JPS60162246A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an image having high quality and high contrast by providing a silver halide emulsion layer contg. >=80mol% silver chloride, a specific amt. of water soluble rhodium salt and specific compd. on a base. CONSTITUTION:At least one layer of silver halide emulsion layer contg. at least 80mol% silver chloride, 1X10<-6>-6.0<=10<-5> water soluble rhodium salt for each 1mol of silver halide and >=1 kind of the compd. expressed by the formula I (R1 denotes an aryl group and may have a substituent. R2 denotes a hydrogen atom or a phenyl group which may have a substituent or an alkyl group of 1-3C) is provided on a base to obtain a silver halide photosensitive material. The water soluble rhodium salt is adequately added in the stage of emulsifying the silver halide.

Description

Detailed Description of the Invention 10. Background of the Invention (Technical Field) The present invention relates to a light-sensitive material for photolithography for printing.

(Problems with the prior art) In recent years, in the field of printing and photolithography, the colorization and complexity of printed matter has increased, and color scanners have been developed. (There is a demand for this. In particular, the use of a bright room in the turning process greatly contributes to improving work efficiency, and the rate of using a bright room is increasing year by year. This result comes from both improvements in equipment such as printers and improvements in photosensitive materials.

In terms of photosensitive materials, silver halide photosensitive materials called light-sensitive materials have been developed that have ultra-low sensitivity and can be handled in bright rooms. The photosensitive material is given so-called 1-lith development and 1-process suitability.

Efforts have been made to improve the quality, but the quality, gamma of the photographic characteristic curve, fogging, undercuts, halftone dots, quality, etc. are insufficient.

On the other hand, as a technique for obtaining a high-contrast image comparable to the one-stage development process, patent disclosures can be found regarding several attempts. For example, JP-A No. 52-ISA17 and JP-A No. 5
3-40899 etc. Furthermore, techniques for obtaining high-contrast images using hydrazine compounds include Nos. 53-77616, 53-84714, 53-137133, 54-37732, 54-40629, and 55-
No. 52050, No. 55-90940, No. 56-678
No. 43 et al.; disclosed. In the processing method in the image forming method using these series of hydrazine compounds, the pH value of the developer containing the hydrazine compound or the p of the processing developer of the photographic material containing the hydrazine compound is
It is said that the i value is relatively high (.), which is considered to be annoying, and has the disadvantage of limiting the useful life of the developer.

On the other hand, in JP-A No. 56-106244, a high-contrast image can be produced at a relatively low p by containing a hydrazine compound and an amount of an amino compound to promote development.
It is assumed that it can be formed from H (11 to 11.5).

However, there have been no examples of application of these high-contrast image forming methods to "bright room photosensitive materials" using these hydrazine compounds in the technology disclosed so far. As a result, we were able to establish a technical application method for high-contrast contrast enhancement technology using these useful hydrazine compounds to bright room light-sensitive materials, which currently have the highest demand for high quality.

■5 Purpose of the Invention The first purpose of the present invention is to provide high-quality, high-contrast images for use in bright rooms!・Provides a silver rodanide photographic material. The second object is to make it possible to apply the high contrast enhancement technology using a hydrazine compound to a silver halide photographic light-sensitive material for bright room reversal.

(2) Structure of the Invention The above-mentioned objects can be achieved by the present invention as described below. That is, it contains a small (also called (capital) mol%) silver chloride, and /%0 water-soluble rhodium salt per mole of silver genide.
This could be achieved using a silver/10 silver genide photographic material containing 0 mol to 6.0 x 10 -'' mol and containing at least one compound represented by the following general formula (1).

General formula (1) %Formula% In the formula, R1 represents an aryl group and may have a substituent χ. In addition, the island has a hydrogen atom or a substituent 4, l:
Iyz represents a nyl group or an alkyl group having 1 to 3 carbon atoms.

(Specific explanation of the structure of the invention) Hereinafter, the configuration of the present invention will be specifically explained in detail.

The silver halide used in the present invention may be silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide, but the amount of silver chloride depends on the composition ratio of silver halide. (I) mole% or more, more preferably the silver chloride content is (a) mole%
That's all.

When the silver chloride content decreases, the safety under bright indoor lighting, which is important as a bright room light-sensitive material, deteriorates. This reduces the workability of the light-sensitive material (hereinafter referred to as "photosensitive material"), and the material cannot be put to practical use. The light emission distribution of a commonly used bright indoor light is on the longer wavelength side than the wavelength of 4Q Onm. As the silver chloride content decreases, the overlap between the emission wavelength of a bright indoor light and the specific sensitivity of silver halide particles increases, so the safety of bright indoor lights deteriorates. Conceivable.

The water-soluble rhodium salt used in the present invention includes:
Examples of rhodium dichloride, rhodium trichloride, and hexadiol include ammonium rhodate, but preferred is a trivalent rhodium halide complex compound such as hexachlororhodic acid (III) or a salt thereof.

In the present invention, the amount of water-soluble rhodium salt added is 1.0X10-' mole to 6.0X10-' mole per mole of silver halide.
'It's a mole. If the amount of water-soluble rhodium salt is less than i, o -' moles, the sensitivity will not be reduced to the level required for a photosensitive material which is the object of the present invention.

In other words, an emulsion which is not subjected to any of the various chemical sensitizations well known in the art is referred to as an original emulsion. Assuming that the sensitivity of the silver oxide primitive emulsion is 100, the amount of water-soluble rhodium salt added in a commonly used light-sensitive material is approximately 1, OXl0-'mol/AgX1.
The original emulsion sensitivity in molar terms is approximately 1-10. On the other hand 1
．． When adding 0X10-' mole/AgX1 mole, KFi
The original emulsion sensitivity is approximately 1000. Since this is 100 to 1000 times the sensitivity limit required for a normal light room photosensitive material, it is difficult to use a primitive emulsion with higher sensitivity than this as a normal light room photosensitive material. The reason is that
This is because commonly used exposure apparatuses have disadvantages such as the proper exposure time being too short and the safe time under indoor lighting being too short. So 1. When adding OXl0-' mol/AgX 1 mol, it is preferable to use the second desensitizer together. A specific desensitizer is chloride #2.

Examples include inorganic desensitizers such as iridium chloride and organic desensitizers such as pinacryptol yellow and phenosafranine.

Further, an organic dye having K absorption at a wavelength of 350 to 450 nm, such as tartrazine, may be used in combination. If the water-soluble rhodium salt alone is used to desensitize to the required limit, preferably it is added in an amount of 5×10 −′ mol/AgX 1 mol or more.

On the other hand, the amount of water-soluble rhodium salt added is 6,0XIOmol/A
If gX exceeds 1 mol, the contrast enhancement effect of the hydrazine compound will be significantly reduced. That is, a water-soluble rhodium salt was added in an amount up to 1.0 x 10 mol/AgX mol. In order to obtain a high-quality light-sensitive material capable of achieving the purpose of the present invention, the amount of dorazine compound added to the emulsion is 2.0 x 10-s to 10. X
Addition of 10-" molar amount is sufficient. However, if the addition of the water-soluble rhodium salt reaches 6.0 x 10 mol/AgX 1 mol, the amount of hydrazine compound added necessary to achieve high contrast is 2 XIO-" mol- lXl0-'Mo1
/Ag X 1 mol is also required. For example, as mentioned above, the amount of water-soluble rhodium salt added in the case of a commonly used light-sensitive material is approximately IXl0-'mol/AgX
In 1 molar amount, the human didine compound is 1 x 10-1
Even if 1 mol/1 mol of AgX is added, the intended high-quality light-sensitive material cannot be obtained.

From the above, the amount of water-soluble rhodium salt added is more preferably 3.5 Xl0-' mol/AgX 1 mol or less.

These phenomena are unknown facts until now. Although the mechanism of this phenomenon must wait for detailed study, the present inventors have speculated as follows. That is, it has been relatively well known for a long time that human didine compounds have electron-donating properties to silver halides, and they are also used as developing agents in U.S. Pat. No. 3,782,94.
It is also described in No. 9 etc. On the other hand, in the case of rhodium compounds in silver halide, the rhodium atoms act as folded electron acceptors, and in bright room photosensitive materials, they act as photoelectron acceptors and act as desensitizers. It is clearly superior to many bright room photosensitive materials technologies including No. i49030. However, this electron donor (hydrazine compound)
When silver halide grains KI [I] containing an electron acceptor (water-soluble rhodium salt) are present, it is thought that the character of the electron donor, that is, the contrast enhancement effect, will be significantly suppressed. In other words, there seems to be no other way than to reduce the amount of mineral and electron acceptor (water-soluble rhodium chloride) in order to effectively bring out this high contrast effect.

The need for the addition amount of the water-soluble rhodium salt used in the present invention to be small compared to the amount normally used is based on sufficient consideration of the electronic balance between electron donors and electron acceptors, as described above. Because it has to be.

This point is the content disclosed for the first time by the present invention.

In the present invention, the water-soluble rhodium salt is preferably present at the time of preparing the silver halide emulsion, but the time of preparation refers to the emulsification and physical ripening process, and the water-soluble rhodium salt is added at any time during this process by any method. do it. However, the preferred addition time is during emulsification, and a particularly preferred method is to add a water-soluble rhodium salt to the halide solution to produce #i.

This is because, in order to maximize the desensitizing effect of rhodium, rhodium atoms must be uniformly distributed from the interior to the surface of silver halide grains, and for this reason, it is preferable to add rhodium atoms to the halide solution.

Next, the hydrazine compound represented by the general formula (1) according to the present invention is shown as follows.

R1-NHNHCORt R1 Hough 1J-# group. In particular, a phenyl nucleus whose electron-withdrawing property derived from Hammett's sigma value is smaller than +0.30 is preferable. Hammett's sigma value can be determined relatively easily from literature.

An unsubstituted phenyl group is considered as one of the preferable groups. Furthermore, as preferred substituents for the aryl group, halogen groups (e.g. fluoro group, hydroxyl group), alkyl groups (e.g. methyl group, ethyl group, n-propyl group, inbutyl group, n-butyl group, inbutyl group) are preferable. , n-hexyl group, n-1'f-l group, tert-octyl Mr,
n-decyl group, n-dodecyl group), an alkoxy group, and an acylamino group (for example, an acylamino group, a propanoylamino group, and a benzoylamino group). Particularly preferred are those having a ballast group for photographic additives. The ballast group generally contains 8 or more carbon atoms, and is effective in suppressing the diffusivity in the film layer after coating the emulsion, for example, when the m-tart-pentylphenoxy group is substituted with butylamide, etc. to work.

The island represents a hydrogen atom, a phenyl group which may have a substituent, or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly preferred. Examples of particularly preferred hydrazine compounds are listed below, but the present invention is not limited to the following examples.

(1) −1−+13−2 (1)−3 (1) −4 +l) −5(1) −6 (13−7 +13− 8 (1) −9 Yes! Represented by general formula (1) The compounds can generally be synthesized by reacting hydrazines with formic acid, or by reacting human dizines with acyl halides.

, the compound represented by the general formula (1) is used in an amount of ixio-" mole to 0-4 mole per mole of silver halide, and is particularly preferably f'15X10-" moA/ to
5) It is better to add GO-” moA/amount.

In order to add the compound represented by the general formula (1) into the emulsion, a conventional method for adding additives to photographic emulsions can be used. For example, a water-soluble compound can be used as an aqueous solution of an appropriate concentration, and a water-insoluble or sparingly soluble compound can be dissolved in an appropriate water-miscible organic solvent and added to the emulsion as a solution.

The emulsion preparation method in the present invention may be a single jet method such as a forward mixing method or a back mixing method, or a double jet method using a simultaneous mixing method.

If the emulsion preparation method using the simultaneous mixing method shown in Japanese Patent Application No. 58-88186, No. 58-88220, and No. 58-200685 is followed, monodisperse particles can be obtained, which is effective against the effects of the present invention. However, the present invention is not only effective for these monodisperse particles. Further, any method such as an ammonia method, a neutral method, an acid method, or a modified ammonia method disclosed in Japanese Patent Publication No. 58-3532 may be used. The crystal habit of the silver halide grains may be cubic, tetradecahedral or octahedral, or may be tablet-shaped grains as disclosed in JP-A-58-108525. The particle size is preferably 0.5μ or less, but is not particularly limited.

The emulsion prepared under such pressure can also be chemically sensitized using a chemical sensitizer (for example, sulfur sensitization, gold sensitization, reduction sensitization, etc., or a combination thereof).

However, the object of the present invention can be achieved without any chemical sensitization.

Furthermore, the emulsion prepared in this manner may contain stabilizers such as tetrazaindenes, antifoggants such as triazoles and tetrazoles, covering power improvers, and irradiation inhibitors such as oxanol dyes and dialkylaminos. It is possible to add benzylidene dyes, wetting agents, polymer latexes, and other additives used in general photographic emulsions, such as spreading agents and hardening agents.

As the support for the silver halide photographic material of the present invention, commonly used supports such as polyester base, TAC base, baryta paper, laminated paper, glass plate, etc. are used.

As a light source for exposure of the silver halide photographic material of the present invention, a light source rich in ultraviolet rays used mainly in the printing field, such as xenon, metal halide, mercury lamp, or ultra-high pressure mercury lamp, is used.

As the developer used in the silver halide photographic material of the present invention, either a developer used in general silver halide photographic materials or a lithium developer can be used. The developing agents of these developers include dihydroxybenzenes such as hydroquinone, chlorohydroquinone, and catechol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-722 Examples include 3-pyrazolidones such as 4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; Aminophenol, para-aminophenols such as N-(4-hydroxyphenyl)glycine, β-methanesulfonamide ester, ethylaminotoluidine, N,N-diethyl-p-
Examples include p-phenylene diamines such as 722 diamine and ascorbic acids, and are used as an aqueous solution containing one or more of such developing agents.

Other developer solutions include preservatives such as sodium sulfite, potassium sulfite, formaldehyde sodium bisulfite, hydroxylamine, ethylene urea, and development inhibitors such as inorganic salts such as sodium bromide, potassium bromide, potassium iodide, etc. , 1-phenyl-5-methylcaptotetrazole, 5
- 1 such as nitrobenzimidazole, 5-nitrobenztriazole, 5-nitroindazole, 5-methyl-benztriazole, 4-thiazoline-2-thione, etc.
organic inhibitors, alkaline agents such as sodium hydroxide, potassium hydroxide, jetanolamine, triethanolamine, 3-diethylamino-1-propertool, 2
-methylamino-1-ethanol, 3-diethylamino-1,2-propanediol, diisopropylamine,
Alkanolamines having a development accelerating effect such as 5-amino-1-pentanol and 6-amino-1-hexanol, sodium carbonate, sodium phosphate, aqueous carbonate solution,
Buffers that have a buffering effect in developing solutions such as aqueous phosphoric acid solutions, salts such as sodium sulfate, sodium acetate, and sodium citrate, sodium ethylenediaminetetraacetate, sodium nitrotriacetate, and hydroxydiaminetriacetate.
Water softeners with chelating effects such as sodium acetate,
Developing hardeners such as glutaraldehyde, solvents for developing agents and organic inhibitors such as diethylene glycol, dimethyl formaldehyde, ethyl alcohol, benzyl alcohol, methyl amigzolin, methyl imidazole, polyethylene glycol, dodecyl bi-IJ dinium bromide, etc. It is constructed by adding a development regulator and the like.

The pH of the developer is not particularly limited, but is preferably in the range of 9 to 13.

An example of the composition of a preferable developer for developing the silver halide sensitive material of the present invention is as follows. Addition of hydrquinone as a developing agent to e011/It and 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone 0.1-21/l or 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.1-211/l.

Sodium sulfite as developer preservative 10-2001
/ or potassium sulfite 10 to 20011/Jl, sodium bromide or potassium bromide I as an inorganic salt development inhibitor
P-1011711, alkanolamines with development accelerating effect 1-5011/11, organic inhibitor such as 5-methylbenztriazole 0.05-219/
l, or 5-nidoμindacy-AI0.01-21
1/l, sodium carbonate 1-50 as buffering agent
It is a developer in which 11/l and 0.1 to 0.0 g/It of rum salt are added, and the pH is adjusted to 11.0 to 12.5 using a suitable alkaline agent (for example, potassium hydroxide).

The silver halide photographic material of the present invention has an image fixed thereon through the processes of fixing, washing with water, and drying after being developed with the developer described above. At this time, there are no particular restrictions on the developing temperature and developing time in the developing process, but the developing temperature is
Preferably, the temperature is 45° C. and the development time is in the range of 15 seconds to 200 seconds.

(Examples) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Silver chlorobromide emulsions 1 to 5 were prepared using the following solutions A, B and C. The amounts of sodium chloride and potassium bromide used in solution C are shown in Table 1 together with the silver halide composition of the prepared emulsion.

[Solution person]

Ossein gelatin 17.9 Polyisopropylene-polyethylene oxydifusuccinate sodium 10% ethanol solution 5IR1 Distilled water 1280 cc [Solution B] Silver nitrate 170 ml Distilled water 410 MJ [Solution C] Sodium chloride Table 1 Listed amount Potassium bromide Table 1 Listed amount Ossein gelatin 11.9 Rhodium trichloride trihydrate 5 Dabolyisopropylene monopolyethylene oxydisuccinate sodium salt 10% ethanol solution 3d Distilled water 412d Table 1 Silver halide composition and Amounts of sodium chloride and potassium bromide added: Water-soluble rhodium salt is added to solution C; CJ, -311,
0 as 5IvAgX1-v-y or 1.9 Xl
0-'-1-k/Ag X 1% is added.

Solution B and solution C were added to solution A by a simultaneous mixing method. Insulation temperature during addition and solution B and solution C at this time
The addition time, the O-Stewald ripening time after the addition, and the insulating temperature at that time are such that the average grain size of the silver halide grains after preparation is 0.20 μm, and the grain size distribution is ±0.05 μm of the average grain size. Conditions were appropriately selected so that 90% or more of the particles fell within the range. The conditions are shown in Table 2.

Table 2 Conditions for Emulsion Preparation Add Q) and Q under the conditions shown in Table 2, and after Ostwald ripening, desalt and wash with water in the usual manner. 3
0j+) was added and dispersed by stirring for 55'C (9) minutes to obtain emulsions 1 to 5. Observation using an electron microscope revealed that these emulsions were monodisperse grains with an average grain size of 0.2 μm.

Next, this emulsion was added with 6-methyl-4-hydroxy-1,3,
3m, 7-chitrazaindene as IJil/AgX1
1. mol of 1-formyl-[2-4-42-(2,4-di-t-pentylphenoxy)butylamitodophenyl]hydrazide, which is the above-mentioned dorazine compound, was added. ON
/AgX1 mole was added, and polyethylene glycol was added to 250! / Added 1 mole of AgX, added ethyl acrylate latex gelimer 211/ze, and 2.
51/wl, AgX grains were coated with saponin solution on the Prl'' base using a saponin solution as a spreading agent so that the silver amount was 3.51/wl. It was protected by a hardening overcoat layer containing mucochloric acid as a hardening agent.

The sample thus obtained was wedge-exposed using a light room printer (HBI!!IV-215 manufactured by Oak Seisakusho), and then developed for 9 seconds at ℃ using the developer shown in Table 3 below, followed by fixing, washing with water, and drying. I did this.

Table 3 Composition of developer (Developer 11) Hydroquinone 34# 1-phenyl-4,4-dimethyl-3-bizolide yO
・23II Ethylenediaminetetraacetic acid disodium salt lll3-diethylamino-1,2-propanediol 151!5-
Ethylbenzotriazole 0.49 Nag sol
761 NaBr 311 1mol/jt phosphoric acid solution 400 mtpH11,4
Make it IIt with soaking water to which Na0)lk is added.

Table 4 shows the results of the development process.

Table 4 Photographic performance set of each sample Sensitivity at a density of 2.5 IC, expressed as a relative sensitivity value with Emulsion 5 as 100.

Φyi Toshiba Sho FX, 4DBWΦNU anti-fading light about 20
When irradiated under 0/I/Tx, the maximum time without capri in the unexposed area was shown. In normal plate-making work, a minimum addition is necessary. If the application is limited, about 10 minutes is possible, but if it is not longer than 30 minutes, the work will be hindered.

*1 Obtained by connecting density 0.3 to 3.0 points on the photographic characteristic curve. 6311 Δ, indicated by X, is necessary, and O indicates high quality.

From the results shown in Table 4, the following can be said.

The higher the ratio of AgCJ in the silver halide composition of the sample, the lower the sensitivity and the longer the light room safety time.Also, in terms of detuning, all samples had very high contrast. Although they are of high quality, (1) Samples (1-1) and (1-2) with a light room safety time of 2 minutes or less cannot be used for normal plate-making work.

Ql From the above, the performance required as a light-sensitive material can be achieved by samples (1-3), (1-4) and (1-5) of the present invention.

Example 2 Using Emulsion 5 shown in Example 1, the hydrazine species to be added was evaluated. Among the sample preparation methods shown in Example 1, only the hydrazine compound to be added was changed to the following compounds, and the others were the same. Furthermore, the same developer as in Example 1 was used.

After performing wedge exposure in the same manner as in Example 1, a sample was obtained through the processes of development, fixing, washing with water, and drying.

The hydrazine compounds used here are shown below (1)
-1(11-2 +1)-3 (1) -4 (Comparison) Table 5 Hydrazine compounds used, their addition amounts, sensitivity, and hardness All hydrazine compounds were approximately 2 moles/Ag.
X1 mol was added.

From the results shown in Table 5, the following can be said.

1. Sample without addition of hydrazine compound (2-1
) has low sensitivity but is very soft and cannot be put to practical use.

2. In hydrazine compounds, (1) -1 and (11
-2 has practicality, but is more non-diffuse (1)
-3 and (11-4 have a higher contrast enhancement effect per mole added, and hydrazine compounds having a non-diffusible group are preferable.

3. Among hydrazide compounds, the t-pentyl form had almost no effect.

4. From the above, the hydrazine compound according to the present invention is extremely useful in achieving the object of the present invention.

Example 3 One type of silver chlorobromide emulsion was prepared using the following solutions A, B and C. At this time, the amount of rhodium chloride trihydrate in Solution C was added as shown in Table 6.

[Solution A]

Ossein gelatin 17II Polyimp tetrabirene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 5d Distilled water 1280cc [Solution B] Silver nitrate 1701 Distilled water 4101t [Solution C] Sodium chloride 74.81N Potassium bromide 2.389 Ossein Gelatin 11g Polyethylene propylene polyethylene oxydisuccinic acid ester sodium salt 10% ethanol solution 5a Rhodium trichloride trihydrate Table 6 amounts listed Distilled water 412d Solution AKffI Solution B and Solution C were mixed simultaneously at 40°C 4
Additions were made in 0 minutes. After the addition was completed, Ostwald ripening was carried out at 40°C for 10 minutes, followed by desalting and washing with water according to the usual method, and then an aqueous solution of ossein gelatin containing 600 ml of ossein gelatin.
Add 317 (containing 30g of ossein gelatin) to 55
The mixture was stirred for 30 minutes and dispersed to obtain each emulsion.The emulsion had monodisperse particles with an average powder size of 0.20 μm.

A coating emulsion was prepared using the same hydrazine compound as in Example 1, coated, and dried to obtain a sample. At this time, the sample (3-1
For 2), 1 mole of 1011Q/AgX was added to the same emulsion as in (3-10) with sodium thiosulfate pentahydrate.
After chemical ripening at 50°C, 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer in an amount of 111/AgX1 mol. For this sample only, no hydrazine compound was added and other additives were the same as those for samples (3-1) to (3-11), and the sample was obtained after coating and drying using the same method.

After the samples obtained in this way were subjected to wedge E under the same exposure conditions as in Example 1, samples (3-1) to (3-11)
was processed with the developer shown in Example 1. Sample (for 3-12HC, Konishiroku Photo Industry developer CD
It was developed with M-621 at 38'C.

The samples thus obtained were evaluated for photographic characteristics such as sensitivity, high contrast liquid, and light room safety time, and the results are summarized in Table 6. The sensitivity is expressed as a relative sensitivity when (3-12), which is a sample obtained by processing a commonly used bright room photosensitive material with a common rapid access developer, is taken as 100. Other evaluation methods were based on Example 1.

Table 6: Rh-11 added to each sample and photographic performance From the results shown in Table 6, the following can be said.

1. Rh (J3@3H, O addition amount is 1.OX 10-
'mol/AgX less than 1 mol (3-1), (3-2
) has higher sensitivity than the normally used light-sensitive materials, and also has a very short light-room safety time, so it cannot be used in practical use.

2, RhC1,-3Il! 0(r) addition amount is 1. OXl
0-' ~1. Those in the range of OXl0-' mol/A,

3, 8hC4”3H1017) Addition amount force 5.OXl0
-' ~1. Those in the range of OXl0-' mol/AgX 1 mol have performance equivalent to or higher than that of ordinary light-sensitive materials (3-12) and can be put to practical use.

4.RhCJs “3%Om dosing cuff, OXl0-
' % # / Ag
There are problems in terms of photographic performance and quality, and it is considered that it cannot be put to practical use.

5. RhC1m'3HzOf) addition amount F
ii, ox10-'! k ~5. High quality with high contrast within the range of OXl0-' mol/AgX 1 mok,
We were able to obtain a photosensitive material with a long light room safety time.

Procedural amendment April 18, 1985 Patent application No. 17607 of 1988 2 Title of invention: Halogenated silver silicide photographic light-sensitive material 3, person making the amendment Relationship to the case Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 26-2, 1 Sakura-cho, Hino-shi, Tokyo Column 6 of ``Detailed explanation of the invention'' in the specification Contents of amendment (1) ``Problems with the prior art'' on page 2, line 2 of the specification was corrected to "prior art and its problems."

(2) Page 2, line 17 It says "halftone dot 9 quality" but it has been corrected to "halftone dot quality".

(3) On page 13, line 3 from the bottom, it says "I can do it." For example, the compound (1)-1 is prepared by adding 29y of P-tolylhydrazine to 30g of formic acid kept warm at 5°C.
After adding to the solution while stirring, heat (55°C) and add 1
The reaction was allowed to proceed for 5 minutes. This was cooled on ice, and the resulting crystals were separated and purified by recrystallization with 150 d of acetonitrile. In this way, colorless needle crystals 12.9 were obtained. ” he corrected.

(4) Page n, line 12 First, I corrected "68 degrees Celsius" to "60 degrees Celsius."

Claims (1)

Scope of Claims: Contains at least mol % of silver chloride, and contains 1X10-' mol to 6.0X10-' mol of water-soluble rhodium salt per 1 mol of silver halide, and has the following general formula ( 1)
1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing at least one type of compound represented by the following. General formula (1) ToriNjutsuaiCOchi [In the formula, R1 represents an aryl group and may have a substituent. Also, - represents a hydrogen atom, a phenyl group which may have a substituent, or an alkyl group having 1 to 3 carbon atoms. ]