DE1472791A1 - Photographic silver halide emulsions with increased sensitivity - Google Patents

Description

AGFA-GEVAERTAG!

472791 '

PATENT DEPARTMENT LEVERKUSEN

Za / Pk

Photographic silver halide emulsions with increased sensitivity.

The present invention relates to a method for increasing the sensitivity of photographic emulsions by adding aliphatic sulfonium compounds. The sensitivity of a photographic emulsion is low affect each other in two ways. First of all, it is possible during the so-called chemical ripening the production of emulsions by means of a longer ripening period or by adding suitable substances such as thiosulphate or other, mostly sulfur-containing preparations to increase the sensitivity. The second type of sensitivity increase a photographic emulsion

AG 104 909811/1111

frt'iUii-tjli * ^T K) T] «kind; ;; I, "bs. * ¹ ■■ ·. ' 2jU 3 c.es Audi .. j ι:,; ...;.;. V \ J. 0.

with the addition of so-called development accelerators or chemical sensitizers. These are usually added to the already ripened emulsion.

For example, compounds with an onium structure (such as quaternary Ammonium, phosphonium and ternary sulfonium salts) and very often also polyalkylene oxides and polyalkylene oxide derivatives describe. With the last-mentioned class of substances in particular, there has been no shortage of attempts that have been achieved Sensitivity gains through modification of the derivatives or through combined use together with other connections to increase. However, none of these connections meet those required by practice Properties in full measure, be it that the increase in sensitivity is unsatisfactory or that with the awareness-related veil prevents application.

The invention is based on the object of finding new chemical sensitizers which do not have the above disadvantages possess and with the help of which an increase in the sensitivity of photographic halosilver eenalsions without the Causing undesired fogging becomes possible.

AG 104 -Ia-

909811/1111

It has now been found that particularly high sensitivities of the halide silver emulsions can be achieved if an aliphatic or araliphatic sulfonium salt is added to the emulsions, the aliphatic radicals of which are substituted with hydroxyl, carboxyl or epoxy groups in combination with polyethylene oxides.

The sulfonium salts to be used in the manner according to the invention correspond to the following general formulas:

and R-S Z δ H 2 X, respectively

where mean:

E = a straight or branched chain, saturated or olefinically unsaturated aliphatic radical up to 6 carbon atoms, represented by at least one hydroxyl, carboxyl or epoxy group is substituted | the aliphatic chains can be through heteroatoms, especially oxygen interrupted.

Z β alkylene with up to 18 carbon atoms, preferably with up to to 6 carbon atoms, it being possible for this radical to be substituted by hydroxyl, carboxyl or epoxide groups; the alkylene chain can also be interrupted by heteroatoms, in particular ether oxygen, such groups are, for example Xethylene ether, or aralkylene such as xylylene.

AG 104- - 2 -

909811/1111

τ U72791

X = an "any anion such as halide ions for example Chloride or bromine, perchlorate, paratoluene sulfonate, Methanesulfonate and the like.

The above substituents can of course carry any further substituents, with these further substituents the only requirement to be made is that they do not have the sensitivity-increasing effect of the compounds and no adverse effects on the photographic properties of the inventive Sensitizer-treated emulsions cause. The following compounds have proven to be particularly suitable: -

HO-CH ₂ CH ₂ -S-CH ₂ CH ₂ -OH

Cl "

OH

HO-CH ₂ CH ₂ -S-CH ₂ CH ₂ OH CH ₂ CH ₂ -OH

Cl

HOOC-CH ₉ -S-CH ₉ -COOH CH ₂ -COOH

Cl

HO-CH ₉ -CH

' ^J .CH ₂ CH ₂ -OH
CH ₂ CH ₂ -OH

2 cl

HO-CH ₂ CH ₂

A-G 104

^ ₂₂ ^ -CH ₂ -S

GH ₉ CH ₉ OH 909811/1111 ^{2 2}

2 Cl "

HO-CH ₂ CH ₂ -S-Ch ₂ CH ₂ -OH Cl '

VI

CH ₂ -CH-CH ₂ OH OH

HO-CH ₂ CH ₂ -S-CH ₂ Ch ₂ -OH Cl "VII

HO-CHgCH «© © CH ₂ CH ₂ -OH

-CH ₂ CH ₂ -S '2 Cl VIII

HO-CH ₂ CH ₂ CH ₂ CH ₂ ^X -0H

HO-CH ₂ CH ₂

^^ 2 Cl "IX

S.
HO-CH ₂ CH 4 OH

HO-CH ₂ CH ^ © 0 CH ₂ CH ₂ -OH

S-CH ₂ CH ₂ -O-CH ₂ CH ₂ -S 2 Cl "X

^N CH ₂ CH ₂ -0H

The sulfonium salts used in the manner according to the invention can be prepared in a known manner. In most cases it is suitable to react suitable sulphides, e.g. Thiodiglycol, with mono- or bis-halides. The production of two compounds is given in detail below. The remaining ^ connections can be made in a similar manner will.

A-g 104 -A-

9 0 9811/1111

Connection li t

12.2 g (0.1 mol) thiodiglycol. And 25.5 g (0.3 mol) ethylene chlorohydrin are heated with 60 ml of water for 13 hours on a water bath. The water is then distilled and the solid residue recrystallizes from alcohol. Yield 10g. - Pp. 126 - 127 °

Compound V ;

12.2 g (0.1 mol) of thiodiglycol and 8.7 g (0.05 mol) of 1,4-di (chloromethyl) benzene are refluxed in 250 ml of methanol for 6 hours. The solvent is then distilled off and the solid residue is recrystallized from methanol / water.
Yield 5.5 g - mp 133-135 °

Any desired polyalkylene oxides or derivatives thereof can be used in combination with the above sulfonium compounds. The molecular weight of these polyalkylene oxides should be over 300, preferably be about 1500-10 000. Useful products of this type are, for example, those of the following formula:

R. ο (· CH _2. CH _2. 0 R

wherein R is hydrogen, alkyl, such as ethyl, dodecyl or oleyl, acyl, preferably acyl radicals of an aliphatic carboxylic acid, such as lauric acid or oleic acid or a phenyl group, such as Denotes phenyl or p-dodecylphenyl; η should in general be an integer between 8 and 200. Are pretended

AG 104 - 5 -

909811/1111

Products with molar weights between 1500 and 10,000. Such polyethylene oxides are described in US patents 2 240 472 or 2 400 532.

Likewise suitable as chemical sensitizers are derivatives of phosphoric acid with polyalkylene oxide chains. Such Products are described in French patents 1,364,351, 1,396,860, 1,423,680.

The compounds are condensation products of spirocyclic acids Pentaerythryte-di-phosphoric acid monohalides with polyethylene glycols, which contain about 3 to 100 ethylene oxide units. They correspond to the following formula:

0 JQ CH ₉

s 2

_v 0
\ "

0 CH ₂ . CH ₂ ) _m -

OH

where R _{1 is} hydrogen or an alkylene oxide chain with 3 to 100 alkylene oxide units, m is an integer between 1 and 10. "This group of chemical sensitizers also includes condensation products of amidophosphate acid derivatives with polyethylene glycols of the type mentioned above. Such compounds are identified by the following Formula shown:

HO- (• CH ₂ -CH ₂ -O- ^

P-0-4-CH ₂ .CH ₀ -O ±,

^l 2 ^{w 7} IT

Here, R ₂ denotes hydrogen, alkyl, aryl or aralkyl and AG 104 8Öa8ßU / 11 11

Can nusammen R is alkyl, aryl οdar Aralkylj R _g and R j the ftur complete a 5- or 6-glieflrigen heterocyclic. Represent rings · necessary Eingglieder "is has the meaning given above, ρ let a Ganee pale" wipe O and 100 "q is β wipe 1 and 5 * You erflndungegemäSen epirocycllschen Quattraärsalse can also sit advantage in combination with the German patent, ... .. · A 50,595 IXa / 57b described vernetstsn or non-crosslinked water-soluble quaternization are ton tertiary polyamines used with bifunctional PoIyalkylenoxldderivaten *

The addition of the compounds according to the invention in combination with polyalkylene oxides or polyalkylene oxide derivatives results in a higher sensitivity than the additions of only the respective individual components tohter synergistic effect on * The substances can with the same effect must also be set for the developer.

• - ♦

The inventive compounds are the emulsion in

Quantities of 0.3 to 30 g per hal of halogen silver »preferred 0.3 to 1 g per hol of halogen silver sugteetet. You above Quantities correspond to a concentration of 0.1 to 10 g per liter of emulsion «preferably 0.1 to 1 g per liter of emulsion.

Di · polyalkylene oxides or polyalkylene oxide derivatives are in the usual dosages v * rw »n4et« The consistency of the

ί "'^;-'■" ■ ■■ "■■. ■■■■■

_ff .. 909811/1111

BAD ORIOiNAt

J **

Η7275ΐ,

Polyalkylene oxides can be used depending on the the emulsion used varies within wide limits in general, it is also sufficient »2uefctae of 0.3 bit 30 0.3 Me 3 g per mole of halogen halide,

The subjects of the invention can be applied with any halogen emulsion ions. AXs are silver halide Silver chloride, silver bromia or oil fleas thereof »tvtX. with. a low content of silver iodici up to 10 HoX ^ suitable. The silver halide "can be dispersed in four common hydrophilic compounds," beiepitlBv / eiae in carboxyethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and their salts, setters or amides or, preferably, gelatins ♦

The Emuleion may also contain other chemicals before sensitizers, aB quat "? Nary ammonium and phosphonium" owie ternary "sulfonium \ imaalae _f HeduktionsmitteX as tin 'II ~ 3alse, Polyaiulna as Diäthylintriasiin or SehwefeXverbindung' n _f as in the rnjoerikaniöchen Pat # ntachrift X 574 944 besohriebfn "For cheap susceptibility, the abovementioned mul- • ion remote * salts such as Rhutenium" Bhodiu "ialladium, Iridium, Hatin or GoXd" as dite in the "ArtilieX voit Bd ^ iiowelt" wÜe.Phot. 46 »e $ -72 (X95X) has been booked»

The emulsions grains also optically, eenoibilized finely »i * B« »It dtn ttbXicftt» I ^ Jyjltthinfarbetoffen! how baiieohen ode * ÜJ ^

oyenintn, styryl fiber, o ^ on oils

"': ORIGINAL

Sensitizers are described in the work ▼ on Ϊ.Μ. H * mer * fh§ Cyanine Öy «8 and related Gowpounda" (1964)

You! Emulsions contain U- high stabilizers, such as * »B. Feomopolar or saline compounds of mercury * with aromatic or heterocyclic rings (such as mercaptotriazoles), simple mercury salts, sulfonium-mercury double eels, and other mercury compounds. All atabilieators are also suitable A ^ aindenes, preferably tetra or pentaazaindenes, in particular those which are eubstituted with hydroxyl or aroino groups. Such connections are in the article by Birr, % .Wies «Phot. 47, 2-58 "(1992) described" Further suitable stabilizers and inter alia heterocyolic Htroeptονerbindungen, * "B. PhenylKarcaptotetrazol, quaternary benzothiosol derivatives, Benfitriaaol and

The bmulaions can be hardened in the usual way, for example with formaldehyde or halogenated Aldehydes that contain a carboxyl group, such as kucobric acid, bicetones, kethane sulfoaic acid ethers, dialdehydes and the like «

The compounds according to the invention can also contain color couplers. jiigtssttst wt? dt?> "Bi" Jusät * "can Baulsion ij> j «a *« b # litbig # ji Stadiua ihrtif production of a «

RltWioJilir koiSBieii di # same Example It

A broajoditlber-aelattneemuleion, which per liter. 60 g Silver as halogen egg with a silver odide content of 6 moles were added 600 was ßaponih as a wetting agent 200 sig 4 — Biydroscy — 6 — methyl-Ij 313a »7 — tetraazaindene as

Stabiliaator and 10 al of a 10% aqueous solution of formaldehyde.

Tuck emulsion hurdle divided into equal files and den the following substances are added to individual files

Sample I and comparison sample - without addition Sample 2 t 793Jag per hol silver halide of the sensitizer

the following formula {according to the German

Patent specification 1 178 297) t

H ₂ He

Sample 3 t 1 g per mol of silver halide Xthylenebie- (din-butylBUlfonium) -aibromide according to US Pat. No. 2,288,226. * ■ '"'

sample ? * sample 6t sample t * J? Robe sample 9 t sample A-O 104

1 g per hol of silver halide of the substance Hr. I.

1 g per hole of silver halide of substance XV 1 g per hole of silver halide of substance V 1 g per hole of silver halide of substance IX Ig per hole of silver halide of substance X 1 g per hole of silver halide ethylene-bis - {- di-n-bu ^ a. sulfonium) -dibromide and 7§0mg per hol

".- .. 10-, 90 9611/1111.

Al

Silver halide of a polyethylene oxide derivative according to sample 2.

foobe 10 * lg per mole of silver halide of the substance I '- Si 75ping per mole of silver halide a polyethylene oxide derivative according to sample 2.

Sample U t Ig per mole of silver halide of substance IV · .; and 7SQ mg per mole of silver halide of a polyethylene oxide derivative according to sample 2.

Sample Ig I 1 g per mole of silver halide of substance V UjJd _- 750 mg per mole of silver halide of a polyethylene oxide derivative according to sample 2.

Sample } 3 ϊ Ig per mole of silver halide of substance IX

and 793 mg per mole of silver halide of a poly-ethylene oxide derivative according to sample 2.

Sample 14 t 1 »per mole of silver halide of substance X and 750 mg per mole of silver halide of a polyethylene oxide derivative according to sample 2.

The results of the comparison tests can be seen in the following table:

Table II «Yp " developed 8th Sample' - · Pin. 6AO developed S. 42.0 °
like $ yp r 0.06 42 - * '■ "! ■' • r Φ.Ο6 '6 min + 1.0 ° 0.68 0.05
0.06 42
$ 4 · * · ■■ Ms 0.07
0.07 Sample E. 4 +, 5 ^ö 0.58
0.65 0.07 43 0.58 0.06 G
m
te
· ** 1 - ^^ || 0 ^Ο 0.65 0.06 - / i2 44 .0 » 0.56 ö, or "S.
4afc 2 1044 * '. ' 0.68 0.06. " 13th 4th , 0 ° 0.58 0.07 - * 4th ν, ■ - 0.60 0.06 14th
11 - 44 2.5 ° 0.58 0.06 ^ fc- 5 0.65 , 0 ° 0.60 ORlGiNM- 6th • 7th
AG

Example 21 The same procedure was used as in Example 1

described. Xn different parts of the emulsion will be now added the following substances:

Sample I t comparison sample * without addition »

Sample 2 t 75OBg per mole of silver halide of the ionic polyalkylene oxide derivative of the following formula (according to German patent specification. ... ... A 50 595 IXa / 57b) j

_{H 2} C-CH ₂ CH 2 -O-OH ₂ CH ₂

Jf Se—

2 toeylate

Sample 3 1 Ig per mole of silver halide xthylenebie- (din-butylaulfoniunj) dibromide and 79Örof per mole of silver halide of a polyethylene oxide derivative according to sample 2

Sample 4 ? 1 g per mole * of silver halide of Substans I.

and 750Bg per mole of silver halide of a PolyOthylenoxidderivaiee according to sample 2 «

Sample 5 »1 g pfö fm 8 * jS # rnelogenid der Substah · Vf

and 750rag per hol silver halide of a polyethylene oxide derivative according to sample'2. .

Sample 6 : Ig per mole of silver halide of Sub et ant V

and 750ag per mole of silver halide of a PolyätthylenfenÄIJ sample 2 ·

A-Q 104

ia.-

909011/1111

. r ' 147270ί

Erofrt 7 t Xg per HoX SiXfcerhaXogenid der Substans IX

and 75OiBg jpro KoX silver halide tines athyX «noÄidd0riv * t * e gfÄÄfl Jtoit 2.

Ig per KoX silver halide dtr StttNtaiisi X and 75Qpig per Koit silver halide a »FoXy-ÄthyXenoxide έ

The results of the comparison even can be seen in the following t SaIitXXβ

- ". 6 kin, f .. ttttwicktlt S. sample Β "> 0.06 X Type 0.60 0.06 2 + 3.0 ° 0.65 O ₁ Of 3 * 2, O ^Ö 0.64 0.09 4th + 3.5 ° 0.65 O ₁ XO 5 + 2.5 ° 0.60 Οι 07 6th + 4.5 ° 0.60 0.10 -. ' · ■■ ι: ■■ ' 44.0 ° Qi 63 0.07 β 44.0 ° 0.61 Belepiel 3s "- ■ ·". ■. . ·.

Eb was followed in the same manner as in Example 1 described. In different parts of ^one emulsion now be the following · η Substanatri lugefügtj

I t YtraXtichsprot »·» without »ingredient a. ■ *.

A »0 XQ4

SAD ORfGfNAL

sample 2l sample

45 ".

750-5 per mole of silver halide of a simple one Polyethylene oxide with 90 ethylene oxide units.

1 g per mole of silver halide Kthylen-bi «« (- di * · n- »butyl8ulfonlum) -dibromide and 750mg per mole of silver halide of a polyalkylene oxide according to sample 2 *

coarse 4 1 Ig per hol of silver halide of substance IV and ? 50mg per mole of silver halide of a polyethylene oxide according to sample 2 *

The results of the comparative experiments are from the following Table can be seen i

Table 3 t

6 min. developed S. sample E. r 0.06 1 Type 0.68 0.07 2 + 1.5 ° 0.55 0.06 3 + 1.5 ° 0.52 0.06 ■ 4 + 2.0 ° 0.55 Example 4 •

The same emulsion as in Example 1 was redeätelich with 40 mg of the panchromatic sensitizer »of the formula

«CH-6 * C * S

104

- 14 -

909811/1111

and with 20 mg of the orthochromatic sensitizer der Formula

Ov "0,

XJ = CH-C = CH-GH-

NC ₂ H ₅ " _{c +:} ^C 2 ^H 5

per liter and divided into 9 equal parts. The following compounds were added to the individual parts:

Sample 1 : Comparative sample - without addition Sample 2 t 750 mg per mole of silver halide of a substance corresponding to German patent specification No. 1 178 297 (see sample 2 of Example 1).

Sample 3 : 750 mg per mole of silver halide of the sensitizer Substance No. VII from Sample 2 of Example 2.

Sample 4 t 1 g per mole of silver halide of substance No. IV.

Sample 5 t 100 mg per mole of silver halide of substance No. IV and 793 mg per mole of silver halide of a polyethylene oxide derivative according to sample 2.

Sample 6 t 1 g per mole of silver halide of substance No. IV and 750 mg per mole of silver halide of a polyethylene oxide according to sample 3

Sample 7 1 1 g per mole of silver halide of substance No. VII.

ο sample 8 t 1 g per mole of silver halide of substance No. VII

to and 750mg per mole of silver halide of a polyethylene ^ oxide derivatives according to sample 2.

^ Sample 9 t 1 g per mole of silver halide of substance No. VII and 750 mg per mole of silver halide of a polyethylene

A-G IQA

oxide derivatives according to sample 3 »- 15 -

1472741 ^.

■. ■ * ■ '"· * ■

The samples are cast and developed as in Example 1.

Table 4j 6 min • developed S. B. 0.06 sample 0.70 0.08 1 + 2.0 ° 0.80 0.07 2 Of 9? 0.06 3 + 2.0 ° 0.75 0.07 4th + 3.0 ° 0.75 0.06 5 + 4.0 ° 0.80 0.07 6th + 2.0 ° 0.90 0.07 7th + 3.0 ° 0.80 0.08 8th + 3.5 ° 0.80 9

-Q 104 -

909811/1111

Claims (1)

H7279T ' Claims ι 1 * Light-sensitive photographic material with at least 1 Halogeneilberemuleionachicht, which with a ■ Polyethylene oxide derivative is chemiech eensibilieiert, characterized by a content of a sulfonium salt following general formulas} R- ^ 3 X or, Z- ~ —i 2 X " where mean « R = a straight-chain or branched, saturated or olefinically unsaturated aliphatic radical up to 6 C atoms substituted by at least one hydroxyl, carboxyl or epoxy group; % »Alkylene with up to 18 carbon atoms, the alkylene chain can be interrupted by heteroatoms or aralkylene; X 9 any anion. ^! 2. Photographic light-sensitive material according to claim 1, characterized! that a sulfonium eala iat contained, that contains 2 0-hydroxyethyl groups * 3 light-sensitive photographic material according to claim 1, characterized in that the sensitizer is a polyethylene oxide the following formula is included » H, ο --f CBa · CH ₀ · 0>> R · ■ · "■■ .. · ■■■ - '· * ■ ■.. . ". 909811/1111 _BAD JAMiar.fi, ..; Ί .... New ÜWotlaqMfArt, where R is hydrogen, alkyl _e acyl or a phenyl group and η is an integer between 8 and 200 «' 4. Photographic light-sensitive material according to claim 1, characterized in that a polyalkylene oxide of the following formula is included as an additional sensitizer » CH OH where R- is hydrogen or an alkylene oxide chain with 3 to 100 alkylene oxide units, tu is an integer between 3 and 100 and χ is an integer between 1 and 10. 5. Photographic light-sensitive material according to claim 1, characterized in that a crosslinked or uncrosslinked water-soluble quaternization product is used as an additional sensitizer of tertiary polyamines with bifunctional polyalkylene oxide derivatives is used.