DE1472848A1 - Use of butadienyl dyes as light filter and anti-luminous dyes - Google Patents

Description

Copy

25/29 August 20, 1965

Registration number. 119

Eastman Kodak Company, 3 ^ 3 State Street, Rochester, New York State, United States of America

Use of butadienyl dyes as light filters and anti-cancer dyes

The invention relates to the use of new Butadienyl dyes as light filters · and anti-cancer dyes in light-sensitive photographic materials.

The use of light-filtering and anti-light colorants in photographic light-sensitive materials is known. For example, photographic Materials with light-sensitive emulsion layers coated with oversoles, dl «one or more light-filtering Dyes are included to protect the photosensitive emulsion layer from exposure to ultraviolet light to sohUtsen. Especially with color photographic materials such light-filtering layers are often used

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Such light-filtering layers are also known between differently sensitized emulsion layers of a photographic material, for example in order to prepare red and green unsensitized emulsion layers to protect them from exposure to blue light. Finally, it is also known to use such dyes as antihalation dyes To be used in so-called anti-halation layers that are on one or both sides of a transparent Support can be arranged with at least one light-sensitive emulsion layer.

Especially in those cases where the light filtering Dyes are used to protect color-sensitized emulsion layers, the light-filtering compound is said to be do not react chemically, especially not the sensitivity or the color sensitivity of the photosensitive Can affect the emulsion layer. Furthermore, the light-filtering compounds should not turn off

others of the layer in which they are accommodated into a / layer can diffuse, neither in the production nor in the storage of the photographic material. Finally, the light-filtering compounds should be easily decolorable and / or should be before or during the photographic Development process can be easily removed. If necessary, the light-filtering compounds should be in one of the photographic developing baths can be inactivated

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the. Bel the development according to the chemical reversal process For example, is it desirable to use such filtering compounds during negative development inactivated, i.e. bleached and / or removed, in order to prevent the exposure of the silver halide that is still present to facilitate.

All light-filtering dyes have so far been the most varied Dyes have been used. However, it has been found that none of the known dyes have all of the desired ones Has properties. Many dyes are not resistant to diffusion and migrate from the layer in which they are housed are in other layers. In doing so, they influence the sensitivity of the light-sensitive emulsion layers in an undesirable way. Other light filtering Dyes already affect the light-sensitive emulsion layers when the layer in which they are accommodated comes into contact with a photosensitive emulsion layer. Other light-filtering dyes in turn are very sparingly soluble in water, so that they can only be extracted from aqueous solutions with great difficulty Allow to work into light-filtering layers. Finally, other light filter dyes have the disadvantage that they cannot or only with difficulty can be bleached or destroyed during the photographic development process and, as a result, discoloration and staining

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drive in the developed photographic materials

Eb is also professed to use styryl dyes as anti-light dyes in rear view of photographic materials see below · Such styrene dyes are described, for example, in US Pat. No. 1,845,40 * · Es has shown, however, that only a few styryl dyes Absorb your red spectral range · Furthermore, are Styryl dyes, for example that of indolrel, often very unstable "and" was even alkaline with formation Conditions · Many of the known dyes also have the disadvantage that they are more hydrophilic in aqueous solutions Colloids »such as gelatine» polyvinyl alcohol, Albumin, casein and the like · »fall out easily · after all the well-known styryl dyes only soluble in organic solvents »for example in acetone or alcohols» so that they can only be processed from such solutions By means of these solvents, the dyes can then easily be seen in the substrate of the photograph Material penetrate »which in turn has the consequence» that they can only be bleached or destroyed with great difficulty during the remaining photographic development process

The present invention was therefore the task of Orunde » Dye · su develop »which see both as light filter elements also anti-pharmaceutical substances in photographic layers

BADORIGJNAU

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photographic materials are suitable · The dyes should have excellent light absorption properties, better in aqueous and weakly acidic solutions be more soluble than the previously known dyes be and see through photographic developer «or Let the fixer bleach slightly

It has been found that the problem posed by using goose of special butadlenyl dyes can be dissolved.

Accordingly, the invention relates to the use of Butadiene?! Dyes of the formula:

• C (-CH s CH) ₀ - Z

Q

in which meanι

L is a hydrogen or halogen atom;

T and T ₂ one hydrogen tone or together the only biltong eleventh ring anchored to the indole ring * required non-metal atoms,

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R and R ₁ are hydrogen atoms or alkyl groups or together the atoms required to form a cyeloalkane group;

R _{2 is} an optionally substituted AHqrl group;

Z is an aminoaryl, alkoxyaryl or hydroxyaryl group j

X is a slureanone;

η «1 or 2, such that η is only * 1 if the alkyl group R ₂ is substituted by a carboxy or sulfo group,

as light filter and anti-stick dyes in rented apples photograph! see materials.

In the specified pomel, L is a precautionary measure Chlorine, bros or fluorine atom

If T and T _{2 represent} the formation of a high metal sheet required to form a ring that is attached to the indole length, then the ring can be in the * and ^ positions, the 5- «nd <* S% oll« agon or the 6- and 7- 3 positions to be anchored

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Besitsen R and R ₁ dl · meaning of alkyl groups, such loading sitsen this vorEugsweise 1 to 18 carbon atoms, particularly 1 to 4 carbon atoms · forming R and H ₁ gemelnaasi the * for forming a Cyoloalkangruppe atoms necessary, it may for example consist of a Gjrelopentan or cyclonexan group.

R ₂ can, for example, be a carboxyalkyl group, for example a carboxyethyl, β-carboxyethyl, γ-carboxypropyl,! -Carboxybutyl, «-carboxypentyl-,« -carboxyhexyl group and the like. R ₂ can also mean a hydroxyalkyl group have, such as, for example, an A-hydroxyethyl, -hydroxybutyl or “hydroxyhexyl group. R ₂ can also have the meaning of a carboxyalkylearbaoyloxyalkyl group, for example a carboxymethylearbaaoyloxylthyl group or A-carboxyethylcarbamoyloxy, poxyethylcarbamoyloxy, poxyethylcarbamoyloxy- & thyl-, toyloxy- carboxyethylcarbamoyloxy- & thyl-, toyloxy- -, A-Carboxylthylearbomoyloxypropylgruppe and the like «R ₂ can also have the meaning of an alkoxy · earbonylalkyl-orarbajioyloxyalkylgruppe, for example an XthoxyttarbonylmethylearbaHoyloxyäthylgruppe,

η
a methoxyoarbonyltthylcarbsoyloxylthylgruppe, an Xthoxyearbonyltthylearbanoyloxytthylgruppe etc. R _{2 can also} mean a sulfoalkyl group, for example a-sulfoethyl, γ-sulfopropyl, β “sulfobutyl, M-SuIfohexylgXruppe and

BATH ORIGINAL

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If R has the meaning of an alley group », she barks
se preferably 1 to 18 carbon atoms »in particular

1 to 6 carbon atoms.

X consists, for example, of a chloride, brotaide, iodide, perchlorate, thloeyanate, benzene sulfonate, methyl sulfate, Ethyl sulfate, p-toluenesulfonate anion and the like

If Z consists of an aminoary group, this can, for example from a phenyl, toly- or propylphenyl group exist, which is substituted by an amino group Amino group itself, a Dlalkylaalno group, for example an N, N-Dlmethylamino group, a Ν, Ν-Diethylamlno group, a Ν, Ν-dipropylamino group, an N, N-dibutylamino group and the like. Or an alkylamino group such as an N-methylamino, N-propylamino-j N-butylaaino group and The like or an N-alkyl-N-arylamino group, such as, for example an N-methyl-N-phenylamino-; N-butyl-N-phenyleino-; N-Xthyl-N-phenylamino group and the like. The aryl group can be further represented by, for example, alkoxy groups such as Nethoxy, xthoxy, propoxy, butoxy, and the like. Substituted be·

The butadienyl dyes used according to the invention of the specified Formula let see easily, precautionary by He » hits and under reflux conditions, a compound of

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following, formula:

II.

old of a compound of the formula

'n-1

III

0 H-C-CH * CH-Z

which is dissolved in acetic anhydride. L, T ₉ Y ₂ , R ₉ Rj ₉ R ₂ , I, η and Z have the meanings already given.

The butadlenyl dyes used in the invention absorb Surprisingly, long wavelengths lie in what they look to advantage from the known ones Differentiate between styryl dyes and other butadienyl dyes.

Furthermore, see the inventions used Dyes extremely easily by the action of developer solutions, for example p-methylaeinophenol sulfate Hydroehlnonentwloklerlösungen bleach. Because of these properties, the new dyes are particularly suitable in red light absorbent photographic elements. Those substituted by sulfur groups

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Furthermore, new dyes are particularly suitable x only for use with basic carriers, for example the cellulose esters of dimethylamineous acid

The following is the manufacture of some of the inventions usable new butadienyl dyes described

Dye 1

Anhydro-2- (1-p-dJbaethy lamlnophcny 1-1.1-dlmethjl-1,3-butadienyl) -3 - (^ - »ulfobutyl) -lH-beng / e7lndolluMhjdro3iyd

«5Η ₂ ) _ή 3Ο ^β

6.9 g (1 mol) Antydro-3- (4-sulfobutyl) -l _t l, 2-tri "ethyllH-BENK / e7lndoliumhydroxyd and 1 g (1 Hol ♦ 100% excess) of p-Dimethjlaalnoelnnaealdehyd In 20 milliliters Esslgsiureanhydrld and received under reflective conditions for 5 minutes. The reaction mixture was then chilled over Naoht, whereupon the precipitated crystalline dye was filtered off, washed on a Buchner funnel old acetone and dried.

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material after two Umkristalllsatlonen of methyl alcohol of a 4M Jtigen was 4 g _# 2 ₉ · yield according The melting point of the dye was "wipe 220 and 221 ° C.

Dye 2

Anbjrdro- »5-ehloro-» 2- (fr-p-dlmethylamlnophenyl-1,3-butadlonyl) 3.3-methyl-1- (fr-sulfobutyl) -3H-indollum hydroxide

3.3 g (1 mole) of anhydro-5-chloro-2,3,3-trimethyl-1- (4-sulfobutyl) -3H-indolium hydroxide and 3 »5 g (1 mole + 100 % excess) p-methylamino-aldehyde were in 25 ml of acetic anhydride were dissolved and refluxed for 20 minutes. The reaction mixture was then refrigerated overnight, whereupon the crude dye was precipitated from the solution by adding an excess of ether while stirring. The Xther was decanted off from the sticky precipitate, whereupon the dye was made to crystallize by adding acetone and stirring. The crystalline dye was then filtered off, washed with acetone on a Buohner funnel and dried

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Recrystallization from a mixture of 50 % methyl alcohol and 50 % water was 1 g of pure dye, corresponding to a yield of 22 % with a melting point of 245 to 246 ° C dec. obtain.

Dye 3

Anhydro-5-chloro-2 - (* tp-methoxypheny1-1,3-butadleny1) -3 «3-dlmethy 1-1- (4-sulfobutyl) -SH-indollum hydroxide as reaction components 3.3 g (1 mol) of anhydro-5-chloro-2,3 »3-trimethy1-1- (4-sulfobutyl) -SH-indolium hydroxide and 3 * 0 g (1 mol ♦ 100 % excess) p- Methoxylnnamaldehyd were used. In addition, the concentration of acetic anhydride was reduced to 20 ml. The yield of pure dye was 1.3 g, corresponding to a 30% yield. The melting point of the dye was between 297 and 298 ° C dec.

dye

3-Carboxyinethylcarbamoyloxyfithyl-2- (4-p-dJmethylamlnophenyl.1 ₉ 3-butftdienyl) -1, l-dimethyl-1H-benzZft7indollumiodid

(CH ₃ ) ₂

(-CH-CH),

(CH ₂ ) ₂

0-CO-NHCH ₂ COOH

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3 »33 g (1 mol) l, l-dimethyl-2- (1-p-dim'ethylaminophenyl-.l _t 3-butadienyD - ^ - ethoxycarbonylmethylcarbamoxyethyl-lH-benz / V-indoliuraiodid and 0.4 g (1 Mol ♦ 100 % excess) Sodium hydroxide, dissolved in 2 ml of water, was dissolved in 200 ml of absolute ethyl alcohol. The solution was then refluxed for 10 minutes. The yellow precipitate which separated out was filtered off and then suspended in a small amount of water Acetic acid was then added to the water suspension, whereupon the dyestuff which had formed back was filtered off, washed with a small amount of acetone and dried 186 to 187 ° C dec.

Dye 5

2- (Mp-Dimethylamlnophenyl-l _a 3 "butadienyl) -3-ethoxycarbonylmethylcarbamoyloxyethyl-l, l-dlmethyl ~ lH-benz / e7lndollumlodld 3 g (1 mol) l, l-dimethyl-2- (iJ-p-dimethylaminophenyl- 1,3-butadienyl) -3-hydroxyethyl-1H-benz / e-indolium iodide and 5 g (1 mol + 300 % excess) carbethoxymethyl isocyanate were added to 75 ml of dry pyridine, whereupon the mixture was refluxed for 1 hour then allow to cool, whereupon the precipitated crystalline paraffin was filtered off and dried

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0.5 g of pure dye corresponding to a yield of 50 % with a melting point of 230 to 231 ° C. dec · obtained.

Dye 6

2- (4-p-Dimethylaminopheny1-1 »3-butadlenyl) -3-hydroxyethy1-1.1-hydroethyl-1H-benz / e7indollumlodld

18 g (1 mol) 3-Hydroxyäthy1-1,1,2-trimethyl-1H-benzfe / indoliumbromld and 10.3 g (1 mol ♦ 10 % excess) £ -diraethylaminoelnnamaldehyd were added in absolute ethyl alcohol, whereupon the mixture 10 minutes The mixture was then placed in the cold, whereupon the dye was precipitated as iodide by adding sodium iodide with stirring. The dye was then filtered off, suspended in water, filtered off again from the suspension, washed with a small amount of acetone and dried . After two recrystallizations from methyl alcohol, 12 g of pure dye corresponding to a 42% yield with a melting point of 250 ° C. dec. obtain.

Dye 7

3-Carboyäthy1-2 - (^ - p-dimethylarolnophynyl-1,3-butadlenyl) -1,1- dl »ethyl-lH-benzfe./indoliumiodld

6 _# l * lg (1 koi) of 3-carboxyethyl-l, l, 2-trimethyl-lH ~ benz4V * indoliumlodid and p-dimethylaminocinnamaldehyde were mixed in ■ ethyl alcohol, and the mixture 1 hour, heated to RüekfluBtetiperatur long. The mixture was then chilled, whereupon the precipitated paraffin was filtered off,

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washed with a small amount of acetone and dried. After rweimaliger ÜmkristalIieatlon from ethyl alcohol 4.6 g of pure dye in a yield of 5 ¹ were correspondingly * dec% with a Schneispunkt of 17Ί to 175 ⁰ C. obtain.

Dye 8

Anhydro-l «l-dlmethyl-2- (fr-p-dlmethylamlnophenyl-l., 3-butadlenyl) -3- (3-sulfopropyl) -lH-beng / indolium hydroxide

66.2 g (1 hol) of anhydro-3- (3-tulfopropyl) -l, l, 2-trimethyl-IH-bens ^ eJTindoliumhydroxyd and 17.5 g (1 mol + 50 % excess) p-dimethylaminonnamaldehyde were in 500 ml of absolute ethanol mixed, after which the mixture was heated to reflux temperature for 1 hour. The mixture was then kept in the cold overnight, whereupon the precipitated crystalline dye was filtered off, washed with acetone on a Buchner funnel and dried. The yield of purified dye after three recrystallizations from methanol was 51 g, corresponding to a 51% yield. The melting point of the dye was 238 to 239 ° C.

Dye 9

Anhydro ~ 2- (M ~ p-methoxyphenyl-1,3 "butadlenyl) 3.3 ~ dlmethyl ~ 1- (fr-sulfobutyl) -3H-indolluahydro * yd

This dye was prepared exactly as dye 2, but 1 mole of anhydro-2,3,3-

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BATH ORIGINAL

trimethyl-1- (4-sulfobutyl) -3H-indolium hydroxide and 1 mol ♦ 100 % excess of p-methoxycinnamaldehyde used. At the same time, the concentration of acetic anhydride was reduced to 20 ml.

Dye 10

Anhydro-2- (fr-p-dlmethylamlnopheny1-1 _a 3-butadlenyl) -3.3-dlmethyl-1- (* t-Bulfotoutyl) ~ 3H-indolium hydroxide

This dye was prepared as dye 2, except that 1 mol of anhydro-2,3,3-trirasfchyl-1- (4-sulfobutyl) .3H-indoline hydroxide and 1 mol of ♦ 100 % excess of p-methylaminocinnamaldehyde were used as reaction components.

Dye 11

AnhydrO-2- (4-p-dlmethylaminopheny1-1,3-butadieny1) -1 _Λ 1-

dime thy 1-3- (3-8ulfobutyl) -lH-benK / e.7indolimnhydroxyd _> tkmosulfonlert

C-CH «CH-CH * CH - \ TN (CH ,: % # \ / 3

CHg

t «

CHSO ₃ ⁹

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5 »78 g (1 mol) 1,1,2-trimethyl-1H-benz / e / indole, monosulfonated and 2,4-butanesultone In such an excess that a mobile Mixture was obtained, were mixed together and heated over a free flame until the viscous mixture had turned a brown-black color " The mixture was then allowed to cool, whereupon the anhydro-3- (3-8ulfobutyl) -1, 1,2-1H-ben * / e7indolium hydroxide monosulfonate was precipitated in the form of a gray precipitate by adding an excess of acetone with stirring. The gray hydroscopic precipitate was filtered off and dried in am Dissolved refluxing ethyl alcohol (100 ml). 3 »5 g (1 mol) of p-dimethylaminocinnamaldehyde were then added to the solution, and the mixture was refluxed for 15 minutes. The mixture was then placed in the cold. The crude dye was then precipitated by pouring the mixture into 300 ml of acetone with stirring. The precipitated dye was then filtered off, washed with acetone and dried. After two recrystallization aqueous methyl alcohol and acetone gave 3 * 5 g of dye, corresponding to a 31% yield with a melting point of 289 to 29O ° C dec. obtain.

Dye 12

Anhydro-3-carboxyethyl-2- (4-p-dlmethylaminophenyl-1,3-butadienyl) -1, l-dimethyl-1H-benzZeIndollum hydroxide, monosulfonated; Pyrldln salt

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C _C H _K N.HO, S.
5 5 3

CH ₀

t *

coo ^e

5.78 g (1 mol)!, L ^ -trimethyl-lH-benz / e-indole, monosulfonated and propiolactone In such an excess that a mobile mixture was obtained, they were heated together over an open flame until the pesticide constituents were dissolved formed and the solution turned amber. The vessel containing the mixture was then removed from the flame. The reaction proceeded less quickly, with the color of the solution darkening greatly. The highly viscous mass finally obtained was allowed to cool and stirred with an excess of ether. The Xther was then decanted off, whereupon the sticky residue was dissolved in 200 ml of refluxing ethyl alcohol. Then 3 × 5 g (1 mol) of p-dimethylaminocinnamaldehyde were added, whereupon the mixture was heated under reflux conditions for a further 10 minutes. The dye deposited on cooling. It was filtered off and recrystallized twice from ethanol and pyridine. The yield of pure dye was 1.5 g, corresponding to a 43% yield. The melting point of the dye Ug at 226 to 227 ⁰ C dee.

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dye

13th

2- / y-p-Dlmetbylamlnophenyl-1,3-butadieny jj-l-ethy 1-3, 3- dlmethyl-3H-Indollwnlodld

This dye was made like dye 6 with the The exception, however, is that 1,1,2-trimethylindolenine ethodide and

p-Dimethylaminoeinnamaldehyde were used. The yield of purified dye was 32X. The dye possessed a melting point of 238 to 239 ° C dec

The intermediates used in making the dyes can be produced according to the following process:

3-Hydroxyfithyl-1,1-dimethyl-1H-bent / V indolium bromide

10, K g (1 mol) l, l, 2-Trlmethjrl ~ lH-benere / indole and 6.25 g (1 mol) 2-bromoethanol were mixed together and heated together for 20 minutes on a steam bath. The resulting hard cake was then ground under ether, suspended in acetone, filtered and dried. The yield was 15 g (90 %). The melting point of the compound was 159 to 160 ° C dec.

The corresponding ideal of iodine can easily be found in the Broald produced by double conversion with sodium iodide «

(♦ 100% excess 1 mol) of 1,1,2-trimethyl-lH-indol bensüJ and 10 g (1 mol) of ß _{3-carboxyethyl-l>} l _t 2-trimethyl-lH-ben »^ eyindollumiodid 20.9 C - Iodopropionic acid were used with each other

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mixed and heated on the steam bath for 12 hours · The The reaction product was washed with ether, heated to reflux temperature in acetone, filtered and dried Yield of the reaction product which is brownish in color was Ht g, corresponding to a 70% yield. The melting point was 18-182 ° C dec.

Anhydro-SC ^ -sulfobutyD-ll ^ -trimethyl-1H-benE / 'ejrindoliurahydroxyd and anhydro-3- (3-sulfopropyl) »- 1,2-trimethyl-1H-benKle7 ⁱⁿ doliumhydroxyd were after the in the USA No. 2,895,955. Anhydro-2,3,3-trimethyl-1- (4-8ulfobutyl) -3H-indolium hydroxide was prepared from 1,1,2-trimethylindole by the process described in US Pat. No. 2,895,955. ¹ was made in the same way, but using; of 5-chloro-2,3 »3-trimethyl-3H-indole.

In the following Table I are the maximum light absorptions of the dyes described.

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Table I. Dye no, maximum light absorption at one Wavelength of, measured in πιμ

1 615

2,630

3 over 70 ή 625

5 625

6 605

7 620 13 610

The butadlenyl dyes used according to the invention under · » They differ from other butadlenyl dyes because they have a maximum light absorption at wavelengths have «which are considerably longer than the wavelengths in which other butadiene dyes absorb. Farther x declined surprisingly that the increase in parbtlefe by introducing a vinylene group in the inventive Indolenine and Beni ^ ejlndol dyes used are concerned greener than with other heteroeyclic ring systems, the styryl dyes are below. This is done through the The following table shows all the information recorded.

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Abaorptlonsmaxlnm of p-Dlmethylaminoatyryl- and p-dimethylamlnobutnylidene dyes

Heteroeycliachea ring system

Styryl color (mu) butadienyl color

Increase in color depth by introducing a. Vinylene group

(mu)

532.5 31.5

525.0 556.0

31.0

560.0 615.0

55.0

C-

557.0 633.0

76.0

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From the results obtained, it can be seen that of the higher vinyl only the dyes used according to the invention absorb at wavelengths longer than 600 ΐημEe was surprising ^ to find that the invention dyes used a shift in the spectral absorption of 70 mu, based on the corresponding Styryl dyes, occurs while the shift in the spectral absorption of not used according to the invention Butadienyl dyes, based on the dyes eu round lying vinyl logs, only about 31 is rough.

The dyes used according to the invention are sine! on Qrund their ionic nature easily soluble in water and can therefore easily be converted into hydrophilic colloids, such as Gelatine, polyvinyl alcohols, albumin and casein, which are used in the production of filter layers and anti-algae protection layers are used.

The concentration of the dyes used according to the invention in the hydrophilic colloid can be very different depending on the purpose for which the layer is to be used. The ideal concentration can be for easily through every dye and every purpose • a series of experiments can be determined

The drawing shows the structure of 4 different photo- ' graphic materials in which the new butadienyl color

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Fabrics can be used shown:

The material shown in Pig x 1 consists of a carrier 10, for example made of cellulose acetate, cellulose nitrate or to paper, but which coated with an emulsion layer 11 1st. On this emulsion layer 11 is applied an overcugs 12, which consists of a hydrophilic colloid such as gelatin and contains a butadienyl dye.

The material shown in Fig. 2 is a multilayered one color photographic material consisting of a support with several photosensitive layers 13, 14 and 15, which Record light of the red, green or blue area of the spectrum between the emulsion layers 14 and 15 i> t arranged a filter layer 16, which consists of gelatin,! »Which disperses a yellow butadlenyl dye is. The function of the filter layer is to expose the layers under the filter layer to light such wavelengths that are absorbed by the filter dye, su prevent. The dye can be essential Absorb light from other spectral ranges, such as the ultraviolet range of the spectrum "

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The plasma material shown in Fig. 3 has an antihalation layer with a butadienyl dye. Daa film material is also applied to the carrier 10 with an emulsion layer 11 on one side of the support and an anti-liohthof layer 17 with a butadienyl color on the other Side of the carrier

Pig 4 shows a plumb material made from a carrier 10 with an anti-inflammatory layer 18 and an emulsion layer 11. In this case the anti-inflammatory layer is applied Twelve carriers and light-sensitive gelatin silver halide modules arranged slightly. In In this case, the anti-halation layer has the task of absorbing light passing through the light-sensitive aelatlnallberhalogenldemulalalonaschicht arrives and from the surface of the carrier back into the emulsion layer is reflected.

The use of the new butadienyl dyes is extremely simple be dissolved by alcohol and waaaer, whereupon the solutions obtained are aqueous solutions aa hydrophilic Colloids can be added or a solution a hydrophobic colloids, for example cellulose acetate phthalate or a cellulose ester of methylaminoalgaic acid · So 10 milligrams of the dye 1 in

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5 milliliters of methanol are dissolved, whereupon the solution by adding water to a volume of 20 milliliters can be diluted. 10 milliliters of a 10-liter photographic gelatin solution, the 0.5 milliliters of a 15-day saponin solution was added «The mixture can then be on a suitable carrier in strength of, for example, 10 to 20 mg of dye can be applied per 0.0929 m.

However, the dyes can also be introduced into a binder layer from a solution. This is how it is, for example If possible, a layer on a cellulose triacetate film of alkali-soluble cellulose acetate phthalate, which is then washed with a 1-L solution of a dye, e.g. of dye 2 in a mixture of 95 t of alcohol and 5 l of water or an aqueous alcoholic solution of a mixture of 0.4 l of the dye anhydro-S-chloro-2-p-dieethylaninostyryl-3,3-dimethyl-1- (4-sulfobutyl) -3H-indolium hydroxide and 1 I of dye 2 is treated.

The following examples are intended to illustrate the invention in more detail:

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example 1

1.5 grams of the dye »1 were dissolved in 37» 5 ml of water, whereupon this solution was added to 4.5 liters of a 5% strength aqueous gelatin solution. The mixture was then applied as an anti-halation backing layer to the back of a support which had a fine photographic silver halide emulsions layer on the upper side.

After the photographic material was exposed to light, the exposed material was dissolved in a developer of the following composition developed:

N-methyl-p-aminophenol sulfate 2 g Sodium sulfite (dehydrated) 90 g Hydroquinone 6 g Sodium carbonate, monohydrate 52.2 g Potassium bromide 5 g

filled up with water sum liter

The material was then placed in a normal sodium thlosulfate fixer bath fixed. The dye was completely removed from the photographic material.

Example 2 A photographic material as in Example 1

described structure, but this time it was

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at «lle of dye 1 dye 4 is used In the development and fixation described in Example 1, there was no more dye in the photographic Material.

Example 3

A mixture of dye 1 and an aqueous gelatin solution » prepared as described in Example 1, was applied to a photosensitive silver halide emulsion layer which was on a conventional carrier, applied. After exposure of the photographic material, development and fixing of the exposed material in that described in Example 1 Way, no more dye could be found in the material described.

Equivalent results were described with the others Get dyes.

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Claims (3)

Claims
JL) Use of butadieny! Dyes of the formula: wherein mean; L is a hydrogen or halogen atom; T and T _{2 are one} hydrogen atom or together the sur formation of an ankondenalerten to the indolenine ring Ring's required Niohtmetallatone; R and R ^ are one atomic atom or alkyl group or joint formation of a cycloalkane group required atons; R _{2 is} an optionally substituted alkyl group; Z is an aminoaryl. Alkoxyaryl or hydroxy ary! groupι 909810/0832 X is a sulfur anion; η si or 2, such ₉ that η only then * 1 1st, if the alkyl group R ₂ is substituted by a carboxy «or sulfo group» as light filter and anti-candy dyes in light-sensitive photographic materials » 2) Use of anhydro-2- ( ⁱ lp-diHiethylaminophenyl-l, idloethyl-l, 3-butadienyl) -3- ( ⁱ "-eulfobutyl) - lH-b" ni / e71ndoliu "- hydroxide; 3-carboxyethyl-2- (4-p-dlraethylaitinophenyl ~ l, 3-but * dlenyl) -l, l-diMethyl-lH-b «niAe / indoliuraiodidj anhydro-5-ehloro-2- (4-p-dlmethylaminophenyl- 1,3-butadienyl) 3,3-dlaethyl-1- (^ - sulfobutyl) -3H-indollu «hydroxide; of the aonosulfonated pyrldlnsalses of anhydro-3 ~ earboxyfithyl-2- (4-pd ± methylnophenyl-1 _t 3-butadlenyl) -l "ldl" ethjl "> lH-bensA71ndollumhydroxyd or 3-carboxyethyloarbaaoyloxylthyl (4- carboxyethyloarbaaoyloxylthyl -l _v 3 * butadienyl) -l, l-dl * etbyl-lH-b * n «^ 7iodoliuiniodid according to claims 1 · 3) Use τοη ButadienyIfarbatoffen according to claims 1 and Arranged in a top of a silver halogen lamp Liohtriltersehioht * 909810/0832 U) Use of butadleny dyes according to Claims 1 and 2 in a light filter layer arranged between a silver halide emulsion layer and its support. 909810/0832