
isclosure 17643, December 1978 ( Research Discl.
osure I) and Mees, The Theory of the Photog
It can be prepared by a method described in raphic Process and the like. These include the preparation of ammonia rubber emulsions, the preparation of neutral or acidic emulsions, and other known methods. In these methods, a water-soluble silver salt and a water-soluble halide are generally mixed in the presence of a protective colloid, and the temperature and the temperature are adjusted to a value suitable for silver halide precipitate formation.
Adjusting pAg, pH value, etc. is 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. Compounds and techniques useful for chemical sensitization of silver halide are known and are available at Research Disclos.
ure I and the references cited therein.

The dyes of the silver halide of the formula (I), Research Dis
It is sensitized by any known method, such as that described in closure 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. dye/
The silver halide emulsion is mixed with the dispersion of the color image-forming coupler immediately before coating or prior to coating (eg, 2 hours before). Two hours before is preferred because the dye of formula (I) improves the stability of the silver halide / color image forming coupler in gelatin dissolved.

The dyes of the formula (I) themselves are used for sensitizing silver halides, but also exhibit a sensitizing effect on other silver halides over a wide or different wavelength range or make the silver halides stronger. It can also be used in combination with other sensitizing dyes that sensitize.

In a preferred embodiment of the invention, the dyes of formula (I) are used for sensitizing silver halide in photographic emulsions which can be coated as a layer on a photographic element. Essentially any type of emulsion (eg, surface-sensitive emulsions or non-fogging latent image forming emulsions, negative working emulsions or direct positive working emulsions, such as surface fogging emulsions, etc., for example Research Disclosur)
eI etc.) can be used.

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), gelatin derivatives Natural products such as (eg, acetylated gelatin, phthalated gelatin, etc.), and others described in Research Disclosue 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),
Binders described in Research Disc-losure I, such as acrylamide polymers, polyvinyl acetal, polymers of alkyl and sulfoalkyl acrylate and methacrylic acid, hydrolysates of polyvinyl acetic acid, polyamides, polyvinyl pyridine, methacrylamide copolymers and related compounds thereof Is included. Excipients can 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,
Chemical sensitizers such as palladium, iridium, osmium, rhenium, phosphorus or combinations thereof are included. Chemical sensitization can occur at pAg values of 5-10, pH values of 5-8, and temperatures of 30-80 ° C., Research Disclosure , June 1975,
No. 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,
Also included are development modifiers such as development inhibitor releasing couplers, timed 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.
It is described in arch Discloruse I and the references cited therein.

The emulsion may also contain a whitening agent such as a stilbene brightener. Such brighteners are known and have been used to neutralize stains.
Many of the dyes of formula (I) (eg, where R ₁ is fluorine)
Less dye stain than other dyes.

And silver halide sensitized by the dye of formula (I). The emulsion layers are coated simultaneously or sequentially with layers containing various additives known as photographic elements, such as other emulsion layers, subbing layers, filter dye layers, interlayers or top layers. 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, medical scalpel coating, stretch flow coating, and curtain coating, among others. 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 either 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,
The red-sensitive layer also has a cyan coupler. The photographic compositions of the present invention are advantageously utilized in blue sensitive layers of color photographic elements. These color image forming couplers are well known with an array of other elements, for example, Research
Disclosure I.

Photographic elements containing the compositions of this invention can be prepared by known methods such as Rese.
arch Disclosure I or James, The Theory of the Pho
It can be developed by a photographic developer using many developing compositions described in tographic 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.

〔Example〕

 The present invention is further described in the following examples.

Synthesis Example 1 Preparation of Dye 1 16.5 g of anhydrous-5-fluoro-2-methyl-3-sulfopropylbenzothiazolium hydroxide, 19.5 g of anhydrous-2-hydroxyiminomethyl-1- (3-sulfopropyl ) -Naphtho- [1,2-d] -thiazolium hydroxide, 412 ml of dimethylformamide and 7 ml of acetic anhydride were heated to 60 ° C and 12 ml of triethylamine were added. The mixture was heated to 90-95 ° and cooled. The precipitate is filtered off, washed with dimethylformamide, acetone and ether, respectively and air-dried to 28.8
g of crude dye 1 were obtained.

Crude dye 1 was suspended in 325 ml of boiling pyridine and 42 ml of water were added. A precipitate precipitated immediately. The mixture was cooled and filtered. The solid was washed with pyridine followed by acetone and air dried. 17.8 g of this product were suspended in 180 ml of boiling pyridine, 37 ml of water were added and the mixture was filtered. The filtrate
Upon precipitation with 300 ml of pyridine, a precipitate precipitated out, and the mixture solidified upon boiling the mixture. 15 per precipitate obtained
This procedure is repeated with 7 ml of pyridine and 43 ml of water, and further diluted with pyridine to 350 ml. The resulting precipitate was filtered and dried to give 14.3 g of Dye 1, λmax = 441 nm (in methanol), ε = 7.38 × 10 ⁴ .

Examples 1 and 2 Dyes 1 and 2 Each was a gold sulfide sensitized silver chloride emulsion containing 0.44 mmol / mol of silver (particle size 0.
7 μm) 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 following formula The dispersing coupler was added to the dye / silver chloride emulsion just before coating. The elements include, above and below the emulsion layer,
The gel upper layer (1076 mg / m ² ) and lower layer (1076 mg / m ² )
It was the coat of m ^2).

The elements are exposed to white light (ultraviolet and heat absorbing filters on a 3000K tungsten source) or a light source designed to mimic a color negative print exposure light source (Wratten 65M and 140Y filter on a 3000K tungsten source). This element is processed by a three-stage color development operation (45
Seconds, 35 ° C), bleach fixation (45 seconds, 35 ° C), and stable or water washing (90 seconds, 35 ° C), and then dried (60 seconds, 6 ° C)
0 ° C). The composition of the above solution is as follows.

1) Color developing solution 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 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 blocking agent 0.8 ml Potassium carbonate 25.0 g Water was added to adjust the pH to 1, and the pH was adjusted to 10.12.

2) Bleach fixative 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 1 to adjust the pH to 6.2.

3) Stabilizing solution Sodium citrate 1g Water was added to 1 to adjust pH to 7.2.

The λmax and relative speed (relative to the control dye) of the sensitized emulsion are shown in Table I below.

The results in Table 1 show that the emulsion containing the dye of formula (I) was significantly faster than the control dye. For comparison, when these dyes were used for sensitization of silver bromoiodide (2.7% iodine) emulsion, no significant difference was observed between the speed of the formula (I) and the speed of the control dye. Thus, the speed increase observed in these examples was not obtained with silver halide emulsions other than high chloride emulsions where the present invention is useful.

Examples 3 and 4 For comparison, dye 1 according to the invention and control dyes B, C
And D in the same manner as in Examples 1 and 2 (excluding the gelatin lower layer 30).
And 76 mg / m ²⁾ and the element was prepared. The control dye C is the compound 1-1 of EP 256,858 and the dye of Example 5 of U.S. Pat. No. 4,250,244.

The element was exposed to a color negative print exposure source, developed according to the methods of Examples 1 and 2, and the relative photographic speed was measured. The results are shown in Table II below.

Table II Dye Speed 1 871 B 23 C 389 D 126 The results in Table II show that the dye of formula (I) was significantly faster than the control dye for emulsions useful in the present invention.

〔The invention's effect〕

Photographic compositions wherein the dye of formula (I) comprises silver halide with a high silver chloride content have increased sensitivity to blue light.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Pamela Mac Ferguson New York, USA 14425, Farmington, Yarn Road 5955 (56) References JP-B-59-11094 (JP, B2) JP-B-63-23530 (JP) , B2) JP 6-12427 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/12

Claims (1)

(57) [Claims] 1. A spectrophotometer comprising a dye having the following structure (I):
Sensitized, at least 80 mol% silver chloride and 1 mol
Photographic composition containing silver halide containing less than 1% silver iodide
Stuff: (Where R₁Is halogen, substituted or unsubstituted phenyl
R or a substituted or unsubstituted styryl group; R_TwoAnd R_ThreeAre each independently a substituted alkyl group,
Lucenyl or substituted aryl, anionic soluble
Z is required to complete a substituted or unsubstituted naphthyl ring.
Indicates the key atom, and X⁺Is a cation, but the structure (I) has the following structure (II):(Where R is (CH_Two)_ThreeSO_ThreeH or (CH_Two)_ThreeSO _Three NH (C_TwoH_Five)_ThreeTo
))).