CN85108256A - Light-sensitive silver halide photographic material - Google Patents

Abstract

Be coated in the light-sensitive silver halide photographic material on the base material, comprise one deck silver halide emulsion layer and one deck hydrophilic colloid layer at least at least, wherein, in one deck silver halide emulsion layer and hydrophilic colloid layer at least, add useful below triphenyltetrazolium () compound of general formula (1) expression.Wherein, R ₁, R ₂And R ₃Each represents hydrogen atom, or Hamett σ _PValue is the group of negative, Be meant negative ion; But, R ₁, R ₂And R ₃Can not be hydrogen atom simultaneously.

This light-sensitive silver halide photographic material in lithography, can be used to form netty images, and its contrast is very big, at high temperature, high humidity stable storing, can not damage its performance.

Description

Light-sensitive silver halide photographic material

The present invention sets forth a kind of new light-sensitive silver halide photographic material that can be used to form photographic image.Literary composition specifically, novel light-sensitive silver halide photographic material involved in the present invention, the big netty images that can present a contrast, this material has very big purposes in lithography.

So far, people have known and have utilized light-sensitive silver halide photographic material that very big photographic image presents a contrast.For example, the light-sensitive silver halide photographic material that disposal is made up of chlorine silver bromide or chlorosulfonylation silver emulsion, making big netty images of contrast or the former figure of lines, is a kind of famous method, wherein, the average particle size of the silver halide fine-grain in the emulsion, approximate or be lower than 0.5 micron, its distribution of particle sizes is narrow and even, the content of silver chloride in the emulsion, for example, be 50 or greater than 50 grammol.In the shadow, the concentration of sulfite ion is little in the alkalescence that adopts, and only contains p-dihydroxy-benzene and make developer.

This light-sensitive silver halide photographic emulsion is called as lithographic plate type light-sensitive silver halide photographic material.It generally is used for the variable density of the continuous tone of original copy is converted to the aggregate of site in imprint lithography, the site is changeable, and each density partly of its area and image is directly proportional.In order to realize this conversion, adopt lithographic plate type light-sensitive silver halide photographic material, make netty images.This method is, takes a picture to original copy by netting twine half tone or contact screen plate device, develops with so-called lithographic plate type developer or developer solution then.Sulfite ion concentration in the developer solution is very little, and, wherein only contain the p-dihydroxy-benzene developer.This lithographic plate type light-sensitive silver halide photographic material; even adopt the high common developer solution of sulfite ion concentration; handle with developer solution as commercially available processing photographic paper; its gamma value (r is a contrast factor); can not surpass 5 or 6 yet; the result usually can produce striped, must avoid occurring this result concerning forming the site as far as possible.So in fact, with the photographic material that above-mentioned lithographic plate type developer solution is used, as shadow tone negative and positive the time, prevention produces striped and is considered to vital.Above-mentioned lithographic plate type developer solution, J.A.C.Yule has play-by-play (J.Franklin InstItute.V.239.P.221(1945) on magazine), wherein only contain the p-dihydroxy-benzene developer basically, this developer solution that contains the low concentration sulfite ion plays antioxidant to developer.

This developer solution keeping quality is poor, is subject to autoxidation.Therefore, in order to make shadow tone negative and the positive that makes, remain good quality, the activity that the lithography person need control developer solution remains unchanged, and this activity can be passed in time and be descended, thereby unavoidably makes troubles to operation.

Because it is very big to improve the keeping quality benefit of lithographic plate type developer solution, to this, people have made great effort.But the good developer solution that calls continuously of obtained improvement and keeping quality is compared, as Mitouer/p-dihydroxy-benzene developer solution, phenidone/p-dihydroxy-benzene developer solution is still fully not enough.

Nowadays, utilize the phenidone/p-dihydroxy-benzene developer solution that contains the high concentration sulfite ion, done some and attempted, so that the method for making the hard contrast image to be provided, this method is developed applicable to lithography.For example, the method that Japanese uncensored patent publication No. 106244/1981 is disclosed, employing be hydrazine (being hydrazine) compound, in developer solution, add and can make the amino-compound that develops and quicken in right amount, can make the image of hard contrast.In addition, in the light-sensitive silver halide photographic material that Japanese patent application publication No. (17825/1984,17818/1984,17819/1984,17820/1984,17821/1984,17826/1984,17822/1984 etc.) discloses, contain tetrazolium () compound.

But, in the technology of previous employing hydrazine compound, need be adjusted to the PH of developer solution up to about 12, like this, just cause the stability problem of developer solution.In addition, also produced the black splotch that is referred to as black pepper, thereby caused serious defective in the application on the spot at non-area of image.

In addition, in the technology of the tetrazolium () compound that discloses after a while, though it does not resemble the defective the previous technology, no matter on hard contrast and net-point quality, it is very satisfactory all can not to say so.This means that the situation of reality is in the former technology, also to can be described as to have reached fully with the lithography field without any a kind of material and will make the performance that significantly improved requirement is consistent recently.Like this, just, to the method that adopt tetrazolium () compound hard contrast image be further improved.

The object of the invention provides a kind of light-sensitive silver halide photographic material, this material can solve existing the problems referred to above of silver emulsion of using tetrazolium () compound, and this material contrast that provides is very big, and it is left in high temperature, the high humidity environment, it is stable that its performance still keeps, and undergoes no deterioration.

By intensive research, the inventor finds, if be coated in the light-sensitive silver halide photographic material on the base material, comprise one deck silver emulsion and one deck hydrophilic colloid at least at least, wherein and add useful below the triphenyltetrazolium () compound of general formula (I) expression, get final product so that the problems referred to above are resolved, thereby reach purpose of the present invention.

General formula (I):

Wherein, R ₁R ₂R ₃Each represents the σ of hydrogen atom or Hamett _pValue is the group of negative, x ^-Be meant negative ion; But R ₁R ₂And R ₃Can not be hydrogen atom simultaneously.

If be coated in the light-sensitive silver halide photographic material on the base material, comprise one deck silver emulsion and one deck hydrophilic colloid at least at least, wherein, the silver halide grain that emulsion layer is contained is to form in the presence of water-soluble rhodium salt, the consumption of rhodium salt is 1 * 10 ^-7-5 * 10 ^-7Grammol/every grammol silver halide, meanwhile, in one deck hydrophilic colloid at least, at least a the triphenyltetrazolium () compound that also adds useful following general formula (I) ' expression, even the light-sensitive silver halide photographic material that obtains thus at high temperature, is deposited in the high humidity environment, it is stable that performance still keeps, and undergoes no deterioration.

General formula (I) ':

Wherein, R ₁, R ₂And R ₃Each represents the σ of hydrogen atom or Hamett _pValue is the group of negative, X ^-Be meant negative ion, but R ₁, R ₂And R ₃Can not be hydrogen atom simultaneously.

The implementation method explanation of recommending

As mentioned above, requirement of the present invention, with in the triphenyltetrazolium () compound of general formula (I) or (I) ' expression, the substituent R of phenyl ₁, R ₂And R ₃, be meant the σ of hydrogen atom or Hamett _pValue is the group of negative, σ _pValue is to show electrophilic degree, σ _pFor negative just refers to electron withdraw group.

In some papers, can find the Hamett σ of phenyl substituent _pValue, for example, at Journal of Medical ChemistryV.20.P.304(1977), C.Hansch etc. point out σ in its report _pFor the group of negative can comprise, as methyl (σ _p=-0.17, hereinafter all refer to σ _pValue), ethyl (0.15), cyclopropyl (0.21), just-and propyl group (0.13), isopropyl (0.15), cyclobutyl (0.15), normal-butyl (0.16), isobutyl (0.20), just-amyl group (0.15), cyclohexyl (0.22), amino (0.66), acetylamino (0.15), hydroxyl (0.37), methoxyl (0.27), ethoxy (0.24), propoxyl group (0.25), butoxy (0.32), amoxy (0.34) etc.These groups are useful substituting groups of general formula in the present invention (I) or (I) ' compound.

General molecular formula (I) and (I) ' compound, each substituent R wherein ₁, R ₂And R ₃Carbon number, the suggestion addition sum be no more than 4, from net-point quality, total carbon atom number preferably is no more than 2.Also advise R ₁, R ₂And R ₃All be substituted in the contraposition of phenyl ring.On the other hand, in these substituting groups, have at least one be hydrogen atom for well, more specifically say R ₁, R ₂And R ₃Arbitrarily that can be a hydrogen atom, again with R ₁Better for hydrogen atom, they are the compound of being recommended equally.If R ₁, R ₂And R ₃In arbitrarily that is a hydrogen atom, so, all the other two substituting groups, have at least one more desirable with alkyl.If two substituting groups are alkyl, these two alkyl preferably have identical carbon number, advise that also they are identical alkyl.

With the compound used therefor of the present invention of general formula (I) or (I) ' expression, its object lesson is as follows, and but, compound used therefor never only limits to these examples:

The tetrazolium () compound that the present invention is used can be with reference to as Chemical Reviews, Vol.55, and PP.335-483, the method that is disclosed is easy to be synthesized.

The consumption of tetrazolium () compound is pressed contained every grammol silver halide calculating in the light-sensitive silver halide photographic material, and its scope is preferably about 1 milligram～10 grams, and is better up and down with 10 milligrams～2 grams again, is good about restraining with about 10 milligrams～1 especially.

Light-sensitive silver halide photographic material of the present invention comprises base material and is coated on the silver emulsion of one deck at least and one deck hydrophilic colloid at least on the base material.Silver emulsion can directly be coated on the base material, perhaps is coated on the hydrophilic colloid layer that does not contain silver emulsion of insertion.Hydrophilic colloid then both can be coated on the silver halide emulsion layer, also can be used as protective seam, was coated between base material and the silver halide emulsion layer.In addition, if be coated with the multiple emulsion layer, every layer of so used emulsion can have different light sensitivity, as ISO and low speed.In this occasion, silver halide emulsion layer can be placed on two-layer between, the hydrophilic colloid layer is then used in the middle layer, also can add one deck middle layer between silver halide emulsion layer and protective seam.The used tetrazolium of the present invention () compound can be added in silver halide emulsion layer and/or above-mentioned various hydrophilic colloid layer.

The best approach of implementing light-sensitive silver halide photographic material of the present invention is, tetrazolium () compound is joined silver halide emulsion layer, and silver halide emulsion layer and the contained hydrophilic colloid of hydrophilic colloid layer, usefulness be gelatine derivative.

With tetrazolium () compound dissolution in suitable aqueous solvent and organic solvent, perhaps after dissolving, sneak into again such as in this class matrix of gelatin or derivatives thereof, perhaps this compound is dispersed in the emulsion fluid, adopt these methods, just can join silver halide emulsion layer and/or hydrophilic colloid layer to tetrazolium () compound.The present invention can adopt top any method.

The used tetrazolium of the present invention () compound can reach good image performance when using separately.Even two or more such compound is cooperated use by proper proportion, image performance is not had deleterious effect yet.In addition, the used tetrazolium () of the present invention can also cooperate use by proper proportion with the tetrazolium () compound beyond this invention scope.

Tetrazolium of the present invention () compound can join silver halide emulsion layer, and this is a kind of good implementation method.Another kind of good implementation method is, tetrazolium () is joined near the silver halide emulsion layer hydrophilic colloid layer of (wherein containing hydrophilic colloid), perhaps by insertion one deck middle layer, joins contiguous hydrophilic colloid layer.

Also have a kind of implementation method to be, tetrazolium of the present invention () compound can be dissolved in the appropriate organic solvent, methyl alcohol for example, alcohols such as ethanol, ether, esters etc. directly are coated in the potpourri that obtains on the outermost layer of silver halide emulsion layer of sensitive photographic material then.

Among the present invention,,, can obtain special excellent results to reduce the water wettability of tetrazolium () if, use at combined form with negative ion and tetrazolium of the present invention () compound chemical combination mutually.This negative ion can comprise, for example, and the acid group of mineral acid (as perchloric acid), organic acid acid group (as sulfonic acid and carboxylic acid), and anionic activator.More specifically say, it can comprise the alkyl benzene sulphonate salt anionic that carbon number is few, and is as to a toluenesulfonic acid salt anionic, right-the dodecyl benzene sulfonate negative ion, alkyl bitter edible plant sulfonate anionic, the lauryl sulfate negative ion, tetraphenyl borate salts, dialkyl sulfosuccinate succinate negative ion is as two-2-ethylhexyl sulfo-succinic acid salt anionic, Aethoxy Sklerol sulfuric ester negative ion, as the ceteth sulfate anion, stearate negative ion, polyacrylate negative ion etc.

These negative ion can mix with tetrazolium of the present invention () compound earlier mutually, join the hydrophilic colloid layer then.They also can join silver halide emulsion layer separately, or add the hydrophilic colloid layer that contains (or not containing) tetrazolium of the present invention () separately.

Water-soluble rhodium salt of the present invention can be used for, the dichloride rhodium can be comprised, rhodium chloride, six radium chlorides acid ammoniums etc. are preferably used the halide complex of trivalent rhodium, as chlordene rhodium (III) acid or its salt, or the rhodium chloride trihydrate.

The water-soluble rhodium salt consumption of every grammol silver halide can be 1.0 * 10 ^-7-5.0 * 10 ^-7Grammol is if consumption is lower than 1.0 * 10 ^-7Grammol just can not satisfactorily reach hot and humid stability goal of the present invention.Otherwise, if consumption is higher than 5.0 * 10 ^-7, just can increase the desensitization of water-soluble rhodium salt pair silver halide.This situation is that the skilled person who is engaged in this technology is familiar with, and like this, just is difficult to reach desired light sensitivity.

Among the present invention, water-soluble rhodium salt can just exist when silver halide grain forms.This place, " during formation " the words is meant that silver halide is emulsified and is subjected to this section of physical ripening process.Rhodium salt also can add with classic method in the random time in this section process.Add when but, rhodium salt is preferably in emulsification.Preparing emulsion with the halide solution that adds water-soluble rhodium salt, is more suitable method.The distribution of rhodium ion in silver emulsion to every silver halide grain, should be tried one's best evenly.Rhodium salt distribution for every crystal grain has no particular limits.The rhodium salt distribution of grain surface and crystal grain inside can be uniformly, also can bias toward grain surface or inside.

The silver halide that light-sensitive silver halide photographic material of the present invention is used, chlorine silver bromide preferably, wherein the ratio of Agcl/AgBr is 100/0～2/98, is good with 90/10～50/50 especially.

In addition, the preferably single decentralized of silver halide grain, its mean grain size is 0.15～0.40 micron, the distribution coefficient of grain size (representing) with (grain size distribute standard deviation/mean grain size) be 15/0 or below.

Silver halide emulsion layer of the present invention, promptly silver emulsion is wherein advised preparation in the following method: according to double-jet method, with water-soluble silver halide and halid aqueous solution, add hydrophilic colloid aqueous solution, just can be made into silver halide photographic emulsions.The adding speed of silver halide and halide solution will make the speed of growth of silver halide grain in hydrophilic colloid be no more than the critical speed of growth.Start at from beginning to mix, to be equivalent to whole adding 1/30～1/ 5 period in period, the E of hydrophilic colloid aqueous solution _AgValue remains on certain steady state value in 140～200 millivolts of scopes substantially.From now on, be equivalent to period of half at least in whole adding period, E _AgValue remains on 80～140 millivolts of certain steady state values substantially.

" the silver halide speed of growth is no more than the critical speed of growth " the words is meant the supersaturation concentration that does not have new nucleus in solution, and this nucleus can produce new silver halide grain.

By in current system, in fact forming crystal grain, change the different adding speed of silver ion and halide ion simultaneously, and from reaction vessel, sample, use electron microscope observation, to confirm wherein to have or not new nucleus to produce, can determine the above-mentioned critical speed of growth thus.

E _AgThe notion of value is well-known to the skilled person who is engaged in this technology.It is meant the current potential with the silver of numeric representation, E _AgValue can adopt argent electrode and the saturated Ag/Cl contrast electrode of binode type to determine.

For example, in the uncensored patent publication No. 197534/1982 of Japan, disclosed E _AgNumerical value.

The silver halide that the present invention is used can utilize various chemical sensitizers to carry out sensitizing.They can comprise, for example, active gelatin, and the sulphur sensitizer (as sodium thiosulfate, the arylthio urea, thiocarbamide, and aryl isothiocyanate), selenium sensitizer (as N, N-dimethyl seleno urea and seleno urea), reductibility sensitizer (as trien and butter of tin), and various noble metal sensitizer.The latter's typical case has chloraurin acid potassium, auri potassium rhodanide, potassium chloroaurate, 2-auro-sulfo group benzothiazole chloromethanes, ammonium chloropalladate, potassium chloroplatinate, sodium chloropalladite etc.Every kind of sensitizer can use separately, also two or more sensitizers can be cooperated use.If adopt golden sensitizer, available ammonium thiocyanate is made auxiliary agent.

The used silver emulsion of the present invention, available one or more sensitizing dyes carry out optical sensibilization, thereby make each desired wavelength photoreceptor district obtain photonasty.Employed sensitizing dye can comprise numerous species, the present invention can with the optical sensibilization dyestuff cyanine is arranged, merocyanine, three nuclears or four nuclear merocyanines, three nuclears or four nuclear cyanine, styryl dye, half cyanine, full utmost point cyanine, oxygen alcohol, half oxygen alcohol etc.In the structure of these optical sensibilization dyestuffs, be preferably with basic group,, or have as rhodamine as thiazoline and thiazole, 2-thiohydantoin ， oxazolidinedione, berbituric acid, thioberbiture acid, and ring such as pyrazolone are as nitrogenous heteronucleus.These rings can be by alkyl, hydroxyalkyl, and halogen, phenyl, cyano group or alkoxy replace.In addition, this optical sensibilization dyestuff can also with the ring condensation mutually on carbocyclic ring or the heterocycle.Use above-mentioned optical sensibilization dyestuff, especially when adopting merocyanine type sensitizing dye, it can also play and widen the effect of development tolerance except optical sensitization is arranged.

The used silver emulsion of the present invention can also be stablized with the compound that following patent discloses, and these patents are as U.S. Patent number 2,444,607,2,716,062,3,512,982, Deutsches Reichs-Patent publication number 1,189,380,2,058,626,2,118,411, Japanese patent application publication No. 4133/1968, U.S. Patent number 3,342,569, Japanese patent application publication No. 4417/1972, Deutsches Reichs-Patent publication number 2,149,789, Japanese patent application publication No. 2825/1964 and 13566/1974; The examples of compounds of recommending has, for example, 5,6-propylidene-7-hydroxyl-s-triazolo, (1.5-a) pyrimidine, 5,6-tetramethylene-7-hydroxyl-s-triazolo (1.5-a) pyrimidine, 5-methyl-7 hydroxyls-s-triazolo (1.5-a) pyrimidine, 7-hydroxyl-s-triazolo (1.5-a) pyrimidine, 5 methyl-6-bromo-7-hydroxyl-s-triazolo (1.5-a) pyrimidine, gallate fat or (salt) are (as gallate isoamyl fat.Gallate dodecyl fat, propyl gallate, gallate sodium), mercaptan (as 1-phenyl-5-mercapto-tetrazole and 2 mercaptobenzothiazolers), benzotriazole (as 5-bromobenzene and triazole and 5-methylbenzotrazole), benzimidazole (as the 6-nitrobenzimidazole).

Above-mentioned silver halide and tetrazolium () compound can be present in the hydrophilic colloid layer.The hydrophilic colloid that the present invention uses is gelatin preferably.Except that gelatin, hydrophilic colloid can also be, as the colloid albumin; agar, Arabic gum, alginic acid; the cellulose acetate of hydrolysis, acrylamide, imidization polyamide; polyvinyl alcohol (PVA), hydrolysed polyvinyl acetate, gelatine derivative such as phenyl carbamyl gelatin; acidylated gelatin, and (see U.S. Patent number 2,614 with the gelatin of phthalate; 928 and 2,525,753); or being connected to the gelatin graft polymerization thing of vinyl monomer, the indication monomer is as styrene, acrylate; methacrylic acid; and methacrylate (is seen U.S. Patent number 2,548,520 and 2; 831; 767) these hydrophilic colloids also can be used on the photographic coating that does not contain halogenation, as antihalation layer; protective seam, the inside such as middle layer.

Base material or carrier material that the present invention is used mainly contain, for example, and herbarium paper, coated has poly paper, Dampler Ace, glass plate, cellulose acetate, nitrocellulose, dacron polyester film, polyamide membrane, polypropylene screen, polycarbonate membrane, polyester film, polyamide membrane, polypropylene screen, polycarbonate membrane, polystyrene film etc.Select that a kind of base material for use, depend on the purposes that light-sensitive silver halide photographic material is prepared.

Be used in the photosensitive material of the present invention on the above-mentioned carrier material, having one deck at least is silver halide emulsion layer or hydrophilic colloid layer, wherein, is added with tetrazolium of the present invention () compound in described one deck at least.But, the structure of photographic material preferably as protective seam, is coated in the hydrophilic colloid layer on the silver emulsion, and reaches desired thickness, and its thickness is advisable with 0.1～10 micron, is good with the 0.8-2 micron especially.

Silver halide emulsion layer of the present invention and hydrophilic colloid layer only otherwise damage effect of the present invention, can also add various photograph adjuvants, as the gelatin plastifier, rigidizer (hardener), surfactant, image stability agent, UV absorbers, anti fouling agent, PH correctives, antioxidant, antistatic agent, thickening agent, the crystal grain improver, dyestuff, mildewproof agent, whitening agent, developing powder correctives, matting agent etc.

The present invention especially recommends the various adjuvants that use, wherein, compound as thickening agent and plastifier is disclosed in the following patent, and these patents are, for example, U.S. Patent number 2,960,404, Japanese patent application publication No. 4939/1968, Deutsches Reichs-Patent publication number 1,904,604, the uncensored patent publication No. 63715/1973 of Japan, Japanese patent application publication No. 15462/1972, belgian patent numbers 558,143, object lesson has styrene/sodium maleate multipolymer, asuro etc.; Rigidizer (hardener) then can comprise the aldehyde type, epoxy type,

The piperazine type, the reactive halogen type, Vinyl-Sulfone Type, isocyanate-based, sulfonate type, carbodiimides type, mucochloric acid type, and acyl group type hardener; UV absorbers can comprise as U.S. Patent number 3,253,921 and British Patent No. 1,309, the compound that is disclosed in 349, especially more following compounds, 2-(2 '-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3,5-two-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3-the tert-butyl group-5-butyl phenyl)-and the 5-chlorinated benzotriazole, 2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-the 5-chlorinated benzotriazole etc.; Dyestuff in the adjuvant can comprise the compound that discloses as following patent, and these patents are U.S. Patent number 2,072; 908, Deutsches Reichs-Patent numbers 107,990, U.S. Patent number 3,048; 487,515,988, these compounds can be added in protective seam, emulsion layer or the inside, middle layer.In addition, as the surfactant of coating aid, emulsifying agent, coating solution perviousness promoter, defoamer, or the reagent of the various physical properties of sense of control luminescent material, can comprise the compound that discloses as following patent, these patents are British Patent No. 548,532,1,221,980, U.S. Patent number 2,992,101 2956,884, French Patent (FRP) number 1,395,544, and Japanese patent application publication No. 43125/1973, these compounds comprise that especially granularity is the silica gel and the polymethyl methyl esters of 0.5-20 micron.

The sensitive photographic material that contains tetrazolium of the present invention () compound in silver halide emulsion layer and/or the hydrophilic colloid layer can develop in the presence of with the compound of following general formula (II) expression.

General formula (II):

Wherein, R ₁Be meant at 5-or the locational nitro of 6-, R ₂Be meant that hydrogen atom or carbon number are the alkyl of 1-5, M is meant hydrogen atom, alkali metal atom, alkaline earth metal atom, or kation (as ammonium ion).

Compound with general formula (II) expression can comprise the nitro indazole as 5-, 6-nitro indazole etc.But the present invention never is limited to these compounds.

To be dissolved in organic solvent with the compound of general formula (II) expression, as diglycol, triethylene glycol, ethanol, diethanolamine, and triethanolamine, or be dissolved in alkali (as NaOH), or be dissolved in acid (as acetic acid), add developer solution then.Also can directly add developer solution without the step of dissolving.

With the compound of general formula (II) expression, the concentration range in developer solution is every liter of about 1-1000 milligram, and the scope with about 50-300 milligram is good again.

The developer of using for silver halide black and white sensitive photographic material of the present invention can be described below, and this class developer class developer can cooperate use with the compound that above-mentioned general formula (II) is represented.

HO-(CH=CH-) _n-OH type developer: exemplary is a p-dihydroxy-benzene, and other example has catechol (catechol), 1,2,3,-thrihydroxy-benzene and derivant thereof; ascorbic acid, chlorohydroquinone, bromo quinhydrones; the isopropyl quinhydrones, methylbenzene quinhydrones, methylnaphthohydroquinone; 2,3-dichloro hydroquinone, 2; the 5-dimethyl hydroquinone, 2,3-two bromohydroquinones; 2,5-resacetophenone, 2; 5-diethyl quinhydrones, 2,5-two-right-phenethyl quinhydrones; 2,5-two-Benzamido quinhydrones, 4-chloro catechol; 3-phenyl catechol, 4-phenyl catechol, 3-methoxyl catechol; 4-acetyl group 1,2,3,-thrihydroxy-benzene, 4-(2-hydroxyl benzoyl) 1,2,3,-thrihydroxy-benzene, sodium ascorbate etc.

HO-(CH=CH-) _n-NH ₂The type developer: exemplary is the amino-phenol that ortho position or contraposition replace, or amino-pyrazol quinoline ketone.It comprises the 4-amino-phenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6 phenylphenols, 4-amino-2 phenylphenol, 3, the 4-diaminophenol, 3-methyl-4,6-diaminophenol, 2, the 4-diamino resorcin, 2,4,6-triamido phenol, N-methyl-para-aminophenol N-beta-hydroxyethyl-para-aminophenol, right-the hydroxyphenyl aminoacetic acid, the amino naphthol of 2-etc.

H ₂N-(C=C-) _nNH ₂The type developer: they comprise, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-2 amino-N, N-diethylaniline N-(4-amino-3-methyl-phenyl) morpholine, p-phenylenediamine (PPD), 4-amino-NN-dimethyl-3-hydroxyanilines, N, N, N, the N-tetramethyl-para-phenylene diamine, 4-amino-N-ethyl-N(beta-hydroxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N-(beta-hydroxyethyl) aniline, 4-amino-N-ethyl (beta-methoxy-ethyl)-3-methylaniline, 4-amino-3-methyl-N-ethyl-N-(Beta-methyl sulfonamide base ethyl) aniline, 4-amino-N-J base-N-r-sulphur butylaniline, the 1-(4-aminophenyl) pyrrolidine, 6-amino-1-ethyl, 12,3,4-tetrahydrochysene quinone, the amino julolidine of 9-(aminojulolidine) etc.

The heterocyclic type developer: they comprise the 3-pyrazolidone, for example, and 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-methylol-3-pyrazolidone; Also comprising 1-phenyl-4-amino-5-pyrazolone, 1-(is right-aminophenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5-amino-uracil etc.

Except developer recited above, the developer that is disclosed in the books and periodicals below the present invention also can actually use, they are " The Theory of the Photographic Process " the 4th edition, the 291-334 page or leaf, and Journal of the American Chemical Society, Vo1.73, Page 3,100(1951).These developers can use separately, also two or more developer can be cooperated use.But, adopt back kind way, better effects if.

The present invention also can add sulphite such as potassium sulfite and ammonium sulfite and make antiseptic in developer solution.Even if the use antiseptic can't damage effect of the present invention.This can think one of characteristics of the present invention.Also can adopt azanol and hydrazide compound to make antiseptic.In addition, also can adopt in the black-and-white developer alkali metal hydroxide and carbonate commonly used, or amine makes the buffering agent of developer solution, with the PH of control developer solution.Also can in developer solution, add inorganic development restrainer such as potassium bromide, and organic development restrainer such as benzotriazole, or the reagent such as ethene tetraacethyl (IV) diamines of adding energy trap metals ion, and development accelerant such as methyl alcohol, ethanol, phenmethylol, poly-alkoxy ether.Also can be added with the natural saponin of surfactant such as alkylaryl sodium sulfonate in the developer solution, saccharide, and the Arrcostab of top compound.In addition, hardener such as glutaraldehyde can also be arranged, formalin, and glyoxal, and ionic strength adjustor such as sodium sulphate

The used developer solution of the present invention can also contain alkanolamine and dibasic alcohol is made organic solvent.The example of alkanolamine has monoethanolamine, diethanolamine and triethanolamine, and to be good with triethanolamine, the alkanolamine consumption is every liter of developer solution 5-500 gram, and is best with 20-200 gram effect.The example of dibasic alcohol has ethylene glycol, diglycol, propylene glycol, triethylene glycol, the 1.4-butylene glycol, 1.5-pentanediols etc. are good with diglycol again, the dibasic alcohol consumption is every liter of developer solution 5-500 gram, with 20-200 gram effect for well.These organic solvents can separately or cooperate use.

Light-sensitive silver halide photographic material of the present invention, the developer processing with containing above-mentioned development restrainer can obtain the fabulous sensitometric characteristic of storage stability.

According to the developer of above-mentioned preparation, its pH value is 9-12, and but, from keeping quality and photographic property, pH value preferably is chosen in 10-11.

Light-sensitive silver halide photographic material of the present invention can be processed under various conditions.As for processing temperature, preferably be no more than 50 ℃ as development temperature, especially to be no more than 30 ℃ for good.Development time generally can be finished at three minutes, especially with two minutes best results, adopts this development time, often can reach desirable result.Except developing, also available procedure of processing has, and for example, washing stops showing, and is stable, photographic fixing, and the also available post bake that gives, neutralization etc.These steps can suitably be saved.In addition, these procedure of processings can be with so-called manual development method (developing and frame develops as disc type), or mechanical development method (as cylinder development and suspended automatic development) is implemented.

The present invention will be with the following examples detailed explanation of making comparisons.

Embodiment 1

Utilize following solution (A, B, C) preparation chlorine silver bromide emulsion.

Solution A:

Bone collagen gelatin 17 grams

Polypropyleneoxide-polyethylene oxide two

5 milliliters of 10% ethanolic solutions of sodium butyrate

1280 milliliters of distilled water

Solution B:

Silver nitrate 170 grams

410 milliliters of distilled water

Solution C:

Sodium chloride 40.9 grams

Potassium bromide 35.7 grams

Polypropyleneoxide two sodium butyrates

5 milliliters of 10% ethanolic solutions

Bone collagen gelatin 11 grams

407 milliliters of distilled water

Solution A is remained on 40 ℃, add sodium chloride then, make E _AgValue remains on 160 millivolts.

Adopt the twin-jet nozzle method, add solution B and solution C inward, the mixing agitator of use can be referring to the uncensored patent publication No. 92523/1982 of Japan and 92524/1982.

In whole 80 minutes reinforced periods, progressively increase the charging rate (seeing Table I) of these solution, keep E simultaneously _AgNumerical value is constant.

The table I

Reinforced time solution B solution C

(branch) (ml/min) (ml/min)

0 1.13 1.11

10 1.13 1.11

20 2.03 1.99

30 3.17 3.11

40 4.57 4.48

50 6.22 6.10

60 8.13 7.97

70 10.29 10.01

80 12.74 12.49

Begin reinforced after 5 minutes, with the sodium-chloride water solution of 3 mol, with E _AgValue is changed into 120 millivolts from 160 millivolts.After this, before mixing was finished, this numerical value remained unchanged.

In order to keep E _AgNumerical value is constant, controls E with the sodium-chloride water solution of 3 mol _AgValue.

Measure E _AgNumerical value, employing be argent electrode and the saturated Ag/Agcl contrast electrode of binode (double junction) type (referring to the uncensored patent publication No. 197534/1982 of Japan).

In addition, solution B and solution C reinforced, employing be flow velocity adjustable type roller tube volume pump (a kind of pump that can control flow velocity).

In the reinforced process, survey sample emulsion, to determine not having new crystal grain to produce in the system with electron microscope.

In the reinforced process, also will use 3% nitrous acid solution, the PH of the hierarchy of control is constant in 3.0.

Reinforced finishing, emulsion must be through Ostwald ripening, then with classic method desalination and washing.Then, add the aqueous solution (containing 30 gram bone collagen gelatins) of 600 milliliters of bone collagen gelatins,, make 750 milliliters of emulsions 55 ℃ of dispersed with stirring 30 minutes.

After this, emulsion must be through golden sulphur sensitizing, and add 6-methyl-4-hydroxyl-1,3 inward, 3a, 7-four benzazole used as stabilizers.Also add the 1-(beta-hydroxyethyl)-3-phenyl-5-((3-r-sulfopropyl-α-benzoxazole quinoline pyridines)-ethylidene) sulphur glycolylurea makes sensitizing dye, and its consumption is 150 milligrams of every grammol silver (hereinafter being write as " .../1 grammol Ag ").To be divided into 20 parts through the emulsion of optical sensibilization, every part by 700 milligrams/1 grammol Ag amount, be with substituent triphenyltetrazolium () chloride respectively shown in the adding table 2, add triisopropyl bitter edible plant sodium sulfonate (600 milligrams/1 grammol Ag) in every duplicate samples again, saponin (3.5 grams/1 grammol Ag), and styrene/maleic acid (2 grams/1 grammol Ag), then they being coated on the dacron chip base, thickness is 4.0 gram/rice ²Also to be coated with one deck gelatin protective seam (1.2 gram gelatin/rice on the emulsion layer ²), wherein contain (10 milligrams/meter of diethyl succinate sulfonic acid ²) make spreading agent, (25 milligrams/meter of formalin ²) make hardener.The coating drying is just made sample (sample 1-20).

As shown in table 2,1-10 number is the sample of making according to the present invention, the tetrazolium () salt that every duplicate samples is contained, its σ _pValue is negative.What the o.11 sample was used is the tetrazolium () salt of unsubstituted.The 12-20 sample is a reference examples, wherein the substituent σ of tetrazolium () salt _pValue is positive number, i.e. CF ₃(σ _p=0.54), NO ₂And COCH (0.78), ₃(0.50).

Every duplicate samples is broken into two, and wherein a slice is by sensitometer, and uses wedge, with the exposure of tungsten lamp stepwise; Another sheet is by a GN type R(150L) contact half tone (by Dainippon Screen Mfg CO, Ltd-is that big Japanese silk screen Co., Ltd. makes), carry out shadow tone (photograph mesh) exposure with xenon lamp.

Table 2

Be with substituent triphenyltetrazolium () compound

Table 2

Sample number R ₁R ₂R ₃

Sample of the present invention

1 H H CH ₃

2 H CH ₃CH ₃

3 CH ₃CH ₃CH ₃

4 H C ₂H ₅C ₂H ₅

5 H OCH ₃OCH ₃

6 H CH ₃OCH ₃

7 H OCH ₃CH ₃

8 OCH ₃H H

9 OCH ₃CH ₃CH ₃

10 H CH ₃nC ₁₂H ₂₅

Control sample

11 H H H

12 H H CH ₃

13 H CF ₃H

14 CF ₃H H

15 H CF ₃CF ₃

16 H H NO ₂

17 H NO ₂H

18 H COCH ₃H

19 H COCH ₃COCH ₃

20 COCH ₃COCH ₃COCH ₃

Utilize automatic processing machine to process above-mentioned sample strip, developing machine has the developing tank of 40 liters of capacity, and adopts the developer solution of following described prescription and commercially available stop bath.

Development conditions:

The step temperature-time

Develop 28 ℃ 30 seconds

28 ℃ of photographic fixing 20 seconds

Washing room temperature 20 seconds

Developer formula:

Constituent A

150 milliliters of pure water

Disodium ethylene diamine tetraacetate 2 grams

100 milliliters of potassium sulfites (55% aqueous solution)

Sal tartari 50 grams

P-dihydroxy-benzene (quinhydrones) 15 grams

200 milligrams of 5-methylbenzotrazoles

30 milligrams of 1-phenyl-5-s-based tetrazolium

Potassium bromide 2 grams

Constituent B

Diglycol 50 grams

3 milliliters of pure water

25 milligrams of disodium ethylene diamine tetraacetates

0.3 milliliter of acetic acid (90% solution)

110 milligrams of 5-nitro indazoles

500 milligrams of 1-phenyl-3-pyrazolidone

During use, top constituent according to the order of A and B, can be dissolved in 500 ml pure waters, be mixed with 1 liter of developer solution.

Adopt those samples of wedge exposure, after developing, draw their characteristic curve, to measure the exposure range and the gamma value (γ) of curve toe, the toe exposure range of indication, be logH value (logE) scope of optical density from 0.1-0.5, the γ value is meant that optical density is the tangent value (slope) of that part straight line of 1.0-2.5.

As for by the lithographic plate camera,, then evaluate the net-point quality of the dot pattern of respectively throwing the net that forms with those samples that xenon lamp carries out shadow tone (photograph mesh) exposure.

Adopt Pyatyi finger-length measurement system, evaluate net-point quality.In this system, if observed fine hair shape mist (or fading) around the site is regarded as so-called 50% site ^*(at this moment, the site of image partly equates with transparent part area).Wherein, the little person of the idea of fine hair shape mist then is expressed as " 5 ".That is to say that " 5 " mean that net-point quality is good, " 1 " means that net-point quality is very poor.If 50% site etc.

^*The translator annotates: halftone negative or printed matter comprise site part and transparent part, and when two part areas equated, the site partly was referred to as 50 percent site or transparent respectively with transparent part.

Table 3

The exposure range γ value net-point quality of sample number toe

(logE) (grade)

The present invention:

1 0.03 18 4.5

2 0.03 20 4.75

3 0.04 16 4.25

4 0.04 17 4.25

5 0.03 21 4.75

6 0.03 24 4.75

7 0.03 23 4.75

8 0.04 18 4.5

9 0.04 17 4.0

10 0.06 15 3.75

Reference examples:

11 0.08 10 3.0

12 0.13 8.0 2.75

13 0.13 7.8 2.75

14 0.14 7.5 2.75

15 0.15 6.8 2.5

16 0.20 6.3 2.0

17 0.20 6.2 1.5

18 0.22 5.8 1.0

19 0.19 6.2 2.0

20 0.23 5.9 1.5

Level does not surpass " 3 ", and it is qualified that such numerical value generally just can not be counted as.

The above results is shown in table 3.

As shown in table 3, adopt substituent the triphenyltetrazolium () compound of being with of the present invention, can obtain very good toe acutance and net-point quality.The tetrazolium () compound that the 12-20 sample is used, its phenyl substituent all are electron withdraw groups, and they are inapplicable fully to the lithographic plate photosensitive material.In addition, what the o.11 sample was used is not to be with substituent triphenyltetrazolium chloride, though effect is not too satisfied, can actually use.But, it is compared with used those compounds of the present invention, its performance difference is tangible.

The tetrazolium () compound that the present invention is used has to electron substituent group group, by the light-sensitive silver halide photographic material that they are made, can reach very high contrast and good net-point quality, and these materials also have good especially lithography piece performance.

Example 2

Solution A below utilizing, solution B, solution C, preparation chlorine silver bromide emulsion.

Solution A:

Bone collagen gelatin 17 grams

Polypropyleneoxide-polyethylene oxide

5 milliliters of 10% ethanolic solutions of two sodium butyrates

1280 milliliters of distilled water

Solution B:

Silver nitrate 170 grams

410 milliliters of distilled water

Solution C:

Sodium chloride 38.0 grams

Potassium bromide 41.7 grams

Rhodium chloride three water contain the thing consumption and are shown in table 5

Polypropyleneoxide-polyethylene oxide

3 milliliters of 10% ethanolic solutions of two sodium butyrates

Bone collagen gelatin 11 grams

407 milliliters of distilled water

Solution A is remained on 40 ℃, adopt double-jet method to add solution B and solution C inward, stir with mixing agitator simultaneously, this stirrer is disclosed in Japanese uncensored patent publication No. 92523/1982 and 92524/1982.

Table 4

Reinforced time solution B solution C

(minute) (the milliliter number/minute) (the milliliter number/minute)

0 1.13 1.11

10 1.13 1.11

20 2.03 1.99

30 3.17 3.11

40 4.57 4.48

50 6.22 6.10

60 8.13 7.97

70 10.29 10.01

80 12.74 12.49

In 80 minute reinforced period, their charging rate increases (as shown in table 4) gradually in solution A and solution B, to form silver halide grain.At initial 5 minutes that mix, the E of emulsion _AgValue remains on 160 millivolts.After 5 minutes, with the sodium-chloride water solution of 3 mol, with E _AgBe adjusted to 120 millivolts.After this, keep E by sodium-chloride water solution _AgBe worth constant.

Behind reinforced the finishing, emulsion must be through Ostwald ripening, then with classic method desalination and washing.Then, add 600 milliliters of bone collagen gelatin aqueous solution (containing 30 gram bone collagen gelatins) inward, disperse to stir 30 minutes, make 750 milliliters of emulsions at 55 ℃.

Adopt argent electrode and the saturated Ag/AgCl contrast electrode of binode type (binode that is disclosed with Japanese uncensored patent publication No. 197534/1982 constitutes electrode), measure E _AgValue.

In addition, solution B and solution C reinforced, employing be flow velocity adjustable type roller tube volume pump.

In the reinforced process, survey sample emulsion, to determine not having new crystal grain to produce in the system with electron microscope.

In the reinforced process, also will use 3% nitrous acid solution, the PH of the hierarchy of control is constant in 3.0.

EM-1 to EM-7 emulsion shown in the table 5 is to be made by the consumption of change rhodium chloride trihydrate.

Table 5

The Rhcl that adds ₃3H ₂The O amount

Emulsion number microgram/grammol Ag grammol/grammol AgX note

EM-1 0/reference examples

EM-2 10 3.8 * 10 ^-8Example of the present invention

EM-3 30 1.1×10 ^-7″

EM-4 60 2.3×10 ^-7″

EM-5 90 3.4×10 ^-7″

EM-6 150 5.7 * 10 ^-7Reference examples

EM-7 200 7.6×10 ^-7″

EM-1 to the EM-7 emulsion that makes with electron microscope observation is to measure vertical average particle size of silver halide.Found that sample all is cubic crystal, and have good monodispersity.

Emulsion must be through golden sulphur sensitizing, and add 6-methyl-4-hydroxyl-13,3a, 7-four benzazole used as stabilizers in emulsion.Also add the 1-(beta-hydroxyethyl)-3-phenyl-5-((3-γ-sulfopropyl-α-benzoxazole quinoline pyridines)-ethylidene) sulphur glycolylurea makes sensitizing dye, and its consumption is 150 milligrams of every grammol silver.

After this, in emulsion, add 2 respectively again, 3-two-right-tosyl-5-phenyltetrazole () chloride (example compound (2), consumption is 700 milligrams/1 grammol Ag), right-neopelex (400 milligrams/1 grammol Ag), saponin (3.5 grams/1 grammol silver) and styrene-maleic acid copolymer (2 grams/1 grammol Ag).This emulsion is coated on the base material, and the silver amount is 4.0 gram/rice ², the gelatin amount is 2.0 gram/rice ²On emulsion layer, also to be coated with one deck gelatin protective seam, wherein contain 1-decyl-2-(3-isopentyl) (30 milligrams/meter of succinates-2-sodium sulfonate ²) make spreading agent, (25 milligrams/meter of formalin ²) make hardener, the gelatin consumption of coating is 1.2 gram/rice ²

The above-mentioned sample of making is divided into two groups, and one group of former state is retained, after another group is controlled at 25 ℃ of humidity and places in 80% the environment, and with waterproofing packing material seal parcel, and 50 ℃ of heating 72 hours, to evaluate its stability.Two groups of samples all adopt tungsten light source, use wedge to expose.

Utilize automatic processing machine to process above-mentioned specimen, developing machine has the developing tank of 40 liters of capacity, and adopts the developer solution of following described prescription and commercially available stop bath.

Development conditions:

The step temperature-time

Develop 28 ℃ 30 seconds

28 ℃ of photographic fixing 20 seconds

Washing room temperature 20 seconds

Developer formula:

Constituent A

150 milliliters of pure water

Disodium ethylene diamine tetraacetate 2 grams

100 milliliters of potassium sulfites (55% aqueous solution)

Sal tartari 50 grams

P-dihydroxy-benzene 15 grams

200 milligrams of 5-methylbenzotrazoles

30 milligrams of 1-phenyl-5-mercapto-tetrazole

Potassium bromide 2 grams

Constituent B

Diglycol 50 grams

3 milliliters of pure water

25 milligrams of disodium ethylene diamine tetraacetates

0.3 milliliter of acetic acid (90% solution)

110 milligrams of 5-nitro indazoles

500 milligrams of 1-phenyl-3-pyrazolidone

During use, top constituent according to the order of A and B, can be dissolved in 500 ml pure waters, be mixed with 1 liter of developer solution.

With the sample after developing, draw characteristic curve, to measure the acutance of toe.To reach optical density 2.5 needed exposure reciprocal values, determine light sensitivity.Regard 100 as if EM-4 emulsion is made the light sensitivity of sample, then available relative sensitivity is represented the light sensitivity of sample.In addition, the acutance of toe is that optical density is that the exposure region of 0.1-0.5 is represented (logH value logE).Numerical value does not mean that the toe acutance of sample possesses desired good characteristic.

Table 6

Undressed sample is through heat treated sample

EM light sensitivity toe acutance light sensitivity toe acutance

EM-1 180 0.04 60 0.28

(reference examples)

EM-2 140 0.04 70 0.18

(reference examples)

EM-3 120 0.04 90 0.07

(example of the present invention)

EM-4 100 0.03 90 0.05

(example of the present invention)

EM-5 80 0.03 75 0.05

(example of the present invention)

EM-6 40 0.03 38 0.04

(reference examples)

EM-7 10 0.03 9 0.04

(reference examples)

From shown in the table 6, as can be seen, emulsion of the present invention has very high contrast, deposits under high temperature, high humidity, and its performance is constant substantially.And contain the EM-6 and the EM-7 of a large amount of water-soluble rhodium salt, then be difficult to reach the light sensitivity that is suitable for actual use.

Example 3:

Routine 2EM-4 is made the sample that scribbles emulsion by last routine comparison method, and what prepare just that coating solution uses is tetrazolium () compound as shown in table 7.By wedge, sample is done the exposure of shadow tone (photograph mesh) stepwise, develop by example 2 methods, thereby the light sensitivity and the net-point quality of every sample are passed a judgement.

Table 7

Triphenyltetrazolium () compound

Sample number R ₁R ₂R ₃

The present invention:

1 H CH ₃CH ₃

2 H CH ₃H

3 H OCH ₃H

4 H CH ₃OCH ₃

Reference examples:

5 H H H

6 H H CF ₃

7 H NO ₂H

8 H H COCH ₃

The substituent Hamett σ of above-claimed cpd _pValue is :-CH ₃(0.17) ,-OCH ₃(0.27) ,-CF ₃(0.54) ,-NO ₂(0.78) ,-COCH ₃(0.50).

Adopt Pyatyi finger-length measurement system, evaluate net-point quality.In this system, if observed fine hair shape mist (or fading) around the site is regarded as so-called 50% site (at this moment, the site of image partly equates with transparent part area), wherein, the little person of idea of fine hair shape mist then is expressed as " 5 ".That is to say that " 5 " mean that net-point quality is good, " 1 " means that net-point quality is very poor.If the grade of 50% site does not surpass " 3 ", it is qualified that such numerical value generally just can not be counted as.

From forming the needed exposure of 95% dot density, calculate light sensitivity.If No. 1 sample light sensitivity is regarded as 100, just the sample light sensitivity is represented with relative sensitivity.

The above results is shown in table 8.

If shown in 8, as can be seen, 1-4 sample of the present invention and 5-8 sample are contrasted, the former has good net-point quality, deposits in high temperature, high humidity environment, and their performance does not almost have any variation.

From top example as can be seen, light-sensitive silver halide photographic material of the present invention has very high contrast.When carrying out shadow tone (mesh photograph) exposure, this material list reveals good net-point quality, passes in time, and its quality of stability is also fine.

Table 8

Undressed sample is through heat treated sample

Sample number net-point quality light sensitivity net-point quality light sensitivity

(grade) (grade)

The present invention:

1 4.75 100 4.5 90

2 4.5 105 4.25 98

3 4.5 95 4.5 87

4 4.75 100 4.5 92

Reference examples:

5 3.0 120 2.5 80

6 2.75 85 1.5 40

7 1.5 90 1.0 50

8 1.0 80 1.0 30

Claims (18)

1, a kind of light-sensitive silver halide photographic material that is coated on the base material, it comprises one deck silver halide emulsion layer and one deck hydrophilic colloid layer at least at least, it is characterized in that in one deck silver halide emulsion layer and hydrophilic colloid layer at least, add useful below the triphenyltetrazolium () compound of general formula (I) expression.

General formula (I):

Wherein, R ₁, R ₂, R ₃Each represents hydrogen atom, or Hamett σ p value is the group of negative, X

Be meant negative ion; But, R ₁, R ₂, R ₃Can not be hydrogen atom simultaneously.

2, light-sensitive silver halide photographic material according to claim 1, wherein, the compound of representing with general formula (I) is following with the compound shown in the general formula (I '),

General formula (I) ' be:

Wherein, R ₁, R ₂And R ₃Each represents hydrogen atom, or Hamett σ _pValue is the group of negative, X

Be meant negative ion; But, R ₁, R ₂And R ₃Can not be hydrogen atom simultaneously.

3, light-sensitive silver halide photographic material according to claim 1 wherein, is following with general formula (I) with the compound of general formula (I) expression " shown in compound.

General formula (I) ":

Wherein, R ₁, R ₂, and R ₃Each represents hydrogen atom, or Hamett σ _pValue is the group of negative, X

Be meant negative ion; But, R ₁, R ₂And R ₃Can not be hydrogen atom simultaneously.

4, light-sensitive silver halide photographic material according to claim 1, wherein, R ₁, R ₂And R ₃In any substituting group can be hydrogen atom.

5, light-sensitive silver halide photographic material according to claim 4, wherein, R ₁, R ₂And R ₃In remaining any two non-hydrogen atom substituting groups all be alkyl.

6, light-sensitive silver halide photographic material according to claim 5, wherein, two substituting groups of indication are R ₂And R ₃

7, light-sensitive silver halide photographic material according to claim 5, wherein, the alkyl of indication respectively has the carbon atom of similar number.

8, light-sensitive silver halide photographic material according to claim 7, wherein, the alkyl of indication is mutually the same.

9, light-sensitive silver halide photographic material according to claim 1, wherein, general formula (I) lining substituent R ₁, R ₂And R ₃The total number of carbon atoms be no more than 4.

10, light-sensitive silver halide photographic material according to claim 9, wherein, general formula (I) lining substituent R ₁, R ₂And R ₃The total number of carbon atoms be no more than 2.

11, light-sensitive silver halide photographic material according to claim 1, wherein, the general formula that contains in the material (I) compound, its consumption are the about 1-10 milligram of every grammol silver halide.

12, light-sensitive silver halide photographic material according to claim 1, wherein, the X of general formula (I) lining is a negative ion, it can reduce the water wettability of general formula (I) compound.

13, light-sensitive silver halide photographic material according to claim 1, wherein, the silver emulsion in the emulsion layer is the chlorine silver bromide, the AgCl/AgBr ratio is 100/0～2/98 in the silver halide.

14, light-sensitive silver halide photographic material according to claim 1, wherein, silver emulsion in the emulsion layer, average particle size are the 0.15-0.4 micron, and distribution of particle sizes coefficient (ratio that refers to (distribution of particle sizes standard deviation/average particle size)) is no more than 15%.

15, light-sensitive silver halide photographic material according to claim 1, wherein, silver emulsion in the emulsion layer, its preparation method is as follows: with water miscible silver salt and two kinds of aqueous solution of halogenide, join in the hydrophilic colloid aqueous solution by double-jet method, the charging rate of above-mentioned two kinds of aqueous solution will be controlled at and not allow the speed of growth of silver halide grain in hydrophilic colloid aqueous solution surpass the critical speed of growth; The E of hydrophilic colloid aqueous solution _AgValue is counted from beginning reinforced the mixing, is being equivalent to will to remain on certain steady state value in 140～200 millivolts of scopes substantially in 1/30～1/5 period in whole reinforced period, after this, is being equivalent to whole reinforced period at least in period of half (1/2), E _AgTo remain on certain steady state value in the 80-140 millivolt scope substantially.

16, light-sensitive silver halide photographic material according to claim 2, wherein, the silver halide grain in the emulsion layer, they are to form in the presence of water-soluble rhodium salt, the consumption of rhodium salt is that every grammol silver halide is 1 * 10 ^-7-5 * 10 ^-7Grammol.

17, light-sensitive silver halide photographic material according to claim 15 wherein, with the compound of general formula (I) ' expression, is following with general formula (I) " shown in compound:

General formula (I) ":

Wherein, R ₁, R ₂And R ₃Each represents hydrogen atom, or Hamett σ _pValue is the group of negative, X

Be meant negative ion; R but ₁, R ₂And R ₃Can not be hydrogen atom simultaneously.

18, light-sensitive silver halide photographic material according to claim 15, wherein, the water-soluble rhodium salt of indication is the halide complex of trivalent rhodium.