DE2035623A1 - Process for the preparation of photographic silver halide emulsions - Google Patents

Description

Fuji Photo PiIn Co. Ltd. Aehigara-Kavlgun, Xanagawa, Japan

Process for producing τοη photographic silver halide

emulsions

According to the invention, photographic silver halide emulsions are produced in a very narrow range of the distribution of grain sizes and a reduced mist formation, which are sensitized to a gold-containing non-ferrous sensitizer) by using a solution of a water-soluble silver halide and a solution of a water-soluble alkali halide of a water-soluble gel at the same time be given, the concentration of the silver ions being kept at a constant value in the range τοη 10 to 10 "* ¹⁰ mol / liter, the silver ion concentration to less than half after the addition τοη 1/20 to 1/2 dee of diluted silver salts This is reduced, the addition is forfcgeetst at this concentration, the Bmulaion is rinsed free τοη water-soluble salia and chemically the Boralslon is sensitized as a result of the non-sensitive sensitizer.

The invention relates to a method of production τοη Silver halide disconnects nlt a very narrow division of the

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torngröfltn and a Terringerten h * belbildung in the sen Billing old a chemical sensing agent, welohee Binding · Containing an Ooldrer bond

A very pure Sllberbromldemulelon old indifferent Crystal shapes and a very narrow distribution of grain sizes can be obtained naoh a Terfahren, whereby the maximum number of nuclei in an early stage of precipitation is formed and the subsequent addition of reagentlan there is merely an increase in the orbit of the nuclei and no longer exists The formation of new nuclei leads to · The increase in sizes the nuclei without the formation of new nuclei can be created the »by a water-soluble silver sale and a water-» liohoe Alkalihalogenld uniformly and gradually sugesetst be, where the conientration of the Silborion $ E In the jSdquI-

—6 elon if the value is constant, choose 1 χ 10 and 1 χ 10. Λοΐ / liter, corresponding to a pAg »value τοη 6 to 10, is held. You train new seeds depends ron the Abstünden evlochen the Kurnern which Eeaktionetesip @ temperature _e of the silver halide LSsliohkeit uni AE®? The addition of the reagents depends on the level of training. It is known that when the completion step takes place close to a pAg value corresponding to τοη stSohlonetrieh equivalent amounts of silver ions and halogen ions, "silver halide" crystals become cubic FL & ohen orhalt®m and that "when they are in the presence of τοη fibereohttesigegi halogen ion, ie at high pAg-Vert, takes place, the crystals obtained have ootaledrl-high heights.

In the channels of the invention it was stated that if the filling in with a high pAg »Begin at the beginning

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the production of τοη crystals aua aisohten silver » halide, ie Silberjodbroaid and Silberohlorjodbroaid is carried out, crystals ait a narrow division of the

Grain sizes will not be obtained know. This is applied to the Tatsaoh · surttok led »that critical stenographic effects

with training τοη flat plate-like grains that

Twin crystals are made of tattao rubbers, occur and dal

new cores by reducing the solubility of the silver halide are formed, therefore silver iodhroaid or SilberohlorjodhroaidkSrner old a narrow division of sizes "attssen reagents with a pAg-

Value within a range practically correspondingly disrupt

ohionetrisoh equiral consents of silver ions and halogen ions are sugesetst in the Eauleion, such as red executed. '

However, it was stipulated that, if the photographic silver iodine or silver chloride emulsions obtained, which contain cubic grains and have a very narrow grain size division, freely τοη water-soluble salsa can be sensed and then also contain an ohea-like sensitiser, which contains an odorous sensitiser. φ are sensitized "so that the photo-sensitivity is increased to a level, an excessive liver formation occurs" and awar even in those files of the Eamlsion "which have only received an insufficient low ripening ·

Ia Rahaen τοη further investigations it has now been found that a photographic silver halide formation with a very narrow division of the grain sizes who * can if the | Cossentration dea Silberiona in the Baral-Bion on less than the hip of those concentration see below

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an early stage of precipitation after the formation of Stable nuclei subsequently reduced at the beginning of the precipitation »the emulsion is free of water-soluble Saleen Is geeptiVlt and then the emulsion with a chemical Sensitizer that contains at least one gold compound is sensitized. When they are of the same exposure and These silver halide ions may be subjected to development achieve the maximum sensitivity without any fog formation »in comparison to the ones described so far Emulsions that provide bits of constant silver ion concentration! the growth of the grains.

The exact Meohanisnus used to make this emulsion is not entirely understandable, but it can be assumed that it is ascribed at least to the following two reasons * First of all, this emulsion was no leverage Seigt, get that the silver halide crystals as far as possible from a reducing atmosphere during the grain formation reaction were guarded, however subsequently the occurrence of a reduction sensitization is avoided during the formation of the grains. Second, while the silver iodobromide or silver chloride oriodobromide crystals exist with a narrow distribution of sizes obtained at low pAg values, in general from a mixture of cubic grains and ootaedrlsohen Grains, while those obtained in the process according to the invention Grains consist essentially of octahedron grains

The object of the invention is therefore a process for the production of silver halide emulsions with

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tintr tthr tngtn Vtrttilung dtr lomgröitn and tin ·? τ · γ-ringtrttn Htbtlbildung bti dtr Stntlblitltrung alt tints ohtaieohtn Stnaibilltator, dtr alndttttnt tin · OoldTtrblnduna; contains.

Bint wtittrt task dtr Irfladung bttttht in Gtlatint-Silbtrhalogtnidtaulaion, dit silver halide body old tintr Narrow distribution of phototepfindility Ubtr dit ESmtr.

Eint wtittr · Abandon the invention btettht in tintr sur Application in photogrtphischtn ltettrialitn tÄucthxfmrb- and eohwÄri-und-wtü-Photogrmphitn gtticntttnBeul β ion.

The maintenance of the phdlographieohtn Silbtrhmlogtnidtmileionen genia dtr Srf indunf will be followed by ia tinstXntn bt- • ohriebeni

Bint solution of silver nitrate and tint Lotung ink alkali Halides become smooth and ultimately subtle Solution, the Gelatint odtr tin Gtlatintdtrirat, wit Btrneteinaäuregelatint, Maleinaäurtgtlatint or PhtlialaÄurtgtlatint contains, under vigorous stirring. iaaoniak in tintr lonstntration -ton f # 5 x 10 bit 1.5 can Torhtrgthtnd

dtr wäßrigtn <} tlatintlötung augttttit wtrdtn, including dit gt · wünaohttn (Jrößtn dtr Silbtrhalogtnidkörntr su trnalttn. VMH * rtnd dtr üteeetiung is iugtgtbtn dit Löaung dtr Btatandttilt where dit lonitntration dtr ßilbtriontn in dtr RtaktlontXtftune on wtnigtr old on dit Hftlftt dtr lonetntration su dtr frtthtn level dtr precipitation is rtrrlngtrl, and the addition for! · gtetted. Toreugtwtiat btettht the btauleion in ink Hitoheilbtrhalogtnid, dat 0,2 bit 10 MoI- ^, lntbtondtrt O ₉ 5 bit 7 Nol · ^ iodide can contain tr »holdtn wtrdtn, vtnn dit bilbtrnitrratlÖung and dit alkali

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Halogtnidlöeung glflohitig iu dtr Otlatlnt ~ odtr aelatintderlratloaung while 6 to 60 "are in budget, laoh dtr removal dtr vatetrltfellohen salad duroh rinsing dlt trhalttnt Baralelon ohtaleoh btl high temperature duroh Addition ink ch.ealeob.tn Stnaibilleatore, dtr alndtettna tint CtoldTtrblndung "holds, etnellltitrt.

Bit IOtungtn dta Alkallnalogtnlda and dta SUbtrnltrsta wtrdtn lu tlntr v & Brlgtn solution lugtattat, dlt utlatlnt or that Gtlatlntdtrlrat In tlntr Konitntratlon τοη contains 0.5-55t. Dlt Sllbtrhalogtnlddlaptrelon obtained is actuated cold rer t and old Waastr by diffusion ODTR using dee Coaoervlerungeverfahrens, 1st wit ta In dtr TJS-Patenteohrlft 2 439 541 described, gevasehen.

Otwttnaohttnfalla can tint aqueous solution ink AlkallbroBide and a great deal of Luaung ink, alkali iodide, gleiohatltlg Be sure to check out the gelatin solution neoht te aöglioh, dlt training of an überohus see of halogen ions in the clock solution

Slnte dtr wee tntlichen characteristics dtr invention btettht In dtr ohtnleehtn Stneibllislerung dtr trhalttnon Ettuleion old an ohtnleohen sensitiser, dtr alndeetene tint Gk) ldrerbind, like Kalluaohloraurat (KAuClan ^), Goldtriohlorid (AuCloyi ₃ ), gold triohlorid (AuCloy 3) and potassium "gold-I-Thiοcyanat (IAu (OHE).) and Kaliuegold-I-Thiooyanat (IAu (CIS ^) contains / Here tin SohweXtletneibiieltr- ■ ittel, such as Hatriuathiosulfat-Pentahydrat, Allylthiocarbaald, ^, Allylotharnstoff, Amaonlue- and / or Alkalithlooyanate and / or Rtduktionaeneibilisltreittel, wit linn-II-Chlorid ausamen old dtr OoldTtrblndtt

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be, woiu ι.B. on pages 114-116 τοη O.l.I. Keea and T.H. Janea, Ibt History of the FhotographicProoeae, 3rd edition »» MaoMillan Co., 1966, rerwieaen. Bit Bnilalon can also be attached to an gold bond and in conjunction with polyethylene glycol, such as In then drive the Üß-patent lifters 2 423 459 and 2 441 389. Dia oheaiaoho awareness of Euulalon is through Ralfen asked for high temperatures during elnea Seltrauaee, among other things to increase photo awareness, bawlrkt ·

The Eauleion preserved on dlasa Valaa is transferred to a Deposits, for example a material «la cellulose triacetate, Cellulose acetate propionate or polyithene terephthalate aufaiogan.

In the case of building areas obtained according to the invention, a wide range of fog formation and a narrow area of the lorneröfien and alnd beaonder aur Terwendunf la photographic aohen Dekehrfarbaitt he lallen or photographed Oalcehraahvars-ttnd-walB-Katarialian suitable. The following Beiapiele dlaatn aur wt & teran Srliutarung the invention, was dia Xaipflndllohktlt duroh dan lur £ ralelung a density daa fabele τοπ +0.1 required Batrag of the development indicated and the development with the application of a eohwex * - und-veifiaa Fntwidenokleretaa follow it with 4 win was carried out
I-llethyl-p-aBinophenol-aulfat 1g

Vaaaar frelee latriuaeulfite 60 g B hydroquinone 10 g

sodium carbonate aKjnohydrate 40 g

Xalluabroaid 5g

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Potassium thiooyanate 1.5 g

0.1 J * potassium iodide 5 S

Fatric hydroxide 2 g Vaseer su 1000 ml VersuohsbeisDiel 1 Bum comparison

This example explains the production of an emulsion, the concentration of silver ions being kept constant during the precipitation of the silver halide crystals was «This emulsion achieved maximum sensitivity with little leverage when chemically treated with a sulfur sensitizer such as sodium sulfate dehydrate is sensitized, but results in a distinctive gag formation gate of the achievement of the maximum sensitivity, if they ohemisoh with a chemical sensitizer that contains a gold bond, is sensitized.

The following! Solutions Σ, II and III have been made

Solution I.

20 g of gelatin and 3.0 g photοgraphischer Kaiiumjodid were dissolved in 1,200 ta distilled water at 50 ⁰ C and 80 ml of 25 ^ -igeθ aqueous ammonia was added.

Solution II

70.1 g of potassium bromide were added to distilled water at 45 "C (• Dissolve and bring the total amount of the solution to 400 ml.

III

100 g Silberniteat were dissolved in distilled water at 45 ⁰ C and brought the Gesantaenge al of the solution to 400th

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Solutions II and IXI were all but identical to solution I with vigorous oiling for about 40 minutes. During the fixing, the formation of the silver ions in the reaction was kept at <* lB8ung b * l 10 " ⁹ mol / liter. When the addition was complete, the ffeaisoh was cooled to 3C and the old 6N sulfur oleic acid was acidified Etuulaion was sensed free of water-soluble salia according to the usual ooervation method and heated to an temperature of 4CK , followed by a complete reading with the addition of 80 g of photographic gelatin. The pH and pAg values were 6.50 to 8 , 50 old 5S ^ Hatriumhydroxyd and 2 ^. Laliuabroaid adjusted · To the obtained silver halide emulsion were sugesetst 6 al Hatrluathionulfafc pentahydrate (0.1 ^) and 2.5 el Ealluotetraohlorat (0.1 Gew. - ^) per hol of silver halide and the ohemisohe ripening at 5O ¹ C for 50 to 90 minutes carried out until the emulsion reached the oaxioale Eapfindliohkeit. Kaoh addition of an "ugahilfanaitteis such as saponin, the Eauleionauf was absorbed and a Aoetatfiln getrooknet. the mean Pro jection area of the grains was 0.55 n ²

example 1

This example describes the preparation of an emulsion according to the invention, which has a very narrow definition the KomgrdSen, a great stability and a reduced If you are too old to become foggy, you will be blinded leveling agent containing is equalized

The following solutions I, II and III were prepared

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- ίο -

Lueung I

20 g of photographic gelatin and 3.0 g of potassium iodide were dissolved in 1200 ml of distilled water at 5 ° G and 80 ml of 25% aqueous ammonia were added.

Solution II

70.1 g of Kai ium brom id were in distilled water at 49 ° C dissolved and the total amount of the solution brought to 400 ml

Solution III

100 g of silver nitrate were in distilled water at 45FO dissolved and the total amount of the solution adjusted to 400 ml

Solutions II and III gradually became simultaneous added to solution I with vigorous stirring. While

10 min after the start of the addition, 1/4 of the solutions became in each case

11 and III were added and during this period the silver ion concentration in the reaction solution was kept at 10 "mol / liter. At the end of the 10 minute period, the silver ion concentration in the reaction solution was reduced to 10 tfol / liter and the remainder the solution of II and added to III while about 30 rs in. Since ο resulting mixture was cooled to 3QTC and 6n sulfuric acid to "leavened. you Enralsion was released felt of water-soluble salts according to the usual Coaoervierungsverfahren and heated at 4oC whereupon _t completely · Dissolution by adding 80 g of phbtographic gelatine · pH value and pAg value were adjusted to 6.5 with 5 $ Hatrumhydroxyd _t and 8.5 «with 2 £ potassium bromide · The mean projection ··» area · of the obtained Grain was about 0.55M.

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To the obtained silver halide emulsion were added 9 al of i-sodium thioeulate pentahydrate (0.1Ji) and 2.5 al Potash gold tetrahalorate (0.1 GFew-ίΟ per mole of silver halide sugesetst and conjugate ripening at 5CFC for about 50 to 90 min carried out until the emulsion reached its maximum Itapfindlioh achieved. Iaoh addition of a * überiugehilfeaittela, like saponin, the Eauleion was made on one Acetate film absorbed and dried »

BtiBPiel Z

Each of the photographlaohen Silberhalogenidenuleionen prepared in Vereuohebeipiel 1 and Lm Example 1, were absorbed on a fiin was ausgeeetst a light source sound 540O ⁰ K duroh a continuous wedge using a Sensitonetere (Toshiba HSQ II-TJP) · The film strip was nin during 4 at 27 ° C kit demo-red indicated eohwars-und-wsiiß-developer, which contained methol and hydroquinone, developed Table I can be seen.

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203.5 523

Table I.

over-sucked File fog relative sensation ""
liohigkeit Examples without relief
rare (min) 0.12 70 Tereuohe-
example 1 40 0.28 84 60 0.4a 99 80 0.06 85 example 1 40 0.07 96 60 0.08 100 80

If the sample was chemically ripened after test example 1 until the relative sensitivity became 100, became a Lever tone obtained 0.42. In contrast hiertu was with the Sample according to Example 1 had a relative sensitivity of 100 with a much lower lever mechanism (0.08) than for the sample naoh Ttrsuehsbelspiel 1 received ·

Example 5

Solutions Σ, II and III were prepared in the following way 1

20 g of photographic gelatin and 3 g of potassium iodide were added dissolved in 1200 al of distilled water at 50 * 3 and add 10 ml 25 ^ -ige «wäirigen imonlak sugesstst ·

Solution II

70.1 & potassium bronze were dissolved in the distilled water at 49 ° C and the oeeaetsenge of the solution was brought to 400 nl,

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100 g of silver nitrate were distilled in Yasser at dissolved and the Gesaataenge of the solution brewed to 400 ml. Solutions II and III were allaählloh and at the same time bugceetet with solution I while stirring vigorously. First were 100 al of solutions II and III during a period β of 10 ain while maintaining the concentration of

• »8 / * silver ions in the reaction solution to 10 mol / LJ, ter exposed. After this 10 ain, the silver ion concentration was reduced to 10 "* ⁹ ' ⁵ mol age and the Rfst of solutions II and III in the course of τοη 30 ain with this silver ion concentration. The older projection area of the silver halide grains obtained was 0.2 λγ. The emulsion was Cooled to $ 50 and acidified with 6N-sulfuric acid. The emulsion was then rinsed to free τοη water-soluble salsa according to the usual organic method and 80 g of gelatin were added, whereupon on 4G * J for dissolution and perfect dispersion of the emulsion was obtained. pH-Vert and pAg -Vert were set to 6.5 with £ 5 Hatriuahydroxydbsvv 8.5 old £ 2 Kaliuabroaid.

The resulting biulsion was then ripened for 60 minutes at 50TC with the addition of 10.5 al latrluathlosulfate pentahydrate (0.1 JO and 2.5 al kallua gold tetrahydrate (0.1 wt _t popular and developed in the Glelohen catfish as in example 1. The aazlaale apples Indllohkeit was obtained at elnea Vebelwert τοη 0.07.

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Example 4

The same procedure was repeated in Example 1, but there was no potassium iodide as a solution, but as a solution. "When" a gothic sensitizer containing the gold compound was sensitized in the same manner as in Example 1, the maximum sensitivity was obtained at a low Hebol value (less than O ₉ IO), and the obtained silver halide photographic emulsion had a very narrow range Grain sizes.

Example, 5

pi, 5

Bas sJ 'ioht procedure as in Example 1 was repeated except that the solution contained 0 g I 1 ₈ potassium iodide and the LB Bung II contained 2.0 g KaIImTi j ο did. When the obtained emulsion was chemically sensitized for 60 mt & at 5CPG with the same sensitizer containing the gold terbinduag in the same manner as in Example 1, the maximum sensitivity was obtained at a low fog value (less than 0.10) and the obtained photographic image was obtained Silver halideoulBiom had a narrow distribution of grain sizes

Example 6

Sa · same procedure as in Example 1 was witdtrholt but cur solution I further sugtsetart 10 g of potassium chloride "If the resulting emulsion ohemisoh for 60 minutes at 5CK with the Ooldrerblndung containing chemical sensitizer in the same manner as sensiblleiert in Example 1 was the maximum sensitivity at a low

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Lebenlwirt (vtnigtr «le 0,10) trhalttn and dl ·« rhalttn · photographed Sllberbalogtiildtmilalon hatt · tint «ag · Ytrttilung dtr IoragreStn.

Btlspltl 7

D * β gltloht ftxf »hrtn if 1 · in Β · 1 · ρ1 · 1 1 vurdt witdtrholt, jβdoohwurdtn 10 g Imllueohlorid« ur solution Σ calls- •• did and the 1 * 1ineJodld not but reading I ₉ but «ur LtlBung II «Ugtgtbtn. ¥ tnn dl · trhmltene Eaulelon lasts 60 aln b »l S (K alt« Inra dl · Öoldrtrblndung «ntbjilttndtn ohtBieohen Sensibilizer In dtr gltlohtn V ·! eint «nitdrlgen Itbtlwtrt (vtnlftr as O ₉ IO) trhalttn and dl · trhmlttnt photograpMsoh · Sllbtrnalogtnldtmuleion had one day T« rt «llung dtr loragröitn.

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Claims (12)

- 16
Fat entane soup IJ method of making a photographic Mixed silver halide emulsion, characterized in that a solution of a water-soluble silver salt and a solution of a water-soluble alkali halide at the same time and gradually to an aqueous, gelatin or gelatin derivative containing solution are added, the concentration of silver ions at a constant value la range of 10 to 10 moles / liter is maintained, then the silver ion concentration to less than half after the completion of the addition of 1/20 to 1/2 of the total Silver alkali solution is reduced, the addition in this Reduced concentration of silver ions continues to form the miscible halide demulsion, which is water-soluble Salts are removed from the emulsion and the bulge nit an ohenisohen Sen ^ sibilieator, which is at least • Contains a gold compound, is ohemisoh sensitized. 2. The method according to claim 1, characterized in that the solution of the water-soluble silver salt and the Solution of the water-soluble alkali halide to the aqueous solution containing gelatin or a gelatin derivative can be added during a period of 6 to 60 n.in. 3 * method naoh claim 1 or 2, characterized in that that the misalignment halide of silver iodobrooid and / or Silberohlorjodbroaid. 4 Process for the production of a photographic SiI 009886/1566 berjodbroaldeaulalon nmoh claim 1, characterized thereby, dsi the water-soluble alkali halide from Elnea Alkallbroaid exists when the aqueous solution of gelatin or The gelatin derivatives also contain an alkali iodide. 5. The process only produces a photographic silver iodine mixture according to claim _1, characterized in that the waeeeriesllohe alkali contains an alkali metal and an alkali iodide if the aqueous solution of the gelatin or the selatin derivative does not contain any alkali halide. 6. Method sur production of a photographlsohen Silberchlor iodbronldeaulaion according to claim 1 ,. daduroh known-rewarded, that the aqueous alkali halide is an alkali broaid contains, if the wäfirlge suffered solution of gelatin or des OelatinederiTats aindeetene contains an alkali iodide. 7 · The method for the production of a photographic silicon-berohlorjodbroaideanilion according to claim 1, because it is well known that the alkali halide is an alkali broald contains if the wiflrlge solving the gelatin or the oelatin deriTat contains at least one alkali chloride DAB contains 8 retracts, for producing a photographieohen SiI-berohlorjodbronideiBulsion according to claim 1, daduroh gekennselohnet, the alkali halide wasserlttsUohe a Alkalibroald, alkali metal iodide and Alkaliohlorid when the wäfirige JJÜBvmg the gelatin or dea delatinederlTats contains no alkali metal halide. 9 Process related claims 1 to 8, because they are recognized, 009886/1566 dal tin · aqueous solution dtr OtIatine or des Gelatinederirate, which still contains watery Amonlak, is used will· 10 · Terfahren na oh claims 1 to 9 »marked thereby that the ohenisohe sensitizer contains Kaliunohloraurat. 11. Method naoh Inapruoh 10, characterized in that da0 the oheaisohe Senaibillaator from a Gtenisoh τοη BatrliathloBUlfat-Pentahydrat and Kalluaohloraurat. 12. Terfahren naoh inapruoh 1 to 11, thereby identified «I do not want the ohenisohe senile fish at 50FC during a Zeitrauaa τοη about 30 to 90 min is carried out. 13 «Photographic Mlaohailberhalogenldevralaion, containing 0.5 bla 7 mol- ^ iodide, produced according to the method the first to 12. 14 · Llohtenjflndliohea Slenent »consisting of a carrier At least one sole on it, the one photograph! according to the dates of the Inaproups 1 to 12, contains 009886/1566