JPH07159918A - Photographic element - Google Patents

Abstract

PURPOSE: To provide a photographic element having satisfactory scratch resistance and low sensitivity to a change of development time. CONSTITUTION: This photographic element has a substrate with a silver halide emulsion layer contg. at least 50% silver chloride, contains a hydrazide nucleus forming agent and an amine booster in the emulsion layer or a layer adjacent to it and can form a high contrast image by the combination. The emulsion is sensitive to radiant rays of 600-700nm wavelength owing to a tricyclic merocyanine dye represented by the formula.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having improved scratch resistance, and more particularly to radiation having a wavelength of 600 to 690 nm, such as helium-neon laser or laser diode dew. It relates to a light-sensitive material exposed to a light source, particularly to a light-sensitive material exposed in a graphic arts device.

[0002]

2. Description of the Related Art Several kinds of silver halide light-sensitive materials are prepared which are sensitive to red radiation having a wavelength of 600 to 690 nm and relatively insensitive to safe light illumination. The sensitizing dye has been previously proposed. For example, British Patent 1 471 701 and European Patent 0 363 104.
The specification describes the use of triheterocyclic dyes for this purpose. For many years, extremely hard photographic images have been required in graphic arts, and the printing industry has used a process known as infectious development to "lith" emulsions (usually high silver chloride content) into hydroquinone with low sulfite concentrations. Obtained by developing in a "lith" developer. However, such low sulphite concentration developer solutions are inherently unstable and are particularly unsuitable for mechanical processing.

In recent years, emulsions containing hydrazide nucleating agents have been used and processed with developers containing conventional amounts of sulfite ion, hydroquinone and / or metol or pyrazolidone. Such developers also contain substantially amine additives as described in US Pat. No. 4,269,929. Alternative developers containing amines are described in US Pat. Nos. 4,668,605 and 4,740,452. For example, U.S. Pat.
No. 43, No. 4,278,748, No. 4,031,127, No. 4,0
A number of hydrazides have been proposed for use in such light-sensitive materials in 30,925 and 3,323,643 and EP 0,333,435.

More recently, amine boosters have been incorporated into high contrast light sensitive materials with the advantage that no special developing solution has to be used to obtain the very high contrasts required by many graphic arts industries. was suggested. Such an amine booster is disclosed in JP-A-60-14.
0340 (1985) and JP-A-62-222241 (1987)
It is described in the publication and U.S. Pat. No. 4,975,354 (European Patent No. 0,364,166). 600-700nm
To prepare silver halide light-sensitive materials which are sensitive to radiation of wavelengths such as helium-neon laser or laser diode exposure sources, especially those exposed in graphic arts equipment. The sensitizing dye has been previously proposed. For example, US Patent No.
5,079,139 describes the use of triheterocyclic dyes having the general formula below for this purpose.

[0005]

[Chemical 2]

In the above formula, Y is S or Se, and L
¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a substituted or unsubstituted methine group, A is N—R ³ , O or S, and B is A is O. Sometimes N-R ⁴
And when A is NR ³ , NR ⁴ ,
S or O, R ¹ , R ² , R ³ and R ⁴ are
Each is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ⁵ is an alkyl group having 1 to 4 carbon atoms, n is 0, 1 or 2,
And X is a counterion, and here R ¹ ,
At least one of R ² , R ³ and R ⁴ is substituted with an acid or acid salt substituent.

[0007]

A problem with such photosensitive materials is that they do not have the desired resistance to scratches when processing them. Another challenge is
That is, the light-sensitive material has a remarkable sensitivity to variations in development time.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a photographic element that has good scratch resistance and low sensitivity to variations in development time. The element comprises a support having a silver halide emulsion layer containing at least 50% silver chloride, and the element comprises a hydrazide nucleating agent and an amine booster in or adjacent to the emulsion layer. booster), and a combination thereof can provide a high contrast image. The emulsion contains a tricyclic merocyanine dye represented by the following general formula:
It is sensitive to radiation with wavelengths of 00 to 700 nm.

[0009]

[Chemical 3]

In the above formula, R ¹ and R ² are each hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and R ³ , R ⁴ and R ⁵ are each 1 to 1 carbon atoms.
5 substituted or unsubstituted alkyl groups, wherein at least one of R ³ , R ⁴ and R ⁵ contains a water solubilizing group, X is a counterion, and n
Is 0 to 3. The sensitizing dyes not only sensitize the emulsion to light at 600-700 nm, but also improve their resistance to scratches and their sensitivity to development time.

[0011]

Specific Embodiment The water-solubilizing group on R ³ , R ⁴ and R ⁵ is a hydroxyl group or an acid group, for example, —OH group,
It is a -COOH group or -SO ₃ H group. Preferably two of R ³ , R ⁴ and R ⁵ contain a water solubilizing group. Specific examples of the alkyl group which R ¹ to R ⁶ may represent are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl or t-pentyl. These alkyl groups may be substituted with a halogen atom, an alkyl-substituted alkyl group, an aryl group or a substituted aryl group. The counterion X is preferably ammonium or an alkali metal, eg Na ⁺ .

The dye may be prepared by known methods.
For example, FM Hamer, Interscience, 1964, "Cyanine Dyes and Related Com
The dye may be prepared by the method described in "Pounds)". They are incorporated into silver halide emulsions in known manner as aqueous or alcoholic solutions. Specific examples of the dye to be used in the present invention include those having the following formula.

[0013]

[Chemical 4]

The dye may be present in the light-sensitive material in an amount of 5-500 mg, preferably 50-250 mg, and more preferably 100-200 mg, per mol of silver halide in the emulsion layer. The photographic light-sensitive material of the present invention can have various structures. For example,
Any of the following structures may be mentioned in which the lower and middle layers are preferably composed of a gelatin / polymer blend. The hydrazide and amine booster may be placed in the emulsion layer, the lower layer or the intermediate layer. The emulsion layer may contain an antifoggant.

[0015]

[Chemical 5]

The silver halide emulsions are preferably of the type that provide high contrast images as required in graphic arts applications. Such emulsions usually have high silver chloride and low silver iodide concentrations and may contain hydrazide nucleating agents. Such emulsions are found in Research Disclosure Item324.
10, November 1983, Kenneth Mason Publications, Emswo
Rth, Hants, United Kingdom.

The preferred amine boosters to be used in the present invention are those described in the above-mentioned European patent specifications, in which they are defined as amino compounds as follows: (1) containing at least one secondary or tertiary amino group, (2) containing within its structure at least three repeating ethyleneoxy units, and (3) at least 1, preferably It has an n-octanol / water partition coefficient (log P) of at least 3, and most preferably at least 4. log P is defined by the following equation.

[0018]

[Equation 1] (In the above formula, X is the concentration of the amino compound.)

Included within the scope of the amino compounds utilized in the present invention are monoamines, diamines and polyamines. These amines can be aliphatic amines, or they can include aromatic or heterocyclic moieties. Aliphatics present in amines,
Aromatic and heterocyclic groups can be substituted or unsubstituted groups. Preferably, the amino compound used in the present invention as the "internal booster" is a compound having at least 20 carbon atoms. Further, it is preferable that the ethyleneoxy unit is directly bonded to the nitrogen atom of the tertiary amino group.

Preferably the partition coefficient is at least 3, more preferably at least 4. Preferred amino compounds for the purposes of the present invention are bis-tertiary amines having a partition coefficient of at least 3 and a structure represented by the formula:

[0021]

[Chemical 6]

In the above formula, n is 3 to 50, more preferably 10
An integer with a value of ˜50, R ₁₂ , R ₁₃ , R ₁₄ and R
₁₅ is independently an alkyl group having 1 to 8 carbon atoms, R ₁₂ and R ₁₃ together represent an atom necessary for completing a heterocycle, and R ₁₄ and R _{13 Fifteen} represents the atoms necessary to complete the heterocycle together.
Another preferred group of amino compounds is at least 3
And a bis-secondary amine having a structure represented by the following formula.

[0023]

[Chemical 7]

In the above formula, n is 3 to 50, more preferably 10
Is an integer having a value from 50 to 50, each R being independently a straight chain or branched, substituted or unsubstituted, alkyl group having at least 4 carbon atoms. Specific amine boosters are listed in EP 0,364,166. The amine booster may be present in the emulsion in an amount of 1 to 25 g, preferably 1 to 10 g, and particularly preferably 1 to 3 g per mol of silver halide. Any hydrazide compound which functions as a nucleating agent and which in combination with the amine booster provides a hard tone can be used in the practice of this invention.

The hydrazide compound is incorporated into the photographic element. For example, a hydrazide compound can be incorporated into the silver halide emulsion layer. Alternatively, the hydrazide compound can be present in a hydrophilic colloid layer of the photographic element, preferably a hydrophilic colloid layer coated adjacent to the emulsion layer in which the action of the hydrazide compound is desired. Of course, it can be present in the photographic element distributed between or in emulsion and hydrophilic colloid layers, such as undercoating layers, interlayers and overcoating layers. Such a hydrazine compound can be of the formula: In the above R ⁷ -NHNHCHO formula, R ⁷ is lower than + 0.30, a phenyl nucleus having a Hammett sigma value derived electron withdrawing properties.

In the above formula, R ⁷ can take the form of a phenyl nucleus that is either electron-donating (positive) or electron-withdrawing (negative), however, phenyl having a high electron-withdrawing property. The nucleus produces a poor nucleating agent. The electron withdrawing or electron donating properties of a particular phenyl nucleus can be evaluated in relation to the Hammett sigma value. Preferred phenyl group substituents are those that are not electron withdrawing. For example, a phenyl group is a straight or branched chain alkyl group (eg, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, n-hexyl, n-octyl, tert-octyl, n-decyl, n-dodecyl and similar groups). The phenyl group can be substituted with an alkoxy group such that the alkyl portion of the alkoxy group can be selected from the above alkyl groups.

Further, the phenyl group may be substituted with an acylamino group. Specific acylamino groups include propanoylamino, butanoylamino, octanoylamino, benzoylamino and similar groups. In one particular preferred form, the alkyl, alkoxy and / or acylamino groups are in turn replaced by conventional photographic ballasts such as ballasting moieties of incorporated couplers and other immobile photographic emulsion additives. Typically, the ballast group contains at least 8 carbon atoms and is an aliphatic and aromatic relatively non-reactive group,
For example, selected from alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, alkylphenoxy and similar groups.

Alkyl and alkoxy groups, including ballast groups, preferably contain 1 to 20 carbon atoms, and acylamino groups, including ballast groups, preferably 2 to 21 carbon atoms. Contains atoms. It is generally believed that some of their ballasted versions have up to about 30 or more carbon atoms in these groups. Methoxyphenyl, tolyl (eg p
-Tolyl and m-tolyl) and ballasted butylamidophenyl nuclei are particularly preferred. Specific examples of particularly preferable hydrazine compounds include the following: 1-formyl-2- (4- [2- (2,4-di-tert-pentylphenoxy) butylamido] phenyl) hydrazine, 1-formyl-2- Phenylhydrazine, 1-formyl-2-
(4-Methoxyphenyl) hydrazine, 1-formyl-
2- (4-chlorophenyl) hydrazine, 1-formyl-2- (4-fluorophenyl) hydrazine, 1-formyl-2- (2-chlorophenyl) hydrazine, and 1-formyl-2- (p-tolyl) hydrazine Can be mentioned.

The hydrazide also contains an adsorption promoting moiety. This type of hydrazide contains an unsubstituted or monosubstituted divalent hydrazo moiety and an acyl moiety. Adsorption promoting moieties can be selected from among those known to promote adsorption of photographic additives to the surface of silver halide grains. Typically, such moieties contain sulfur or nitrogen atoms which can be complexed with silver or which have an affinity for the surface of the silver halide grain. Specific examples of preferred adsorption-promoting moieties include thioureas, heterocyclic thioamides and triazoles. Specific hydrazides containing an adsorption-promoting moiety include 1-
[4- (2-formylhydrazino) phenyl] -3-methylthiourea, 3- [4- (2-formylhydrazino) phenyl-5- (3-methyl-2-benzoxazolinylidene) rhodamine-6 -([4- (2-formylhydrazino) phenyl] ureylene) -2-methylbenzothiazole, N- (benzotriazol-5-yl)
-4- (2-formylhydrazino) phenylacetamide, and N- (benzotriazol-5-yl) -3
-(5-formylhydrazino-2-methoxyphenyl)
Propionamide and N-2- (5,5-dimethyl-
2-Thioimidazol-4-yl-idenimino) ethyl-
3- [5- (formylhydrazino) -2-methoxyphenyl] propionamide may be mentioned. A particularly preferred class of hydrazine compounds for use in the elements of the present invention are sulfonamide substituted hydrazines having one of the following structural formulas:

[0030]

[Chemical 8]

In the above formula, R ⁸ is alkyl having 6 to 18 carbon atoms, or a heterocycle having 5 to 6 ring atoms including sulfur or oxygen ring atoms, and R ⁹ is 1
Alkyl or alkoxy having 12 carbon atoms, X is 1 to about 5 amino alkyl having carbon atoms, thioalkyl or alkoxy, halogen or _{^{-NHCOR 10,, -NHSO 2 R 10}} , -CONR 10 R
¹¹ or a -SO ₂ R ¹⁰ R ^11, wherein, R ¹⁰ and R ¹¹ may be the same or different,
Hydrogen or alkyl having 1 to about 4 carbon atoms, and n is 0, 1 or 2.

R⁹The alkyl group represented by
Can be branched and substituted or unsubstituted
Can be The substituent has 1 to 4 carbon atoms.
Alkoxy, halogen atom (eg chlorine and fluorine)
), Or -NHCOR ^TenOr-NHSO₂R
^Ten(Where R^TenAre as defined above)
Be done. Preferred R alkyl groups contain 8 to 16 carbon atoms.
contains. Alkyl groups of this size are
Gives the formulation significant insolubility, which allows it to be processed during development.
These agents are transferred from the layer on which they are applied to the developing solution.
It is preferred because it reduces the tendency to leach. Compound represented by R
Tricyclic groups include thienyl and furyl.
These groups are alkyl having 1 to 4 carbon atoms.
Or even if it is substituted with a halogen atom, for example chlorine
Good.

The alkyl or alkoxy group represented by R ¹ can be straight or branched and can be substituted or unsubstituted. Substituents on these groups include alkoxy having 1 to 4 carbon atoms, halogen atoms (eg chlorine or fluorine), or —NHC.
It can be OR ¹⁰ or —NHSO ₂ R ¹⁰ where R ¹⁰ is as defined above. Preferred alkyl or alkoxy groups contain from 1 to 5 carbon atoms to give the hydrazide nucleating agent significant insolubility and reduce their tendency to leach out of the coated layer into the developing solution. To do.

The alkyl, thioalkyl and alkoxy groups represented by X contain from 1 to 5 carbon atoms and can be straight-chain or branched. When X is halogen, it can be chlorine, fluorine, bromine or iodine. If more than one X is present, then such substituents may be the same or different. A particularly preferred nucleating agent has the formula:

[0035]

[Chemical 9]

The hydrazide nucleating agent is used in the emulsion in an amount of 40 to 350 mg, preferably 60 to 350 m, per mol of silver halide.
g, and particularly preferably in an amount of 90-270 mg.
The photosensitive silver halide emulsion used in the light-sensitive material of the present invention may contain both silver bromide and silver iodide in addition to silver chloride. Preferably the iodide content is less than 10 mole percent. A preferred emulsion comprises 70 mole% chloride and 30 mole% bromide, although substantially pure silver chloride emulsions may be used. The particles may be doped with rhodium, ruthenium, iridium or another Group VIII metal, as is known in the graphic arts. The emulsion is a negative or direct positive emulsion and may be monodisperse or polydisperse.

Preferably the silver halide grains are doped with a Group VIII metal at a level in the range of 10 ^-9 to 10 ^-3 moles of metal per mole of silver, preferably 10 ^-6 to 10 ^-3 moles. The preferred Group VIII metal is rhodium. The emulsions used and the additives, binders, supports, etc. added to them can be
Disclosure) Item 308119, December 1989, Kenneth Maso
n Publications, Emsworth, Hants, United Kingdom.

The light sensitive silver halide contained in the photographic element may be processed following exposure by processing the silver halide in association with an aqueous alkaline medium in the presence of the developing agent contained in the medium or element. Thus, a visible image can be formed. It is a undeniable advantage of the present invention that the desired photographic element can be processed with conventional developers, as opposed to the specialized developers commonly used with lithographic elements to obtain very high contrast images. When a developing agent is incorporated in the photographic element, the element can be processed in the presence of an activator which is the same developer except that the developer is lacking in the developer composition.

Very high contrast images have a pH in the range of 11-12.3.
Values, but preferably lower pH values, for example 11
Lower pH values, and most preferably pH values in the range 10.3-10.5, are preferably used to process the photographic recording materials described herein. Although the developer is typically an aqueous solution, organic solvents such as diethylene glycol can be included to promote solubility of the organic components. The developer may be a traditional developing agent such as polyhydroxybenzene, aminophenol, paraphenylenediamine, ascorbic acid, pyrazolidone, pyrazolone, pyrimidine, dithionite, hydroxylamine or another traditional developing agent. Or include in combination.

It is preferred to use a combination of hydroquinone and 3-pyrazolidone developing agent. The pH of the developer can be adjusted with alkali metal hydroxides and carbonates, borax and other basic salts. Compounds such as sodium sulfate can be incorporated into the developer to reduce gelatin swelling during the development process. Also, compounds such as sodium thiocyanate can be present to reduce granularity. Chelating agents and sequestering agents such as ethylenediaminetetraacetic acid or its sodium salt can be present. In general, any traditional developing composition can be used in the practice of this invention. Certain specific photographic developers are described in the Handbook of Chemistry and Physics, No. 36.
Edition, Title "Photographic Formulae",
See 3001 et seq. And Processing Chemicals and
Formulas, 6th edition, published by Eastman Kodak Company (1963). Of course, the photographic elements are
It may be processed with conventional developers for lithographic photographic elements such as those illustrated in 3,573,914 and British Patent 376,600.

The support can be any photographic support, for example,
It may be a transparent film or a reflective paper support such as polyethylene coated paper. For paper materials, it is customary to use optical brighteners. They may be incorporated into the light-sensitive material by known methods, for example by dissolving a water-soluble optical brightener in a gelatin supercoat (layer furthest from the support). In some embodiments, water insoluble optical brighteners may be used. It may be absorbed into particles of a polymer dispersion as described in GB 1,504,949 and 1,504,950, or of a coupler solvent prior to incorporation in a layer of the light-sensitive material, for example a supercoat. It may be dissolved in droplets. In each case, there is no or acceptable residual dye stain. The following examples are included for a better understanding of the present invention.

[0042]

【Example】

Example 1 The photosensitive material used in this example consists of a gel underlayer, a photosensitive layer and a gel overcoat,
They were coated on a polyethylene terephthalate base with an antihalation pelloid layer designed to absorb red light. The photosensitive layer consisted of a 70:30 chlorobromide cubic monodisperse emulsion (edge length 0.22μ) with the addition of ammonium hexachlororhodate, which was coated with Ag 3.3 g / m ² . Total gel coverage is 3.
It is 83 g / m ² . Additives contained in the emulsion layer are sensitizing dyes,
2-methyl-mercapto-5-carboxy-6-methyl-tetraazaindene ^{(7.287mg / m 2), 1-} (3- acetamidophenyl) -5-mercaptotetrazole (0.7
11 mg / m ² ), 4-carboxymethyl-4-thiazoline-
Copolymer (C1) (silver) of 2-thione (2.137 mg / m ² ) and sodium salt of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid and 2-acetoxyethylmethacrylic acid (weight ratio 88: 5: 7). 22 g per mol).

Other additives added to the emulsion layer or the layer coated as the lower layer include 3,5-disulfocatechol, disodium salt (97.7 mg / m ² ), and a nucleating agent N3 ( 6.147mg / m ² )

[Chemical 10]

Amine booster B1 of the following formula (61.42 mg
/ m ² )

[Chemical 11] And hydroquinone (222.8 mg / m ² ) plus copolymer C1 (ratio of 0.20 mg / m ² ).

The overcoat consists of gel (0.5 g / m ² ), a surfactant to aid in coating it, as well as matte beads and colloidal silica to aid in film handling. The layer is cured with 3.5% bisvinyl sulfonyl methyl ether (BVSM) of total gel. For photographic evaluation, using a filter for simulating broad red exposure, 10 ^-6 seconds (s), Br
Increased amount with oad band Flash (BBF) sensitometer
The coating was exposed through a 0.1 step tablet. The coating was then processed through Kodak ™ RA2000 Developer, which was diluted 1 + 2 with water. Unless otherwise noted, all coatings were run through the Interpro 20RA-s processor at 35 ° C.
Developed for 30 s, fixed washed, and dried. For sensitivity to pressure, the coatings were abraded with a diamond stylus, loaded with a weight of 100 g and processed without exposure. The level of pressure is measured by the increase in density produced by the needle. The dyes used in the examples were as follows.

[0046]

[Chemical 12]

Three coatings were tested for pressure sensitivity. The dyes in the coating film were as follows. Coating 1 Dye 1 200 mg / Ag 1 mol Coating 2 Dye 2 150 mg / Ag 1 mol Coating 3 Dye 1 200 mg / Ag 1 mol Plus Dye 2 150 mg / Ag 1 mol

[0048]

[Table 1]

Coating 2 alone shows no increase in ABRADED D _min . Example 2 All coatings of Example 1 contained hydroquinone. In order to eliminate any effects that could lead to such results, this compound was omitted from the formulation and two more coatings were prepared. These coatings are as follows: Coating film 4 Dye 1 200 mg / Ag 1 mol Coating film 5 Dye 2 150 mg / Ag 1 mol

[0050]

[Table 2]

As can be seen from these results, the coating film containing Dye 2 alone showed almost no sensitivity to pressure, whereas the film containing Dye 1 showed high sensitivity. Explanation of terms used: D _min Base and fog density (densit
y) ABRADED D _min Base and fog density after abrasion (density) DELTA ABRADED D _min −D _min

Example 3 The photosensitive material used in this example is two layers consisting of an emulsion layer and a gel supercoat, or three layers consisting of a gel underlayer, an emulsion layer and a gel supercoat.
Both formats were coated on a polyethylene terephthalate base with a standard graphic arts antihalation pelloid designed to absorb red light. The photosensitive layer consisted of a 70:30 chlorobromide cubic monodisperse emulsion (edge length 0.22μ) to which ammonium hexachlororhodate was added, which was made of Ag 3.3.
It was applied at g / m ² . The total gel coverage in the two layers is 3.1g / m ²
And the layer gel coverage for the three layer format is 3.83 g / m ² . Another additive included in the photosensitive layer is the sensitizing dye (s), 2-methylmercapto-5-.
Carboxy-6-methyltetraazaindene (7.287mg
/ m ² ), 1- (3-acetamidophenyl) -5-mercaptotetrazole (0.711 mg / m ² ), 4-carboxymethyl-4-thiazoline-2-thione (2.137 mg / m ² ).
And copolymer (C1) (22 g / mol silver).

Added to either the emulsion layer or the lower layer
Another additive is 3,5-disulfocatechol,
Disodium salt (97.7mg / m²), A nucleating agent N1 (6.147)
mg / m ²), Internal booster B1 (61.42mg / m²)and
Hydroquinone (222.8mg / m²) Is mentioned. 3 layer fo
-For mat, 20g / m of Copolymer C1²Include in the lower layer with
It Overcoat is gel (0.5g / m²), And
A surfactant that assists coating
Made of matte beads and colloidal silica to aid
It The layer was hardened with 3.5% BVSM of total gel.
Be converted.

For photographic evaluation, a filter for simulating broad red exposure was used for 10 ^-6 s,
The coatings were exposed through a step tablet with a Broad band Flash (BBF) sensitometer in increments of 0.1. The coating was then processed through Kodak ™ RA2000 Developer, which was diluted 1 + 2 with water. Unless otherwise noted, all coatings were run through the Interpro 20RA-s processor at 35 ° C.
Developed for 30 s, fixed washed, and dried. Three coatings were tested for pressure sensitivity. The dyes in the coating film were as follows. Coating 1 Dye 1 (Comparative) 200 mg / Ag 1 mol Coating 2 Dye 2 (Invention) 150 mg / Ag 1 mol Coating 3 Dye 1 200 mg / Ag 1 mol Plus Dye 2 150 mg / Ag 1 mol

The processor used for the time and temperature test was Inte
It was rpro 20RA-s. This processor has good stirrability during the development process. Further processing was carried out in the same manner on a Kodamatic 65A processor without recycling the developer. All coatings were stepwise tablet exposed and exposed at a density (densit
y) is the actual density point (Practical Density Point, PD
P) was measured.

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

Example 4 The same base coating used in Example 3 was used to investigate the effect of bromide enhancement on coating sensitometry. Increasing concentrations of KBr were added to a sample of Kodak ™ RA2000 Developer and the coating was applied at 35 ° C for 30 s.
Developed and compared for changes in PDP. The four coatings were tested for development latitude at 35 ° C. Coating 1 Dye 1 200 mg / Ag 1 mol Coating 2 Dye 2 (invention) 150 mg / Ag 1 mol Coating 3 Dye 1 200 mg / Ag 1 mol Plus Dye 2 (invention) 150 mg / Ag 1 mol Coating 4 Dye 1 200 mg / Ag 1 Mole Plus Dye 3 25 mg / Ag 1 mol

[0060]

[Table 6]

As can be seen from these examples, the dyes of the invention, such as Dye 2, provide similar spectral sensitization when compared to dyes such as Dye 1, when coated in a nucleation format. It is less sensitive to variations in processing cycles.

[0062]

A photographic element comprising a support having a silver halide emulsion layer containing at least 50% silver chloride, the hydrazide nucleating agent and amine booster in or adjacent to said emulsion layer. The photographic elements containing ## STR3 ## have improved scratch resistance and sensitivity to variations in development time.

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[Procedure amendment]

[Submission date] December 21, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] (In the above formula, R ¹ and R ² are each hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and R ³ , R ⁴ and R ⁵ are each 1 to 5 carbon atoms. A substituted or unsubstituted alkyl group of and
At least one of R ³ , R ⁴ and R ⁵ contains a water solubilizing group, X is a counterion, and n is 0-3) and the tricyclic merocyanine dye of 600-700 nm A photographic element which is sensitive to radiation of the wavelength

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Claims (1)

[Claims] 1. A photographic element comprising a support having a silver halide emulsion layer containing at least 50% silver chloride, said photographic element comprising hydrazide nucleation in or adjacent to said emulsion layer. And an amine booster, the combination of which can provide a high-contrast image, wherein the emulsion has the general formula: (In the above formula, R ¹ and R ² are each hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and R ³ , R ⁴ and R ⁵ are each 1 to 5 carbon atoms. A substituted or unsubstituted alkyl group of and
At least one of R ³ , R ⁴ and R ⁵ contains a water solubilizing group, X is a counterion, and n is 0-3) and the tricyclic merocyanine dye of 600-700 nm A photographic element which is sensitive to radiation of the wavelength