JPH024238A - Hardtone photographic element - Google Patents

Abstract

PURPOSE: To decrease irregular development in a rapid access treatment of a high contrast photographic element by adding a specified component to a coating layer with a synergistic effect. CONSTITUTION: This silver halide photographic element has a negative silver halide emulsion layer which forms a surface latent image and contains a hydrazine compd., and the element is not exposed to active electromagnetic waves to give developing property to the element. To the coating layer of a high- contrast silver halide emulsion containing hydrazide, an accelerating agent for development of silver halide and/or a surfactant selected from among alkoxylated alcohols and fluorine surfactants are added to obtain a high density. The accelerator consists of 3-pyrazolidinon or 2-pyrazoline developer and its amt. is controlled to an effective amt. to decrease eddy patterns. Thus, irregular development of a high contrast film can be decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to photographic elements, particularly those with very high contrast.
The present invention relates to high contrast photographic elements and, more particularly, to the reduction of non-uniform development in high contrast photographic elements in high contrast photographic elements.

BACKGROUND OF THE INVENTION The use of hydrazine in photographic emulsions or developer baths to form high-contrast lithographic images has been known for some time, first in U.S. Pat. No. 2,419,975. It was disclosed in the issue. This photographic system required very high levels of - for development, and the developer bath was short-lived and unstable in air.

U.S. Pat. No. 4,269,929 discloses the use of a high sulfite content in a developer consisting of a mixture of a developer and an alkanolamine with an improved hydrazide in the emulsion, which system provides high contrast An intermediate range (eg, 10.5 to 12.3) can be used to form black-and-white lithographic images.

U.S. Pat. No. 4,560,638 discloses the use of non-ballasted solid hydrazide which is particularly effective in providing improved halftone quality and reduced speckle fog in halftone high contrast images. It is incidentally disclosed that the emulsion may contain a developing agent (column 11 64).
line ~ 12 column 8 line).

U.S. Pat. No. 4,618,574 describes additives for high contrast aryl hydrazide-containing silver halide emulsions that can reduce speckled capri. There K also incidentally discloses the use of a developing agent in the silver halide emulsion (column 14, lines 6 to 19).

European Patent Application No. 155.690 and U.S. Patent No. 4,
No. 693.956 is a contrast promoting agent for use with high-contrast silver halide photographic emulsions containing H-P-R-Y.
t) teaches the use of alcohols and carbinols.

U.S. Patent Application No. 107 filed February 4, 1986
No. 07 teaches the use of contrast promoters in photographic emulsions prior to imagewise exposure of high contrast silver halide photographic emulsions containing hydrazide. This requires a high contrast hydrazide-containing silver halide emulsion or developer to contain a molecular weight bundle of at least 6
00 polyalkylene oxide is disclosed. An example of an effective additive is.

High contrast rapid access lithographic films are particularly susceptible to randomly uneven density across the imaged processed photographic sheet. This defect is caused by a low density screened 7.
This is particularly noticeable in 0% light exposure. Defects range from uneven density across the sheet to random streaks along the entire sheet giving a somewhat wood grain appearance, referred to herein as a spiral (5w1rl) pattern.

Uneven consistency occurs primarily, but not exclusively, in automatic processors. A complication of this problem is that automatic processors do not generate this pattern of defects with any regularity. These patterns include types of edge patterns that occur due to the flow or circulation of developer in the developer tank area, nip roller patterns that occur along the circumference of the rollers, and processing fill patterns that occur due to the passage of the film being processed. This is thought to be due to bubbles being trapped between the pair of rolls.

This type of defect pattern is observed in many different commercially available films, rendering the final product useless for high quality applications.

It is believed that the problems with these types of workpieces are inherent to the use of hydrazide and its interaction with the developer environment. Although the use of ballasted hydrazide tends to alleviate the problem somewhat, ballasting of the hydrazide reduces its reactivity and increases processing time, thus sacrificing photographic speed. The disclosures known so far are not effective in addressing or answering this type of problem.

SUMMARY OF THE INVENTION It has been discovered that the synergistic addition of certain components into the coating layer, alone or in combination, alters the induction time for processing of hydrazine (hydrazide) containing photographic elements. In particular, phenidone type developer (
3-pyrazolidinone developers, especially 1-phenyl-3
-pyrazolidinone developers) and 2-pyrazoline type developers, especially 1-phenyl-2-girazoline developers, and the addition of surfactant classes of alkoxylated alcohols and fluorinated surfactants to the topcoat layer in a vortex-like manner. It was found to reduce the pattern. These additives are believed to initiate sufficient development in the photographic element before any adverse mechanical processing forces take effect, resulting in uniform density films and processing operations.

It is surprising that this approach, especially when applied to high speed formulations, yields material that is virtually defect-free in the very sensitive lower density screened light exposure areas.

Details of the Invention A silver lodenide development accelerator consisting of a 6-pyrazolidinone or 2-pyrazoline developer is added to the coating layer of a high contrast silver lodenide-containing photographic emulsion to reduce swirl patterns. ζ in an effective amount and/or with a molecular weight of 1
Addition of surfactants from the class of alkoxylated alcohols and fluorinated surfactants less than 0.000 at high concentrations reduces uneven development of high contrast films. This is especially true for emulsions containing high speed r, unballasted or short chain ballasted hydrazides.

Silver chloride emulsions for use in the present invention include silver chloride,
It may be silver chlorobromide, silver iodobromide, silver iodochloride, silver iodochlorobromide, or a mixture thereof.

Generally, the iodine content of the silver halide emulsions is less than about 10% silver iodide, based on total silver iodide. Silver lodenide emulsions are disclosed, for example, in U.S. Patent Specification 4.
．． No. 166,742, No. 4,168,977, No. 4,
No. 224,401, No. 4,237.214, No. 4,2
No. 41.164, No. 4,272.614, and No. 4
．． No. 311.871, it is usually a monodisperse or narrow grain size distribution emulsion. A silver halide emulsion is a mixture of emulsions having different grain combinations, for example, as described in Japanese Patent Application No. 57-58137, an emulsion with an average grain size of less than 0.4μ and an emulsion with an average grain size of 0.7μ or more. or a combination of two emulsions both having grain sizes less than 0.4 microns, such as those described in U.S. Patent Application No. 881,081, filed July 28, 1986. A combination of a first silver halide emulsion having an average grain size of 0.1 to 0.4μ, as shown in FIG. It may be composed of.

The silver halide grains of the emulsions of this invention are capable of forming surface latent images, unlike those of the emulsions which form internal latent images.

Surface latent image-forming silver halide grains are most commonly used in negative-working silver halide emulsions, whereas internal latent image-forming silver halide grains are capable of forming a negative image when developed with an internal developer. can be used, but is usually used with a surface developer to form a direct positive image. The distinction between surface latent image forming silver halide grains and internal latent image forming silver halide grains is well known. Generally, certain additional components or steps are required to prepare silver halide emulsions that are capable of forming preferentially an internal latent image instead of a surface latent image.

In the silver halide emulsion of the present invention, precipitation or growth of silver halide grains may be carried out in the presence of a metal salt or a complex salt thereof, such as a rhodium or iridium salt or a complex salt thereof. . According to the invention, the presence of rhodium or iridium is not absolutely necessary to obtain high contrast. Silver octalodenide grains without rhodium or iridium can be used in the present invention, as well as silver halide grains produced or ripened in the presence of rhodium or iridium.

Although the silver denide emulsion of the present invention does not need to be chemically sensitized, it is preferably chemically sensitized. As chemical sensitization methods for silver rhodanide emulsions, known sulfur sensitization using sulfur compounds, reduction sensitization using mild reducing agents, and noble metal sensitization can be used alone or in combination.

Silver halide emulsions include cyanine, merocyanine, complex cyaninya, and complex merocyanine (
i.e., polymethine pigments such as tritetra- and polynuclear-cyanine and merocyanine cutis;
It can be spectrally sensitized by any spectral sensitizing dye from a variety of classes including oxonol, hemioxonol, styryl, merostyryl, and streptocyanin.

The binder or protective colloid for the silver layer(s) of the photographic element is preferably gelatin, but may be partially substituted with other hydrophilic colloids or synthetic water-insoluble polymers in latex form. Or it can be used as a complete replacement.

In addition, the photographic elements of this invention may contain any photographic additives known at the time, such as stabilizers, anti-capri agents, hardeners, plasticizers, other development accelerators, gelatin extenders,
It may contain a matting agent and the like.

To achieve the advantages of the present invention, the hydrazine compound must be present during development of the exposed element. It is necessary that the photographic element contain one or both of a 3-pyrazolidinone or 2-pyrazoline developer and a surfactant before being contacted with the entire developer solution. By "contact with the entire developer" is meant that the exposed element is brought into contact with all of the necessary developer components. A large number of different combinations of developer components may be useful, and a typical developer solution contains at least two developers (not taking into account the above developers of the present invention, of course), an antioxidant (ascorbic acid is also mentioned). (e.g., sulfites), and contrast-enhancing agents (e.g., alkanol-amines, alcohols, or carbinols).

The hydrazine compound can be incorporated into the photographic element or into the developer solution or into both the developer solution and the photographic element.

Preferably, it is present at least within the photographic element itself.

Hydrazine and water-soluble hydrazine derivatives are effective in increasing contrast when incorporated into developer solutions in combination with diarylmethanol compounds incorporated into photographic elements. Preferred hydrazine derivatives for use in the developers or emulsions of the present invention have the formula (wherein R5 is an organic group and R, R?, and R8 are each hydrogen or an organic group. ). The organic groups represented by R5, 'R, , R, and R8 include alkyl groups, aryl groups, arylalkyl groups, and hydrocarbon groups such as aliphatic groups, and such groups include alkoxy groups and , carboxy group,
It can be substituted with a substituent such as a sulfonamide group or a halogen atom.

Other examples of hydrazine-bound conductors that can be incorporated into the developer solution are hydrazides (including aryl hydrazides and formyl hydrazides), acyl hydrazines, semicarbazides, force/I/hydrazides, and aminoburet compounds.

Specific examples of hydrazine derivatives that can be incorporated into the developer solutions of the present invention include U.S. Patent Specification No. 2.419.5.
It is disclosed in No. 75.

In a preferred form of the invention, the hydrazine compound is present in the photographic element, for example in a silver halide emulsion layer or in a hydrophilic colloid layer, preferably in an emulsion layer where the effect of the hydrazine compound is required. Incorporated into the adjacent hydrophilic colloid layer. Of course, the hydrazine compound can also be present in the photographic element distributed between the emulsion layer and a hydrophilic colloid layer, such as a subbing layer, an interlayer, or a protective layer.

Hydrazine compounds suitable for incorporation into photographic elements according to the invention are disclosed in British Patent No. 5g8.108 and US Pat. No. 2,419,974; they include hydrazide, semihydrazide, and amino Water-soluble alkyl, not biuret compound,
Also included are aryl and heterocyclic hydrazone compounds.

Particularly preferred hydrazine compounds for use in accordance with the present invention incorporated into photographic elements are formylhydrazine compounds corresponding to formula (IT)K: where R4 represents a substituted or unsubstituted aromatic group, and R20 is hydrogen, aliphatic groups (e.g. alkyl or substituted alkyl of 1 to 20 carbon atoms), and phenyl substituted with aromatic groups (alkyl, alkoxy, carboxy, hydroxy, carboxyalkyl, etc. of up to 30 carbon atoms) (including substituted aromatic groups such as Examples of aromatic groups represented by R1 are phenyl and naphthyl. Such aromatic groups are described in U.S. Patent No. 4.168,
No. 977 and Canadian Pat.
n-ethyl, isoethyl, n-octyl, n-hexyl, tert-octyl, n-decyl, n-dodecyl, etc.), arylalkyl groups (e.g., benzyl, phenethyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, 2-methyl-propyloxy, etc.), amino groups mono- or di-substituted with alkyl groups, acylaminoaliphatic groups (e.g. acetylamino, benzoylamino, etc.), and one non-electron-withdrawing substituent. The above may be replaced. Such aromatic groups have the formula % as described in U.S. Pat. , aliphatic groups (such as straight-chain or branched alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, alkenyl groups, and alkynyl groups), aromatic groups (such as phenyl groups and naphthyl groups), or Represents a heterocyclic group: R□1 represents hydrogen or an aliphatic group (such as those listed above) may be substituted by a ureido group.

Other hydrazine compounds incorporated into photographic elements for use in accordance with the present invention have the formula % where R1 represents the same as the aromatic group in the previous formula, and R13 is a straight chain alkyl group; an alkyl group of 1 to 3 carbon atoms (e.g., methyl, ethyl, n-propyl, and isopropyl), which may be a branched chain alkyl group, or a phenyl group] be. Here, the phenyl group is substituted by one or more substituents, preferably electron-withdrawing groups, such as a halogen atom (chlorine, bromine, etc.), a cyano group, a trifluoromethyl group, a carboxy group, or a sulfo group. You can. A specific example of the hydrazine compound represented by the above formula is US Pat. No. 4,224,4
It is disclosed in No. 01.

Examples of other hydrazine compounds for use in accordance with the present invention incorporated into photographic elements include those of the formula [wherein R14 represents hydrogen, an optionally substituted aliphatic group; ; m represents 0 or 1; X is a divalent aromatic group (e.g., phenylene group, naphthylene group,
and similar substituted groups); R15
represents a hydrogen atom or an optionally substituted aliphatic group;
and 2 represents a nonmetallic atomic group necessary to form a 5- or 6-membered heterocyclic ring. If expressed by this formula, r
A specific example of a radin compound is U.S. Patent No. 4.272.614.
Disclosed in the issue.

In one particularly preferred embodiment, the hydrazine compound incorporated into the photographic element may be substituted with a ballast group, such as the ballast group of an incorporated color coupler or other non-diffusible photographic emulsion adduct. The ballast group has at least 8 carbon atoms and is
It can be selected from relatively unreactive aliphatic and aromatic groups such as alkoxy, alkylphenyl, phenoxy, alkylphenoxy groups, and the like. Most preferred for the practice of this invention, when the highest rate of development is preferred, the hydrazide has less than 8 carbon atoms, preferably no more than 4 carbon atoms, and most preferably no carbon atoms or at most 1 pendant carbon atom. should have a group.

Such hydrazine compounds can be incorporated into photographic elements in a variety of ways well known in the photographic art. The most common method is to dissolve the hydrazine compound in a high boiling crystalline solvent and disperse the mixture in an emulsion, as described, for example, in U.S. Pat. No. 2,522,027.

The hydrazine compounds incorporated into the developer solution in the practice of this invention are effective at low concentrations. For example, the hydrazine compound is present in the developer in an amount of about 0.001 mol/Jo to about 0.1 mol/Jo, preferably from about 0.002 mol/Jo to about 0.
．． A quantity of 0.01 mol/J3 gives effective results. Hydrazine compounds incorporated into photographic elements are typically silver 1
It is used in concentrations ranging from about 5 x io-' to about 5 x 10-'' moles per mole of silver, preferably from about 8 x 10-' to about 5 x 10-3 moles per mole of silver. It's the amount.

Contrast promoters such as alkanolamines and diarylcarbinol compounds, preferably diarylcarbinols such as the diarylmethanol compounds described herein, are present in the developer bath or preferably prior to contact with the entire developer solution. Incorporated into the photographic element (preferably prior to exposure of the photographic element itself). For example, diarylcarbinol compounds are incorporated into the photographic element prior to or concurrently with coating the emulsion layers. For example, they may be present in a silver halide emulsion layer of a photographic element or in a hydrophilic colloid layer of a photographic element, particularly in a hydrophilic colloid layer adjacent to an emulsion layer where the effect of the diarylcarbinol compound is needed. Can be incorporated. For example, they can be present in a photographic element distributed between the emulsion layer and a hydrophilic colloid layer, such as a subbing layer, an interlayer, or a protective layer.

R, , R of the above formulas (I), (II), and ([)
The aromatic group represented by 2 and R3 includes a naphthyl group, and preferably a phenyl group. The alkyl group represented by R3 in formulas (1) and (II) above includes branched or straight chain alkyl groups, preferably lower alkyl groups (1 to 5 carbon atoms). Such groups may contain substituents,
Such substituents are selected with properties and sizes that do not negatively affect behavior according to the invention. Regarding its properties, such substituents include, for example, alkyl groups, alkoxy groups, cyan groups, dialkylamino groups, alkoxycarbonyl groups, carboxy groups, nitro groups, alkylthio groups, hydroxy groups, sulfoxy groups, carbamoyl groups, sulfamoyl groups, It is a halogen II child fk.

With respect to its size, such substituents preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

Parameters that should be appropriately taken into account are the solubility and boiling point of the diarylcarbinol compounds of the invention. In order to incorporate the compound into the aqueous coating composition used to form the layers of photographic elements according to the invention, the compound should be substantially soluble in water or in a water-miscible solvent. It is.

"Substantially soluble" in water means soluble in water in an amount of at least 1% by weight, and "substantially soluble" in water-miscible solvent means Kr is soluble in water-miscible solvent. It means soluble with a concentration of at least 5% by weight.

The diaryl carbinol compound must have a sufficiently high boiling point so that it does not evaporate during drying of the layer-forming coating composition. The boiling point is preferably higher than 150°C, more preferably higher than 200°C.

Specific examples of diarylcarbinol compounds according to this aspect of the invention include: 1) diphenylmethanol (a, ni, a, benzhydrol) 2) 4,4'-dimethoxydiphenylmethanol 3) 4
．． 4'-dimethyldiphenylmethanol 4) 2.2'-
Dibromodiphenylmethanol 5) 4.4'-Dibromodiphenylmethanol 6) 2.2'-Dinitrodiphenylmethanol 7) 4.4'-Dinitrodiphenylmethanol 8) 2.3'-Dimethoxydiphenylmethanol 9
)2.4'-dihydroxydiphenylmethanol10)
4-methyldiphenylmethanol 11) 4-ethyldiphenylmethanol 12) 2, 2', 4,
The 4'-tetramethyldiphenylmethanol diaryl carbinol compound is preferably used in an amount of from about 10-4 to about 10-1 mole per silver mole, and more preferably in an amount of about 10-1 mole per silver mole. 3 to about 5 x 1
It is incorporated into photographic elements and used in the present invention in amounts of 0"-"molar.

According to the method of the present invention, imagewise exposed silver lodenide photographic elements can be processed with stable aqueous alkaline developers to form high contrast negative images. The slope of the straight line portion of this contrast-enhancing sensitometric curve (referred to as the "average contrast") is the slope between two points located at densities of 0.10 and 2.50 from Capri. be measured. According to the invention, average contrasts of greater than 10 can be obtained by developing the imagewise exposed element in the presence of a hydrazine compound. As a result of the lower concentration of developer and/or surfactant in the photographic element in the development bath, and the preferred presence of diaryl carbinol compounds in the photographic element, the process is similar to that described in U.S. Patent No. 4,269.9.
Conventional rapid access developers (well known The higher the -, the lower the stability of the developer) can be used to obtain the desired high contrast properties.

This can be done with a reduction in the swirl pattern observed on the developed image.

Dihydroxybenzene developing agents used in aqueous alkaline developers for use in the practice of this invention are well known and widely used in photographic processing. A preferred developing agent in this class is hydroquinone. Other useful dihydroxybenzene developing agents are chlorohydroquinone, bromohydroquinone, inzolobilhydroquinone, tolylhydroquinone, methylhydroquinone,
2.3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.5-dibromohydroquinone, 1.
4-dihydroxy-2-acetophenone-2,5-dimethylhydroquinone, 2,5-diethylhydroquinone, 2,5-di-p-7enethylhydroquinone, 2.5
-dibenzoylhydroquinone, 2,5-diacetaminohydroquinone, etc.

3- used in the emulsion (and may or may not be present in the aqueous alkaline developer) in the examples of the invention
Pyrazolidone developing agents are also well known and widely used in photographic processing. The most commonly used developing agents of this class are 1-phenyl-5-hyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-
3-pyrazolidone, and 1-phenyl-4,4-dihydroxymethyl-6-hyrazolidone. Other effective 6-pyrazolidone developing agents are 1-phenyl-5
-Methyl-3-furidone, 1-p-7minophenyl-4-methyl-4-7'robi-3-pyrazolidone, 1
-p-chlorophenyl-4-methyl-4-ethyl-3-
Pyrazolidone, 1-p-aceto-amidophenyl-4,
4-diethyl-6-pyrazolidone, 1-p-β-hydroxy-ethylphenyl-4,4-dimethyl-3-bi5f
')ton, 1-p-hydroxy-phenyl-4°4-dimethyl-6-hirazolidone, 1-p-methoxyphenyl-4,4-diethyl-3-f, y f ! j tons, 1
-p-) Crew 4,4-dimethyl-3-lazolidone and the like.

Preferred aqueous alkaline photographic developing compositions for use in the practice of this invention contain sufficient levels of sulfite preservatives to ensure good stability properties by protecting the developing agent from air oxidation. There is. Effective sulfite preservatives are sulfites, bisulfites, metabisulfites, and carbinyl bisulfite adducts. Typical examples of sulfite preservatives are sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite,
These include potassium metabisulfite and formaldehyde sodium bisulfite salt. Ascorbic acid is also a known preservative to prevent air oxidation of the developer for in-bath use according to the present invention.

Aqueous alkaline developers for use in the practice of this invention can vary widely with respect to the concentrations of the various components contained therein. Typically, dihydrobenzene-based developing agents are used in amounts of 0.040 to about 0.70 mol/l, preferably 0.08 to about 0.40 mol/l:
3-pyrazolidone developing agent is about o, o o i to about 0
．． 0.05 mol/J3, preferably about 0.00-
5 to about 0.01 moles/no: sulfite preservatives are used in amounts of about 0.06 to about 1.0 mole/Jj f) ikte;
Preferably about 0.10 to about 0.70 mol/I! J(
Used in D amount.

In contrast to "lith" developers, which require low levels of sulfite ions, the developers of the present invention can utilize high levels of sulfite ions, and thus the high levels of sulfite ions increase protection from atmospheric oxidation. As a result, the effect of increased stability is achieved.

In practicing the method of this invention, it is preferred to use organic anticapri agents to minimize capri formation in processed photographic elements. Organic anticapri agents may be incorporated into the photographic element, or the developer solution, or both the photographic element and the developer solution. According to the present invention, it has been found that particularly preferred organic anticapriants for use in developer solutions are benzotriazole and/or benzimidazole anticapriants. They have been proven to have a beneficial effect on contrast enhancement. Useful compounds are substituted and unsubstituted benzotriazole and benzimidazole compounds. However, the condition is that they do not contain at least a strong electron-withdrawing substituent such as a nitro group.

In fact, substituted benzotriazoles and benzimidazoles are good at preventing capri, but do not have a beneficial effect on contrast enhancement. As a class, benzimidazoles and benzotriazoles are believed to be useful in the practice of this invention. Regardless of K, as mentioned above, it was difficult to obtain significantly improved performance with benzotriazole and benzimidazole having strong electron-withdrawing groups. Therefore, benzotriazole and benzimidazole preferably do not have a substituent on the aromatic ring that is an electron-withdrawing group as strong as or stronger than a nitro group. Other known substituents such as lower alkyl groups (of 1 to 5 carbon atoms) and halogen substituents (chlorine) have proven to be good substituents for the present invention. The benzotriazole and benzimidazole anti-capri agents and contrast promoters described above are commonly used in amounts effective to prevent capri. However, those quantities can be optimized to obtain the best results in terms of load trust. The effective amount is
When they are contained in the emulsion, they can vary from 1 fern per 100 g of emulsion to 100 m9, and when they are contained in the developing bath (which is preferable), they can vary from 1 f/100 m9 to 1 f/100 g of emulsion.
．． It can vary from 0.01 g to 5 g.

In addition to the essential ingredients specified above, the developer solution can optionally contain any of a wide variety of additives useful in photographic developers, as is well known.

For example, it can contain solvents, buffers, sequestering agents, development accelerators, agents to reduce cellulization of the emulsion layer, and the like.

Surfactants Surfactants useful in the practice of this invention are described in U.S. Pat.
It was found to be limited to the class of ethoxylated or propoxylated alcohols, and fluorinated surfactants, such as those disclosed in No. gj019 and No. 2,915.554.

Ethoxylated or propoxylated alcohols are preferred. The most preferred surfactant example is C! 1lHa40□
AntaroxTM, an ethoxylated (and possibly also propoxylated) hybrid octyl/decyl alcohol with a complex molecular formula of
It is BL-240. The average formula seems to be. These compounds must actually act as surfactants;
and this generally means that at least one surface-active functional group (e.g., a hydroxyl group) has less than 20 total ethoxy and propoxy groups in the molecule (e.g., hydroxyl group).
(preferably less than 16, more preferably less than 10). Preferably, the surfactant has a molecular weight of less than 1,000, more preferably less than 800. Emulphor %T'erg
A number of other commercially available ethoxylated alcohol surfactants can also be used in the practice of this invention, such as itolTM VolpoTM and the like. Other useful surfactants are U.S. Pat. Nos. 3,769,022 and 2,831,766
No. 4,010-0.5 as an auxiliary agent and U.S. Pat.
g1.641 as a surfactant. In appreciating the present invention, it should be noted that the swirl pattern is a development defect rather than a coating defect. Analysis of the layer before development or during less active development does not show these swirl patterns. That means it is not the result of a coating defect.

In order for the developing agent of the present invention to be effective, it must be between 0.001 and 0.
．． It has been found that the developer should be added to the silver halide emulsion layer in an amount of 0.050 g/R". Preferably one developer should be used in an amount of 0.005 to 0.040 g/F712. C, most preferably 0.005 to 0.05
It is 0g1In2. The surfactant is contained in the top coat layer in the range of 0.010 to 0.010 to 0.5g17 door 2,
Preferably the range is 0.020 to 0.411/IIL2, most preferably 0.020 to 0.411/IIL2. -050~0.50 g/m”
should be used within the range of

The combination of both the auxiliary developer in the silver halide emulsion layer and the surfactant in the topcoat layer improves film performance even better than the additive effect of the individual materials. In particular, the induction time to obtain an initial appreciable development can be reduced by the combination of these additives.

There are general references to the use of hydrazide high contrast technology as developing agents in emulsions (e.g., U.S. Pat. Nos. 4,560,638 and 4,618,574).
However, there is no disclosure regarding the phenidone type developer in the emulsion layer. U.S. Patent No. 4,619,886;
No. 4,650,746, and No. 4.168.977.
No. 60-129746 teaches the general use of 6-pyrazolidone type (phenidone type) developing agents in developing baths; It does not suggest the use of drugs. The swirl pattern reduction effect is only observed when the phenidone developer is present in the emulsion (either directly or by migration from other layers), and no effect is observed when the developer is present only in the developer bath. .

These and other features of the invention will also become apparent from the following examples.

Example 1 Coating layer emulsion Potassium bromide spectral sensitizing dye Br1j58 (molecular weight 1 alcohol) Hostapur 5A8-93 0.049 Ag 3.1 g/m" 0.034 F!Zr1L" 0.007 0.043 More than 000 Benzhydrol ascorbic acid 0.041 0.003 Triazine coating layer Inert gelatin Hoatapur Si2-95 (Coating aid) Silica (Matting agent) 0.102 0.704fi/ m2 0.061 0.029 Layer A was coated onto a standard primed and primed polyester base which had been previously coated with an anti-nolation layer on the back side. After 6 days to increase the hardness of Layer A, Layer B was applied over Layer A, and after an additional 3 days to increase the hardness, the film was processed for packaging. This is referred to as coating 1 in the table below.

The following developer compounds were also added to the liquid dominant formulation for layer A above. Among these, 6-pyrazolidinones (coated
Only 5) and the 2-gi Labrins (coatings 8 to 9) produced the effect of the present invention and showed the specificity of these laths.

1. No additives 2.722rnA 6. Phenidone A 4. Dimethene 5. Dimethene 6. Metol A, Metol 8, Pyrazoline (C10H1ON20) 9, 10, Tetrachlorohydrokino 11. 12. Spirobynton 16.〃 14. Zorogyl gallic acid 15.1 Metol is p-methylamine be.

0,'000gm/m25 5 0.004 4 1.5 0.010 3.5 1.5 0.004 4 2.5 0.010 4 2 0.004 4.5 3 0.010 4 3.5 0 .004 4.5 2.5 0.010 4.5 2.2 0.004 5 3 0.010 5 5.5 0.004 4.5 4 0.010 4 3 0.004 4 4 0.010 4 .5 4 Nophenol sulfate and phenidone hii 1-phenyl-3-pyra f IJ syn/.

Chirazoline is 3-methyl-1-phenyl-2-pyrazolin-5-one.

Dimethene S is 4-hydroxylmethyl-1-4-methyl-1-phenyl-3-pyrazolidone.

Dimethene is It is.

Amytol is 2,4-diaminophenol dihydrochlor.

An example of an exposure method: A point light source passed through a Kodak Wratten Series 00 filter was applied to a film sample to which an overlaid Kogutsuk 133-line magenta contact screen was vacuum attached, resulting in a dot density of approximately 70 cm after processing. irradiated with appropriate electromagnetic waves.

Typical fluorinated surfactants have surfactant groups [e.g.
-0(C
H2) a polyoxoalkyl group such as n- (where n is 2 or 6)] K-bonded highly fluorinated (at least 2 of all substituents on the carbons of the group)
/3 is fluorinated) or has a fully fluorinated group. Typical examples are (however, R7 is a highly fluorinated or fully fluorinated group, R is H or an alkyl group having 1 to 4 carbon atoms,
m and p are 2 or 6, and R1 is hydrogen or methyl).

Other fluorinated surfactants have the formula [wherein R2 is as defined above and q is 2 to 6].
p, R'' and R2 and R3 are each independently an alkyl group of 1 to 8 carbon atoms (preferably 1 to 3 carbon atoms), and A is an ion.

Example of development processing solution and conditions: Example of developer (developer at 100'F) 1800.00
g 195.00 g 124.00,! i' io,oo g 7.509 60.00g 5.0011 0.2011 9.25. li' Potassium Hydroxide Potassium Metabisulfite DTPA (40 Ti) Pyruvate Hydroquinone Metol 5-Methylbenzotriazole Potassium Bromide Potassium Chloride Phosphoric Acid Final Volume Part A Working Solution (2,70 g 90.00 g 2.00) 11. 00P)] Fixer applied to 100'F) Water 0.1
2530 J3 Ammonium Thiosulfate 0.
77990-e Sodium sulfite 65.9
096El boric acid 29.2380
10-0.5g1 Sodium acetate 52
．． 8654 9 Acetic acid (glacial acetic acid) 42
．． 3.5 g 9 g total 1, OJ The exposed element was machine developed in the above developer for 30 seconds, then immersed in fixer for 30 seconds and in a water bath before drying. Due to the uniform and low screened tonal density, any aberrations or variable density defects caused by mechanical processing forces were greatly accentuated and resulted in a method for evaluation. The internal term given to this defect was "swirling", which gave it a rating of 0-50. 0 is close to zero observations of any defect, and 5 is a visible grain type defect or other severe processing pattern. The results for the coating additives are included in the table above under the Vortex Evaluator 1 column.

The table shows that the addition of phenidone to the emulsion layer is 0.01 fi/II.
It clearly demonstrates that when used at the optimal level of L2, it improved the "swirl" defect level by 1-1/2 units. In addition to this positive improvement, the phenidone-containing material also visually demonstrated a consistent overall density in the processed film sheet. None of the other auxiliary developers had any appreciable positive effect on these problem areas.

Compared to vortex evaluation body 1 in the table, those shown under the column of vortex evaluation body 2 are layer s K AntarOXTMf3IJ-
It has been demonstrated that adding 240 at optimal levels reduced defect levels.

A synergistic effect is observed when phenidone and ethoxylated alcohol (such as BL-240) are used in combination, with a total effect on "vortex" improvement of at least 6.5%.
It's worth 5 units.

A synergistic effect is achieved, for example, when layer A is coated with the next layer C in coating 2-2 of Example 1.

Inert gelatin 0-704 g/m
”Ho5tapur 8A8-95 0
．． 0 (010~0.5g silica
0.029Ant+arOX BL-240[]-1
41 triazine 0.095
The result is shown in the table below the vortex evaluation body 2, and the defect result is less than 2 units. Each material was exposed and developed according to Example 1. It was also found that a small air pump was required to supply foam to the first pair of inlet rollers of the processor in order to generate a consistent defect pattern.

Example 2 A composite designed with six key variables was coated. Phenidone is added to the layer in a wide range of amounts,
The emulsion layer was similar to the final emulsion of Example 1 except that HA-22 was omitted. The remaining two variables/ranges were now those contained in Topcoat 1-, which contained HA-22 in an amount of 0.1623 g/Ffi. These coatings were also Example 10 Layer C. The materials were different because the two layers were coated simultaneously.The materials were exposed and processed to the desired temperature prior to grading for "vortex" evaluation.

The design level of the variable is as follows: 0.0482 0.560
1.0404g/n”+ 0.05g9
0.2B20 0.9479Cp O,02
620,21150,8123-0,01310,14
100,6767-α0.00318 0
．． 0929 0.5842 Design average value 1.69
A static analysis of the above design variables for the "vortex" response of the unit change yields the following effects:

For phenidone -0,696BL-240I
-0 for C, 824 gelatin
0.0 This design analysis demonstrates not only the synergistic effects but also the independent effects of the variables in the one-pass coating operation.

Claims (10)

[Claims] (1) A silver halide photographic element comprising at least one negative-working surface latent image type silver halide emulsion layer and a hydrazine compound, which has not been exposed to sensitizing radiation by active electromagnetic radiation, (a) a 3-pyrazolidinone or 2-pyrazoline developing agent in reactive combination with the silver halide;
and (b) a surfactant selected from the class consisting of alkoxylated alcohols and fluorinated surfactants in the topcoat layer, in an amount that reduces the swirl pattern. The above-mentioned silver halide photographic element characterized by: (2) A silver halide photographic element which has not been exposed to sensitizing radiation by active electromagnetic waves and which comprises at least one negative-acting surface latent image type silver halide emulsion layer and a hydrazine compound, wherein said element is a contrast-promoting amount of a diarylcarbinol-based contrast promoter in a combination capable of reacting with the silver halide emulsion layer [provided that the diarylcarbinol compound has the formula (I) or (II) R_1R_2R_3COH(I) R_1R_2R_3C (CH_2)_nOH(II) (wherein R_1 and R_2 each represent a substituted or unsubstituted aromatic group, R_3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, and n is a positive 0 to 4 ), and the diaryl carbinol is present in the silver halide emulsion layer in an amount of about 10^-^4 per mole of silver halide.
~10^-^1 mole]; and said element is incorporated in a spiral pattern reducing amount of (a) the 3-pyrazolidinone or 2-pyrazoline developer in the emulsion, and (b) in the topcoat layer. a surfactant selected from the group consisting of alkoxylated alcohols and fluorinated surfactants. 3. The element of claim 1, wherein an alkoxylated alcohol is present in the topcoat layer, and wherein the alcohol is selected from the group consisting of ethoxylated alcohols and propoxylated alcohols. (4) The element of claim (3), wherein the ratio of ethoxy and propoxy groups to each surfactant group is less than 20. (5) The element of claim (4), wherein the surfactant group contains a hydroxyl group. (6) The element according to any one of claims (1) to (5), further comprising the developer in the emulsion layer, the developer comprising a 3-pyrazolidinone developer. (7) The hydrazine has the formula R-NHNH-CR^1, where R is an aromatic group and R^1 is selected from hydrogen, alkyl, and aromatic groups. Elements 1) to (5). (8) The hydrazine has the formula R-NHNH-CR^1, where R is an aromatic group and R^1 is selected from hydrogen, alkyl, and aromatic groups. 6) element. (9) A silver halide photographic element containing at least one negative-acting surface latent image type silver halide emulsion layer and a contrast-promoting hydrazine compound, which has not been exposed to sensitizing electromagnetic radiation. (a) an auxiliary developer in reactive combination with said silver; and (b) a surfactant selected from the class consisting of alkoxylated alcohols and fluorinated surfactants in the topcoat layer. wherein said surfactant is present in said topcoat layer in an amount that reduces swirl pattern.
010 to 0.5 g/m^2, and said surfactant consists of an ethoxylated or propoxylated alcohol in which the ratio of ethoxy and propoxy groups to hydroxyl surfactant groups is less than 16, and said The emulsion layer contains 0.001 to 0 3-pyrazolidinone auxiliary developer.
．． The above silver halide photographic element containing in an amount of 5 g/m^2. (10) A silver halide photographic element comprising at least one negative-acting surface latent image type silver halide emulsion layer and a hydrazine compound for promoting contrast, and which has not been exposed to sensitizing electromagnetic radiation to impart developability. , the element has a contrast-enhancing amount of a diarylcarbinol-based contrast promoter in reactable combination with the silver halide emulsion layer, provided that the arylcarbinol compound has the formula (I) or (II) R_1R_2R_3COH (I) R_1R_2R_3C(CH_2)_nOH(II) (wherein R_1 and R_2 each represent a substituted or unsubstituted aromatic group, R_3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, and n is 0 to (representing a positive integer of 4), and the diaryl carbinol is present in the silver halide emulsion layer in an amount of about 10^ per mole of silver halide.
-Incorporated in an amount of 4 to 10 - 1 mole]
; and said element is a spiral pattern reducing amount of a surfactant selected from the group consisting of (a) a 3-pyrazolidinone developer in the emulsion, and (b) an alkoxylated alcohol and a fluorinated surfactant in the topcoat layer. [provided that the surfactant is present in the top coat layer in an amount of 0.
010 to 0.5 g/m^2, and said surfactant consists of an ethoxylated or propoxylated alcohol in which the ratio of ethoxy and propoxy groups to hydroxyl surfactant groups is less than 16, and said The emulsion layer contains 0.001 to 0 3-pyrazolidinone auxiliary developer.
．． 5 g/m^2].