JPH0419642A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the quality of a reversal character image obtained by a reversal process by forming a nonphotosensitive layer containing a solid dispersion of a specified dye above silver halide emulsion layers. CONSTITUTION:At least one silver halide emulsion layer contains a rhodium salt in an amount of >=1X10<-6>mol in one mol of silver halide and silver chloride in an amount of >=80mol% of silver halide, and an emulsion layer and/or another hydrophilic colloidal layer contains a hydrazine derivative. The nonphotosensitive layer formed above the emulsion layers contains the solid dispersion of the dye having a peak in the wavelength region of 300 - 400nm, thus permitting gradation almost not to be lowered, and the reversal character image to be improved in quality.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic material that can be handled in an environment that can be essentially called a bright room. It relates to photosensitive materials.

(Prior Art) In the field of printing reproduction, there is a need to improve the efficiency of the photolithography process in order to cope with the diversity and complexity of printed matter.

Particularly in the collection and reversing processes, efforts have been made to improve work efficiency by performing the work in a brighter environment, and for this reason it is necessary to work in an environment that can essentially be called a bright room. Progress has been made in the development of photosensitive materials for plate making and exposure printers that can be used for printing.

The photosensitive material for bright room use described in this patent refers to a photosensitive material that can safely use light having a wavelength of 400 nm or more, which does not contain an ultraviolet component, as safelight light for a long period of time.

The photosensitive material for bright room use used in the collection and reversing processes uses a developed film on which characters or halftone images have been formed as an original, and the original and the photosensitive material for reversing are exposed in close contact to form a negative image/image. It is a photosensitive material used to perform positive image conversion or positive image/positive image conversion. It is desired to have the ability to perform positive image conversion ■ It is desired to have the ability to adjust the tone of a halftone image and the in-line adjustment of a character line image, and light-sensitive materials for bright room reversal have been provided to meet this demand. Ta.

However, in the advanced image conversion work of forming cut-out character images by overlapping and repeating, the conventional method using a bright room reversing process using a photosensitive material for bright rooms is not suitable for the light room reversing process using a conventional reversing photosensitive material for darkrooms. This method has the disadvantage that the quality of the extracted character image deteriorates compared to the method described above.

To explain in more detail the method of forming cut-out character images by overlapping, as shown in Fig. 1, transparent or translucent pasting bases (A) and (C) (polyethylene terephthalate usually having a thickness of about 100 μm) are used. (b) A film on which characters or line images are formed (line drawing original) (b) and a film on which a halftone dot image is formed (halftone original) (d).
The halftone dot original (d) is overlapped with the pasted material (e) to form an original, and the emulsion side of the return photosensitive material (e) is brought into close contact with the halftone original (d) for exposure.

After exposure, a development process is performed to form blank white portions of line drawings in the halftone image.

The important points in this method of forming a character image are:
Ideally, negative image/positive image conversion is performed according to the halftone dot area and image line of each of the halftone dot original and the line drawing original. However, as is clear from Figure 1, the halftone original is exposed in direct contact with the emulsion surface of the photosensitive material for return, whereas the line drawing original is exposed on the paste base (c) and the halftone original (black). ) is exposed to the photosensitive material for return through the intermediate layer.

For this reason, if you apply an exposure amount that faithfully converts a halftone original from a negative image to a positive image, the line drawing original will be exposed out of focus through the spacer created by the pasting base (c) and the halftone original (d). The inside of the drawing line in the blank white part becomes narrower. This is the cause of the deterioration of the quality of the extracted character image, but this phenomenon is caused not only by the photographic performance of the light-sensitive material but also by
The exposure light source also makes a large contribution.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photosensitive material that can be used in a bright room under a safelight, and which provides excellent quality of cut-out character images by overlapping. The purpose is to provide materials.

(Means for solving the problem) At least one silver halide emulsion layer comprising silver halide grains containing 1X10-' mol or more of rhodium salt per 1 mol of silver and having a silver chloride content of 80 mol% or more. In a silver halide photographic light-sensitive material containing a hydrazine derivative in the emulsion layer and/or other hydrophilic colloid layer, a dye having a peak at 300 to 400 nm is dispersed in solid form in the upper part of the emulsion layer. The problems of the present invention have been solved by a silver halide photographic material characterized by providing a non-photosensitive layer.

In the present invention, a water-soluble rhodium salt is used to reduce the sensitivity of the silver halide emulsion and improve its handling properties in a bright room.Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used. It is preferable to use Furthermore, complex salts of these can also be used.

The rhodium salt may be added at any time before the completion of the first ripening during hole side production, but it is particularly desirable to add it during particle formation. The amount added is lXl0- per mole of silver.
'Molar or more, especially 2X10-' to 5X10-' moles are preferred.

Further, the silver halide emulsion of the present invention is preferably not subjected to chemical ripening in order to improve its handling properties in a bright room.

This meaning of ``no chemical ripening'' refers to the use of sulfur sensitizers, stannous salts, and amines that react with silver salts to form silver sulfide for the purpose of chemical sensitization, which has traditionally been carried out. Sensitization is carried out at a specified temperature and pH for 1 hour by adding a reduction sensitizer, a noble metal sensitizer such as chlorauric acid salt or gold trichloride, or by using activated gelatin containing a sulfur-containing compound. The degree of sensitization caused by minute amounts of sensitizing substances contained in gelatin, which is usually referred to as inert gelatin, is ignored.

The silver halide in the silver halide light-sensitive material used in the present invention has a silver chloride content of 80 mol % or more, particularly preferably 95 mol % or more of silver chloride.

The average grain size of silver halide is preferably 0.5 μm or less, particularly preferably 0.3 μm or less. Average grain size is a term commonly used and easily understood by those skilled in the field of silver halide photographic science. Particle size means the particle diameter in the case of particles that are spherical or can be approximated to a sphere. Make it into grains. The average particle projected area is also determined by algebraic mean or geometric mean. For details on how to determine the average particle, see C. E. Mees and T. H. Jaw.
The theory of the pho
tographic process 3rd edition, 36~
43 (1966, published by Mamillan).

There are no restrictions on the shape of the silver halide grains, and they may be tabular, spherical, cubic, octahedral, or any other shape.

In addition, the particle size distribution is preferably narrower, and in particular, 90% of the total number of particles is within the particle size range of ±40% of the average particle size.
A so-called monodispersed emulsion containing 95% of the total amount of the monodispersed emulsion is preferred.

In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping p and Ag constant in the liquid phase in which silver halide is produced, that is, the so-called Chondrald double jet method, can be used. According to this method, the crystal shape is regular. A silver halide emulsion with a nearly uniform grain size can be obtained.

The particle formation is preferably carried out under acidic conditions; our experiments have shown that the effectiveness of the present invention is reduced under neutral and alkaline conditions. The preferred pH range is 6 or less, more preferably 5 or less.

Although two or more silver halide emulsion layers can be provided,
One layer is usually sufficient. Coating silver amount is 1g/rrf ~ 8
A range of g/nf is desirable.

/ The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by +).

General formula (1) In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloquine group, an amino group or a hydranno group, and G1 represents a 10- group, -SO.

＼○ OO group, -8〇- group, -P- group, -c-c- group, thiocarbonyl group, or iminomethylene group, A, , A are both hydrogen atoms, or one hydrogen atom is substituted with the other. or represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted anru group.

In general formula (1), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R1 in general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, an unsaturated heterocyclic group (may be fused with an aryol group).

Preferred as R is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amine group, a ureido group, Urethane group, acylamino group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, anano group, sulfo group,
Aryloxysulfonyl group, anol group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide O group, R, -NHCN-C- group, etc. Preferred substituents include alkyl groups (preferably carbon atoms of 1 to 20
), aralkyl group (preferably one having 7 to 30 carbon atoms), alkoxy group (preferably one having 1 to 20 carbon atoms), substituted amine group (preferably substituted with an alkyl group having 1 to 20 carbon atoms) amine group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), Examples include a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms).

The alkyl group represented by R2 in general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a Hensen ring). .

When G1 is a 10-group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydrokinebenzyl group), aryl group (e.g., phenyl group, 3°5-chlorophenyl group, 0-methanesulfone) amidophenyl group, 4-methanesulfonylphenyl group, 2-hydroquinemethylphenyl group, etc.)
Particularly preferred is a hydrogen atom.

R2 may be substituted (as the substituent, the substituents listed for R1 can be used).

〇 G in general formula (I) is most preferably a 10-group.

Also, R2 splits the G, -R, part from the remaining molecule,
There may be a reaction that causes a cyclization reaction to produce a cyclic structure containing an atom of the Cz R2 moiety, such as those described in JP-A No. 6329751 and the like.

Most preferably, A, A, and A are hydrogen atoms.

R or R2 in the general formula (1) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A No. 1-100530.

R1 or R2 in the general formula (I) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜231, 59-201,045, 59
-201.046, 59-201,047, 5
9-201,048, 59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

■-1 ■ 2Hi ■ ■-11 ○ ■ ■-13 ○ To N□■-24 ■-25 ■-26 In addition to the above-mentioned hydrazine derivatives, RESEARCHDISCLO3URE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, 4. 478. No. 928, British Patent 2
, 011,391B, JP 60-179734, JP 62-270,948, JP 63-29,751, JP 61-170゜733, JP 61-270.744,
No. 62-948, EP No. 217,310, or US
No. 4゜686.167, JP-A-62-178,246
No. 63-32,538, No. 63-104゜047
No. 63-121,838, No. 63-129.33
No. 7, No. 63-223,744, No. 63-234,2
No. 44, No. 63-234, 245, No. 63-234,
No. 246, No. 63-294 No. 552, No. 63-306
, No. 438, JP-A-1-100,530, JP-A No. 1-10
No. 5.941, No. 1-105,943, JP-A No. 1983-
No. 10.233, Japanese Patent Application Publication No. 1-90,439, Japanese Patent Application No. Shof
No. 33-105,682, No. 63-114,118,
No. 63-110,051, No. 63-114.119, No. 63-116,239, No. 63-147,339
No. 63-179,760, G3-229,16
No. 3, Patent Application No. 1-18.377, No. 1-18,378
No. 1-18.379, No. 1-15,755, No. 1-16.814, No. 1-40,792, No. 1-4
2.615, 1-42,616, 1-123.
693 and 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention ranges from lXl0-@mol to 5xio per mole of silver halide.
It is preferable that the amount of txio-' mol to 2XlO-' mol is more preferable.

The layer to which the hydrazine derivative used in the present invention is added may be a silver halide emulsion layer, or another hydrophilic colloid layer, or may be added to both the silver halide emulsion layer and another hydrophilic colloid layer. .

The dye having a peak at 300 to 400 nm used in the present invention is a compound represented by the following general formula (II). The preferred absorption peak of this dye is from 300 to 380 nm, and the amount added is such that the inherent sensitivity of silver halide is reduced to 1/2 or less.

General formula (II) [D-(A)y]-Xn D is a coloring light-absorbing compound, and when y is not 0, it may or may not form an aromatic ring. When y is 0, an aromatic ring is formed.

A is an aromatic ring bonded directly or indirectly to D.

X is a substituent having an ionizable proton that is substituted on the aromatic ring of A or D.

y is θ~4, and n is 1~7.

Specific examples of the dye represented by general formula (1) are shown below.

■ ■ しυυh I-3 I-4 Shuutt しυυh しυυ１ If-9 ■-11 しυυn ■-13 H3 C1l.

■-14 ■-15 ■-16 ■-17 ■-18 ■-19 ■-20 The present invention is not limited to the dyes shown above.

In the present invention, the solid disperse dye refers to a solid disperse dye that cannot exist in a molecular state in the intended colored layer due to insufficient solubility of the dye itself, and as a solid of a size that is virtually impossible to diffuse in the layer. means the state of existence.

For details on the adjustment method, see International Application Publication (WO) 881047.
94, European Patent (EP) 0276566A1, JP-A-63-197943, etc., there is a method in which the dye is ground in a ball mill and stabilized with a surfactant and gelatin, and the pH is adjusted after dissolving the dye in an alkaline solution. A method of lowering and precipitating is preferably used. However, the present invention is not limited to these adjustment methods.

The solid disperse dye prepared by these methods can be added in a solid state to the coating solution for a non-photosensitive hydrophilic colloid layer of the present invention.

Two or more of these dyes can also be used in combination.

In the present invention, the dye is added to the camphor that reduces the inherent sensitivity of the silver halide emulsion at 360 nm to 1/2 or less, but the amount added is such that the absorbance at 360 nm is 0.3 or more, and more preferably This is the amount at which the absorbance at 360 nm is 0.4 or more.

It is usually added in a range of 10-''g/bo to Ig/bo, preferably 50 g/bo to 500 g/bo.

The dye used in the present invention is covered by International Patent WO3810479.
No. 4, European Patent EPO 274723A1, No. 2
No. 76.566, No. 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61-205934, No. 4B-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
No. 30429, No. 4040841, Patent Application No. 1-508
No. 74, No. 1-103751, No. 1-307363, etc., and can be easily synthesized according to the method.

There are particular restrictions on various additives used in the photosensitive material of the present invention, such as binders, hydrophilic colloids, gelatin hardeners, surfactants, nucleation promoters, anticapri agents, antistatic agents, polymer latex matting agents, etc. There isn't, but
For example, Japanese Patent Application No. 1-295620, No. 1-290563
No. 1-157142, etc. can be referred to.

In order to obtain ultra-high contrast photographic properties using the above-mentioned silver halide photosensitive materials, conventional infectious developing solutions and US Pat.
It is not necessary to use a highly alkaline developer having a pH close to 13 as described in No. 975, and a stable developer can be used.

That is, for the above-mentioned silver halide photosensitive material, a developer containing a sufficient amount of sulfite ions as a preservative (particularly 0.15 mol/1 or more) can be used, and p)(9,5
As described above, a sufficiently high contrast negative image can be obtained especially with a developer having a pH of 10.5 to 12.3.

There are no particular limitations on the developing agents that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4゜4-dimethyl-1-phenyl- 3-pyrazolidone) aminophenols (e.g. N-
methyl-p-aminophenol) etc. can be used alone or in combination.

The developer also contains alkali metal sulfites, carbonates,
Contains PH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). I can do it.

In addition, if necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (particularly preferably the above-mentioned polyalkylene oxide tS>antifoaming agents, hardeners, film silver stain preventive agents) For example, 2-mercaptobenzimidazole sulfonic acids) and the like may be included.

Specific examples of these additives are listed in Research Disclosure 1.
It is described in No. 76 No. 17643.

The processing temperature is usually selected between 18°C and 50°C,
The temperature may be lower than 18°C or higher than 50°C.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may also contain a water-soluble aluminum salt or the like as a hardening agent.

Next, the present invention will be explained in detail based on examples.

(Emulsion A) ■Liquid: 600ml of water, 18g of gelatin, pH 3,0■
Liquid: AgNOs 200g Water 800at ■Liquid:
KBr 2.8 NaCf75g NHJhCj!
b40 ■ Water 800 + d Mix liquids ■ and ■ in I liquid kept at 40℃ simultaneously on both sides,
The addition was maintained at a constant rate over a period of 20 minutes. After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin was added as a stabilizer to 2-methyl-4-hydroxy-1,3,3a,7-tetraaza without chemical ripening. Indene was added.

This emulsion has a Br of 2%, a grain size of 0.25μ, a Rh content of 1.0XIO-' mol/Ag mol, and the yield of the emulsion is 1 kg.
The amount of gelatin contained was 60g.

(Emulsion B) ■Liquid: Water 950j11 Gelatin 15g PH6,
0 ■Liquid: AgNOs 150g Water 150m ■Liquid: N
aCl21g NH4RhCj! i l■Water 155- ■Liquid: NaCj! 27g water 155g Mix half of the ■solution and ■solution in the ■solution maintained at 40℃ with silver added for a few seconds.3
The remaining amount of solution (2) and solution (2) were simultaneously added on both sides for 8 minutes while maintaining a constant rate. After this, 2-methyl-4-hydroxy-1°3.3a,7-tetraazaindene was added,
Soluble salts were removed in the same manner as in Emulsion A.

This emulsion has AgCff1, grain size 0.1 .mu., Rh content 3.times.10" mole/Ag mole.

The test samples shown in the table were exposed to light using a P-607 printer manufactured by Dainippon Screen Co., Ltd. through a light pattern, developed with a developer having the composition shown below at 38° C. for 20 seconds, stopped, fixed, washed with water, and dried.

Developer Hydroquinone 50.0g N-methyl-P-amino 0.3g Phenol Sodium hydroxide 18.0g 5-sulfosalicylic acid 30.0g Boric acid
20.0g potassium sulfite
110.0g ethylenediaminetetraacetic acid
1.0g Potassium dianasodium 10.0g 5-Methylbenzotria 0.4g Sol 2-mercaptobenzimi 0.3g Dashi
3-(5-mercabutotet) 5-sulfonic acid 0.2g Razol) Sodium benzenesulfonate 6-dimethylamino 1-4.0g Hexanol Sodium toluenesulfonate 15. Add Ogum water and 1j! 17! pH
-11,7 (by adding sodium hydroxide) In the table, r ; (3,0-0,3)/(log (concentration 0.3
-1og (exposure amount to give a density of 3.0)) Extracted character image quality: As described in JP-A-58-190943, a pasted base/film on which a line drawing positive image has been formed (line drawing manuscript) ) / Pasting base / Films (11 originals) on which 1m point images were formed were weighed in this order and brought into close contact so that the protective layer of each film sample and the dot original overlapped face-to-face, and 50% A film sample with a width of 150 IIm was given a suitable exposure so that the halftone dot area was 50% of the dot area on the film sample and was processed as described above. A score of 1 is given to those that can only reproduce the above characters, and a rank of 4.3.2 is set between 5 and 1 based on the sensory evaluation. 2 is the barely practical limit.

(Effect of the invention) As is clear from the table, the present invention has the following advantages:
-17 shows that there is almost no softening of the gradation and the quality of the cut-out characters is good.0 The present invention is capable of producing images with good cut-out character quality without causing deterioration of the gradation by adding a solid dispersion of dye. give.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1゜ Display of incidents 1990 patent application No. 1 No. 23686 2゜ name of invention Silver halide photographic material 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] At least one silver halide emulsion layer comprising silver halide grains containing 1 x 10^-6 moles or more of rhodium salt per mole of silver and having a silver chloride content of 80 mol% or more, the emulsion In a silver halide photographic light-sensitive material containing a hydrazine derivative in the layer and/or other hydrophilic colloid layer, a non-photosensitive layer in which a dye having a peak at 300 to 400 nm is dispersed in a solid state is provided on top of the emulsion layer. A silver halide photographic material comprising: