DE2165594A1 - Color photographic photosensitive materials - Google Patents

Description

PATENT LAWYER »·

DR. E. WIEGAND DIPL-ING. W. NIcMANN

DR. M. KÖHLER DIPL-ING. C. GERNHARDT 2165594 MÖNCHEN HAMBURG TELEPHONE: 55547 «8000 MD NCH EN 15, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

December 30, 1971 W 40 906/71 - Eo / DE

Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa / Japan

Color photographic photosensitive materials

The invention is concerned with color photography and particularly relates to the spectral sensitization of silver halide photographic emulsions comprising a Color ~ suitable for the diffusion transfer process Contains substance developing agents. In particular, the invention relates to the spectral sensitization of a photographic red-sensitive silver halide emulsion suitable for the diffusion transfer process.

Compounds that contain a dye in the molecule and contain a portion for developing the silver halide are essential photographs Elements for forming color images by the diffusion transfer process. Such compounds are commonly referred to as "dye developing agents".

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U.S. Patent 2,983,606 issued to U.K. Patent 804 971, the French patent 1,313,767 and the like indicate that when a photosensitive member containing a color developing agent and contains a silver halide, is exposed and treated with an alkaline treatment composition, in the areas exposed to light, development proceeds and the color developing agent is changed is, .so that it is practically not diffusible, while the dye developing agent is used on the unexposed parts can diffuse, and thus when the photosensitive member treated in this way is brought into contact with an image receiving element to obtain the dye transfer image, and in this case a positive color image is formed because the density of the image is inversely proportional to the amount of exposure.

The dye developing agents which can be used according to the invention are described in various literature references. These compounds act as developing agents for silver halides and as a dye. The dye developing agent does not substantially diffuse into a colloid layer than hydrophilic organic colloid of the photographic emulsion at a neutral hydrogen ion concentration, but rather can diffuse into such an emulsion layer in the presence of an alkaline treating solution. The in Dye developing agents useful in the present invention are disclosed in Australian Patent Specification 220,279, US Pat German patent specification 1 036 640, British patents 804 971, 804 973 and 804 975, the Belgian Patent 554,935, French Patent 1,168,292 and 1,313,765, Canadian Patent 577 021 and 579 038 and U.S. Patents 3,320,063, 3 255 001, 2 992 106, 3 297 441, 3 134 762, 3 236 643,

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3 134 763, 3 236 645, 3 134 764, 3 134 672, 3 134 765, 3 183 089, 3 135 734, 3 135 604, 3 173 906, 3 222 169, 3 183 090, 3 201 384, 3 246 985, 3 208 991, 3 142 565, 3 218 312, 3 230 086, 3 262 924, 3 275 617, 3 077 402, 3 282 913, 3 141 772, 3 299 041, 3 309 199, 2 983 605, 3 047 386, 3 076 820, 3 173 929, 3 239 083, 3 236 864, 3 239 339, 3 252 969, 3 253 001, 3 288 778, 3 209 016, 3 135 606, 3 076 808, 3 126 280, 3 236 865, 3 135 605, 3 255 205, 3 131 061, 3 347 673, 3 347 672, 3 246 016, 3 245 790, 3 086 005, 3 295 973, 3 307 947, 3 230 082, 3 230 085, 3 019 107, 3 019 254, 3 022 354, 3 256 269, 3,230,084, 3,232,995, 3,236,873 and 3,252,990.

The dye developing agents generally contain a color component and at least one developing group for the silver halide in the molecule. The term "developing group for silver halide" means one suitable for developing the silver halide
Group. A preferred developing group for the silver halide is a hydroquinonyl group. The developing group can also consist of an o-dihydroxyphenyl group, an o- or p-amino-substituted hydroxyphenyl group. In general, the developing group contains a benzoloid type developing group, that is, an aromatic group which upon oxidation forms a quinonoid group, that is, a quinone material. The dye unit of typical dye developing agents among the various dye developing agents
consists of an azo dye unit or an anthraquinone dye unit or group. In the context of the present description, a dye developing agent containing an azo dye unit is used as an "azo dye developing agent" and an anthraquinone dye unit

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Paraffin developing agent containing the entity as "anthraquinone dye developing agent" designated.

The azo dye developing agents are well known or anthraquinone dye developing agents, the typical ones Illustrate examples of paraffin developing agents according to the invention for reducing sensitivity of the silver halide photographic emulsion when contained in the emulsion. This effect of the. Paraffin developing agent is particularly noticeable in spectrally sensitized photographic silver halide emulsions, even if the absorption of light by the pigment developing agent is neglected.

This reduction in sensitivity caused by the paraffin developing agent is not only observed, if the colorant developing agent is directly in the silver halide emulsion, its red-sensitive area spectrally sensitized, but also when the paraffin developing agent is incorporated into the red-sensitive Silver halide emulsion is indirectly incorporated or a layer containing the paraffin developing agent in contact with the red-sensitive silver halide emulsion layer is brought. This is believed to be due to the diffusion of some of the paraffin developing agent from the developing agent containing layer into the photosensitive emulsion layer.

An object of the invention is a red-sensitive emulsion layer for photographic photosensitive ones Silver halide materials for diffusion transfer process, which require a pigment developing agent, the photosensitive emulsion layer being one has high red sensitivity in the presence of the colorant developing agent.

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The foregoing and other objects of the invention are accomplished with a red sensitized silver halide emulsion by a combination of at least one sensitizing dye according to the following general formula I and at least one sensitizing dye corresponding to the following general formula II achieved:

R ₁ - N - C = CH - C = CH - 6 = N ₊ - R ₂ CO _n-11 D

wherein Z is a non-metal atom grouping necessary to complete a naphthothiazole ring or naphthoselenazole ring, wherein the naphthalene ring of each of these rings can optionally be substituted, Z * one for forming a naphthothiazole ring, a benzothiazole ring, a naphthoselenazole ring or a benzoselenazole ring, where each benzoselenazole ring is not necessary, this ring being optionally substituted by the benzoselenazole ring R can be a hydrogen atom, a lower alkyl group or an aryl group, R ₁ and R ₂ an alkyl group such as a methyl group, \ thylgruppe or n-propyl group, or a substituted alkyl group such as a ß-acetoxyethyl group, a γ-acetoxypropyl group or a hydroxyalkyl group such as a β-hydroxyethyl group, -hydroxybutyl group, an alkyl group substituted with a carboxyl group such as a carboxymethyl group, ß-carboxyethyl group, γ-carboxypropyl group, 2- (2-carboxyethoxy) ethyl group and the like, one with a sulfo group substituted alkyl group, for example a β-sulfoethyl group, a γ-sulfopropy group, a γ-buty group, a cf-sulfopropyl group, a 2-hydroxy-1-sulfopropyl group, a 2- (3-sulfopropoxy) -äthylgruppe, 2-acetoxy-i-sulfopropyl group, a 3-methoxy-2- (3-sulfopropoxy) propyl group, a group 2- / 2- (3-sulfopropoxy) -äthoxyäthy% J, a

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- b -

2-Hydroxy-3- (3 ^l -sulfopropoxy) -propyl group and the like and similar radicals, where at least one of the radicals R ₁ or R _{2 represents} an alkyl group substituted by a hydroxyalkyl group or a carboxyl group or an alkyl group substituted by a sulfo group , X is an anion and η is the number 1 or 2, where η has the value 1 if the dye of the general formula I is an intramolecular salt,

R, - fr - C = CH - C = CH - C = N, - Rc (O _n . A ¹ ^ 4 + 5 ^xy m-1

in which Z ₂ and Z, which can be the same or different, represent the non-metal atom grouping necessary for the formation of a benzothiazole ring or a benzoselene ring, the benzene ring of each of these rings being optionally substituted, R is a hydrogen atom, a lower alkyl group or a Aryl group, R, and Rc have the same meaning as R and R ₂ in the general formula I, where at least one of the radicals R 1 and R 1 represents an alkyl group substituted by a hydroxyalkyl group or a carboxy group or an alkyl group substituted by a sulfo group , X is an anion and m is a number 1 or 2, m being 1 if the dye of the general formula II is an intramolecular salt.

Examples of naphtothiazole rings and naphthoselenazole rings corresponding to Z of the general formula I include a-naphthothiazole, ß-naphthothiazole, ß, ß-naphthothiazole, α-naphthoselenazole, ß-naphthoselenazole and ß, ß-naphthoselenazole.

Examples of naphthothiazole rings, benzothiazole rings, naphthoselenazole rings and benzoselenazole rings corresponding to % _A in general formula I include a-naphthothiazole,

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ß-naphthothiazole, ß, ß-uaphthothiazole, benzothiazole, 5-methylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-bromobenzothiazole, 5> 6-dimethylbenzothiazole, 5-cyanobenzothiazole, 5-phenyrbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-hydroxybenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-carboxybenzothiazole, a-naphthoselenazole, ß-uaphthoselenazole, β, β-naphthoselenazole, Benzoselenazole, 5-Methylbeazoselenazole, 5-Cblorbenzo-selenazole, 5-methoxybenzoselenazole, 5-hienylbenzoselenazole, 5,6-dimetb.ylbenzoselenazole. And 5-hydroxybenzoselenazole. . .

Examples of lower alky! Groups and ary! Groups corresponding to R and IW include methyl groups, ethyl groups, n-Propy! groups, phenyl groups, p-methoxyphenyl groups, o-carboxyphenylmethoxyphenyl groups and the like Groups.

Examples of X are chloride ions, bromide ions, iodide ions, perchlorate ions, p-toluenesulfonate ions, and ethyl sulfate ions.

Under "lower alkyl groups" in the general Formulas understood an alkyl group with 1 to 4 · carbon atoms.

The sensitizing dyes used in the context of the invention are known dyes and are, for example, in U.S. Patents 2,503,776, 3,459,553 and 3,177,210, British patents 1,128,840 and 1,137,084, German patents 1,020,037 and 1,811,542 and the French patent 1,573,694 indicated. The sensitizing dyes used in the context of the invention can thus easily in accordance with the information in the above literatures can be prepared and other dyes as described in the above references being represented.

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Examples of sensitizing dyes corresponding to the general formula I which can be used according to the invention are given below, although the sensitizing dyes which can be used in the present invention are corresponding of the general formula I are not limited to this.

/ -CH-O-OH -

(OH ₁ ), SO, ~

OHi

- ι

.1

C ₁ H.

OH-O-OH-:

S ο

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O, H,

-OH-O-OH-:

S β

-Oh-:

(OH,) ι SO ₁ H

> -0Η - 0-0 H

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./-oh- ο-οη- _χ

Examples of sensitizing dyes in the context of Invention corresponding to the general formula II are given below, although those which can be used according to the invention Sensitizing dyes II are not limited to this.

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Η, α

ΙΙ-2 ΙΙ-3

O, H,.

CH-O - GH

GH »

CH ₂ GH ₂ GOOH GH ₂ OH ₂ 000 "

Oh T

-O -OH-

H, 0

O ₁ H ₉

GH-C-OH

So

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II-4

II-5 OH,

- OH— 0 - OH-

(OH ₁ K SO, H

SO,'

OH -

J ₃ SO, H OH,

I. 0 -

OH -

(OH ₁ ), SO, """

II-6

η, σ

• θ OH - O ₈ ■ Η, \ S ο
'+' \
/ ■ " - ί
C. - OH N - I.

II-7 OH-O - CH - <

(OH ₁ CK ₁ O) _x (OH,), S0, H ■ (OH, 0H, O) ₁ (OH,). 30Γ

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II-8

II-9

H,

11-10

GH ₂ OH, OH

O ₁ H ₈

~ 0H

JST

OH ₃ OH ₂ OH

Br

OH,

C ₂ H,

- O - 0 H -

(OHj) ₅ SO ₃ H

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-u-

When using the color developing agents specified above The color image-forming components can be monochromatic images or multichromatic images according to the various in the diffusion transfer process known processes are formed.

Will transmit according to a method for achieving color transfer images by using color development ¹ · at least two light-sensitive Belektiv sensitized emulsion layers formed on a support and the photosensitive material is treated with an image-receiving layer at the same time state in close contact ^.

Pig. 1 of the. accompanying drawing shows an off «? implementation of the process for the formation of a monochromatic Transmission image. A photosensitive element consists of a support A, one of which forms the color image Component containing layer B and a SiI-. Berhalide emulsion layer C built up. A breakable one Cell F, which contains an alkaline treatment compound, is applied to the photosensitive element in type brought that the alkaline processing composition is isolated from the photosensitive element. The image pickup element, is composed of a substrate E and an image receiving layer D. After the photosensitive element has been subjected to light exposure, the image pickup element becomes brought closely to the photosensitive layer, with the cell F inserted between these layers, and then the cell F is subjected to a suitable pressure, for example by pushing the layered elements through a Pair of notched rollers (not shown) are guided, broken, causing the liquid treatment composition in the process broken cell is spread as a layer between the two stacked elements. the

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Treatment mass is in the silver halide emulsion layer G diffuses to develop the latent image formed in this layer. The one in the shift B contained, the colored image-forming constituents are from the unexposed areas of the layer B in the Transferred the image receiving layer D of the image receiving element and 'result in a positive color image in the Light exposure. After at least part of the. the color image forming component on the image pickup element is transferred, the latter is separated from the photosensitive member.

The silver halide emulsion discussed above layer is, for example, made of a blue-sensitive SiI overhalide emulsion layer and a red-sensitive silicon halide emulsion layer formed on a support and the emulsion layers contain a magenta dye developing agent bsw. a cyan dye developing agent. The dye developing agent can be incorporated into the silver halide emulsion layer in the form of grains or may be incorporated in an adjacent to the silver halide emulsion layer Layer be incorporated. The silver halide emulsion layer containing the dye developing agent or a combination of a silver halide emulsion layer and an adjacent one containing the dye developing agent Layer are from the other, the further dye developing agent containing silver halide emulsion layer or the other combination of silver halide emulsion ~ layer and that containing the other dye developing agent adjacent layer by a suitable intermediate. layer, for example a gelatin or polyvinyl alcohol layer, separated.

Another type of natural color photographic light-sensitive material is made of a support with

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a red-sensitive silver halide emulsion layer; a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer and containing the emulsion layers a cyan dye developing agent, a magenta dye developing agent or a yellow dye developing agent. The manner in which the dye developing agents are incorporated in the color photographic material that is same as above ..

In other methods to achieve a multicolored Image are several image recording elements or sheets which are suitable for treatment with more than one liquid treatment mass and suitable color developing agents are contained in the photosensitive elements. A system of this type is shown, for example, in U.S. Patent 2,647 049.

In other methods of obtaining multicolor images, the photosensitive silver halide emulsion layer contains at least two kinds of fine photosensitive grains each selectively sensitized and are arranged in the form of a photosensitive grid. In precise terms, every photosensitive grain is from a silver halide emulsion containing a suitable dye developing agent. For example in the photosensitive screen are fine grains of a blue sensitized emulsion and fine grains of one red-sensitized emulsion alternating in a grid pattern arranged and contain a magenta dye developing agent and a cyan dye developing agent, respectively. One for color photography using the subtractive color method suitable photosensitive grid has a grid pattern of fine grains of a red-sensitive Emulsion, fine grains of a green sensitive emulsion

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and fine grains of a blue-sensitive emulsion which each a color developing agent for the formation of the cyan image, a color developing agent for the formation of the Magenta image or a color developing agent to form the yellow image. Transmission method of this Art are shown in U.S. Patents 2,968,554 and 2,983,606.

In the red-sensitive emulsions used according to the invention, a color developing agent for cyan formation, a color developing agent for forming magenta and a color developing agent for forming yellow are used, however can also use other dye color developing agents, such as black color developing agents and mixtures of the color developing agents listed above will.

The dye developing agents used in the context of the invention are incorporated into the silver halide photographic emulsion or one to the silver halide emulsion layer adjacent emulsion layer incorporated. This slide containing the dye developing agent, can be achieved by applying a coating mass of approx 0.5 to 8% by weight of the dye developing agent, dispersed in a colloidal binder such as gelatin or dissolved in a polyamide binder such as cellulose hydroacetate phthalate, are formed.

The alkaline treatment mass used in the context of the invention consists of an aqueous solution which contains at least one alkaline compound such as diethylamine, sodium hydroxide, potassium hydroxide or sodium carbonate. If the alkaline treatment is mass as a uniform layer on the emulsion layer of the element ^{-lichtempfindlichen-:} wishes to apply by spreading the Behandlungsmasöe "[, the above-mentioned alkaline BeUandiungsmassßi a viscosity improver of a film forming ma-

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terials, which after spreading the mass over the emulsion layer and drying a relatively forms hard and relatively stable PiIm, contain. The preferred film-forming materials as viscosity improvers are high molecular weight polymers, such as water-soluble, versus the alkali solution inactive polymer ethers, for example Hydroxyäthylr cellulose or sodium carboxymethyl cellulose. Other film-forming materials, their suitability for increasing viscosity is practically not affected when placed in an aqueous solution for a long period of time can also be used. Furthermore, alkaline treatment masses which e | n Contain pickling agents, can be used according to the invention. Examples of such Massei are in the Japanese Cited in patent publication 6449/1963. Suitable examples of alkaline treatment compositions are given in given the following examples of the invention. Sometimes it is beneficial, under certain circumstances, apply the alkaline treatment composition to the photosensitive member prior to exposure according to the method described in in U.S. Patent 5,087,816 to apply methods. '

The alkaline used in the context of the invention Treatment masks can continue to use development aids, for example development accelerators such as p-amino- ' phenol, 2,4-disminophenol, p-benzylaminiphenol, hydrochi- non, toluhydroohinone, 'phenylhydroquinone and 4'-methylphenyl hydroquinone contain. As indicated in US Pat. No. 3,039,869, a combination of several Development accelerator such as a 3-pyrazolidone developer and a benzoid developer can be applied. Examples of combinations of the development promoters include Combinations of 1-phenyl "3" pyra2iolidön and p-bensyl-

2 C S 8 3 0/1 G Q 3

aminoplienyl and of 1-phenyl-3-pyrazolidone and 2,5-bisethylaminohydroquinone. These development promoters are usually incorporated into the alkaline "treatment mass, ; however, at least one of these can also previously be in the Silberha.logenidemulsionsschicht or an adjacent layer containing the dye developing agent contains, be incorporated. In the system exposed to pigment developing agent development promoter The silver halide undergoes an oxidation-reduction reaction repeatedly and the development promoter acts as a "catalyst" in this reaction.

The azoene that can be used in the context of the invention Winding means are known connections and are disclosed, for example, in US Pat. No. 3,134,672. Examples for azo developing agents which can be used in the context of the invention are the following compounds j

1) 1-phenyl-3-n-carbobutoxy-4- / p- (2 ^! "» 5'-dihydroxyphenethyl) -phenylazo7-5-pyrazolone,

2) 1-phenyl-3- (F-2'-ethylhexylcarbamido) -4 ~ Zp ~ (2 ', 5'-dihydroxyphenethyl) -phenylazo7-5-pyrazolone,

3) 2- (p-H, lif-diethylsulfonamidophenyl) -3 ~ N-n-butylcarbainidO'-4- / p- (2 ', 5'-dihydroxyphenethyl) -phenylazo7 "-5-pyrazolone,

4) 1-phenyl-3-N ~ n-hexylcarbamido-4 ⁱ -ZP ~ (2 ', 5'-dihydroxyphenylpropy1) -phenylazq7-5 ~ pyrazolone,

5) 1-phenyl ~ 3-trifluoromethyl-4-Z] p ¹ ~ (2 ', 5' -dihydroxyphenylisobutyl) -phenylazo7-5-pyrazolone,

6) 1-phenyl-3-li-ß-tiyaroxyätliylcarbamido - 4- _i 5 - ("2 ', 5' -dihydroxyphenätliyl) -phenylazo_7-5 '" pyrazolon,

7) 1-phenyl-3 ~ li-n-hexylcarbamido-4- / p- (2 ', 5' ~ dihydroxy-4'-. methylphenäthyl) -phenylazo7-5-pyrazolone,

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8) 1-Phenyl-3-ÜT-n-hexylcarbamido-4-Zp- (2 ', 5'-dihydroxyphenethyl) -phenylazo_7-5-pyrazolone,

9) 1-phenyl-3-N-n-heptylcarbainido-4- / p- (2 ', 5'-dihydroxyphenethyl ) -pheny la zo7-5-pyrazolon,

10) 1-Phenyl-3-N-n-hexylcarbamido-4-Zp- (2 ', 5'-dihydroxy-4'-chlorophenethyl) -pheny lazo_7-5-pyrazolon,

11) 1-Phenyl-3-trifluonnethyl-4-Zp- (2 ', 5 ' -dihydroxyphenethyl) -pheny la zo_7-5-pyrazolon,

12) 1-phenyl-3-phenyl-4- / p- (2 ', 5'-dihydroxyphenethyl) -pheny1-azo7-5-pyrazolone,

13) 1-Phenyl ~ 3-N "-cyclohexylcarbamido-4-Zp- (2 ', 5'-dihydroxyphenethyl ) -pheny la zo_7-5-pyrazolon,

14) 1- Phenyl-3-N-n-butyl-carbamido-4- / p- (2 ', 5'-dihydroxyphenethyl) ~ phen3rlazp_7-5-pyrazolone of the following formula:

CH ₂ -CH ₂ - <^ Vn = C- -C -NH-C ₄ H ₉

/ \ ^ N ^. HO N OH

15) 1-phenyl ~ 3-carbethoxy-4- / p- (2 ^!, 5'-dihydroxyphenethyl) -phenylazo_7-5-pyrazolone ₉

16) 1 ~ phenyl-3-methyl-4- / p- (2 ^l , 5'-dihydroxyphenethyl) -phenylazo7-5-pyrazolone

17) 1 - Pheny l-3-arnino-4-Zp- (2 ', 5' -dihydr oxyphen'i. Thy 1) -pheny 1-azo7-5-pyrazolon,

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18) 2- / p- (2 ^f , 5 '-dihydroxyphenethyl) -o-ynethylphenylazo7-4-methoxy-1-naphthol,

19) 2- / 5- ( ² '>5'-Dihydroxyphenäthyl)-phenylazo7-4-iso'butoxy-1-naphthol,

20) 2- / p- (2 », 5'-I) ihydroxyphenäthyl) -phenylazoJ-4 - N-methyl-If-phenylsulfonamido-1-naphthol,

21) 2- / p- (2 ', S'-DihydroxyphenäthylJ-phenylazoy- ^ iDethylsulf on-1-naphthol,

22) 2- ^ m- (2, 5'-dihydroxyphenethyl) ~ phenylazo7-4-n-propoxy-1-naphthol,

23) 2- / p- (2 ', 5'-dihydroxyphenethyl) -phenylazo_7-4-ethoxyethoxyethoxy-1-naphthol,

24) 2- / p- (2, 5'-dihydroxyphenethyl) -phenylazq7-4-methylsulfide-1-naphthol,

25) 2-Zp- (2.5 ^l -dihydroxyphenethyl) -phenylazo7-4-ß-chloroethoxy 1-naphthol,

26) 2- / p '- (2', 5 ^l -dihydroxyphenethyl) ~ a ~ naphthylazo7 ~ 4-methoxy - 1-naphthol, ffC

27) 2- / p- (2 ', 5' '-dihydroxyphenylisohutyl) -phenylazo7-4-methoxy - 1-naphthol,

28) 2- / p- (2 ', 5'-dihydroxyphenylpropyl) -phenylazo7-4-i3opropoxy 1-naphthol,, ■ - "■.

29) 2- / p- (2, 5'-dihydroxyphenylpropyl) -phenylazOLZH-n-propoxy-1-naphthol, '-

30) 2- / p- (2, 5'-dihydroxy-4'-methylphenethyl) -phenylazg7-4-N, TT-diethyl3ulfonamido-1-naphthol,

31) 2- / p- (2 ' _f 5'-dihydroxy-3 ♦, 4'-dimethylphenäthyl ^ phenylazoj-4-methoxy-1-naphthol,

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32) 2- / p- (2 ', 5'-Mhydroxyphenethyl) -phenylazq7-4 ~ acetyl ~ 1-naphthol,

33) 2- / p- (2 ', 5'-dihydroxy-4' -methylphenäthylj-phenylazo / -4-methoxy1-1-naphthol,

34) 2- / p- (2 ', 5 ^l -dihydroxy-4 ^l ~ methylphenethyl) -phenylazo7-4-n-propoxy-1-naphthol,

35) 2- / p- (2 ·, 5'-dihydroxyphenethyl) -phenylazo7-4-β-hydroxy ~ ethoxy ™ 1-naphthol,

36) 2-Zp- (2 ', 5l-dihydroxy-3 ^t , 4', ö'-trimethylphenethyl) -phenylazo7 ~ 4-niethoxy-1-naphthol,

37) 2- / p ~ (2 ', 5'-dihydroxy-3'-roethylphenäthyl) -ph enj lag qj- 4-n-propoxy-1-naphthol,

38) 2- / p-3 ', 4' -dihydroxyphenethyl) ~ phenyiazo_7-4-n-propox5 '- 1-naphthol,

39) 2- / p- (2 ', 5' ~ Mhydroxyphenethyl) -o ~ i) iethoxyphenylazq7-4 ~ N, N-dimethylsulfonamido-i-naphthol,

40) 2- / jp- (2 ', 5'-dihydroxyphenethyl) -phenylazo7-4-hexyloxy - 1-naphthol,

41) 2- / p- ( ^{2.5 t} -dihydroxyphenethyl) -phenylazo7-4-cyclohexyl-1-naphthol,

42) 2 ~ / p- (2 '^' - Dihydroxyphenäthyl ^ phenylazoJ ^ -isopropoxy-1-naphthol,

43) 2 ~ / p- (2 ', 5'-dihydroxyphenethyl) -phenylazo7-4-n-propoxy-1-naphthol,

44) 2- / p- (2 ', 5 ^l -dihydroxyphenethyl) -phenylazo7-4 ~ ethoxy-1-naphthol,

45) 2-Zp- (2.5 ^tl -dihydroxyphenethyl) -phenylazo7-4-raethoxy-1 naphthol,

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■ t

46) 2- / p- (2 ^! F 5 '- "Dihydroxyphenätbyl) -plienylazo74-acetamicLo-1-naphthol,

47) 2-Zp-Ca ¹ , 5 ^r ~ I> ihydroxyphenäthyl) -phenylazo7-4-ainino-1-naphthol,

.48) 2 ~ / p- (2 ^!, 5'-Dihydroxyphenäthyl) -pTienylazq7 "4-sulfo-1-naphthol,

49) 5-Ainino-8- / p- (2 ', 5'-di-hydroxyphenethyl) -phenylazg7 ~ 1 ~ napbtliol,

50) 5-ß-Hydroxyäfhylamino-8 ~ / p- (2 ^t , 5 ^! -Dibydroxyphenätliyl) -pheiiy la ζο / -1 -naphthol,

51) 4-Zp - (^ ¹ , 5 ^! -Dihydroxyphenethyl) ~ plienylazo7-5 ~ acetane] ido-1-naphthol,

52) 1-Z5 ~ (2 *, 5'-dihydroxyphenethyl) ~ o-raethoxy ~ phenylazg7 ~ 8-acetam3, do-2 ~ naphthol,

53) 1-Zp- (2 ', 5'-Dihydroxyphenäthy1) -phenyla so7 ~ 2-naphthol,

54) 4-Zp ~ (2 ', 5'-dihydroxyphenethyl) -phenylazo7-1-N-ethylaminonaphthol,

55) 4 ~ Zp ~ (2 '»5'-dihydroxyphenethyl) -phenylazq7 ~ 1-naphthylamine,

56) 4- / p- (2 », 5'-Dihydroxypheiiäthyl) -phenylazQ_7-5-hydroxyacenaphthen,

57) 8-Amino-5- / p ~ (2 ', 5 ^r -dihydroxyphenethyl) -phenylazo7-quinoline

58) 2,5-Dimethoxy ~ 4-Zp- (2 '»5'-dihydroxyphenethyl) -phenylazq7-aniline, '

59) 2-Pormyl-4-Zp- (2 ', 5'-dihydroxyphenethyl) -phenylazo_7-plienol _> .

'60) 4-Zp ~ (2 ^f , 5 ^l ~ dihydroxyphenethyl) ~ phenylazo7-3 "-phenyl-isoxa - 1οη-5 ·

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The anthraquinone dye developing agents in the framework Men of the invention are known compounds and, for example, in US Patents 2,983,605 and 2,983,606. Illustrative examples are The following: "

61) 1,4-bis- (p - /! I- (hydroquinonylcarbaiaylmethyl) -amine7- ' phenylamino) anthraquinone,

62) 1,4-bis-hydroquinonylearbamylmethylamino ~ anthraquinone,

63) liv ^ -Bis-Ca-methyl-ß-hydroohinonyläthylaruino) - anthraquinone,

64) 1,4-bis- (a-methyl-ß ~ hydroehinonyl-ethylainino) -5,8 ~ dihydroxy-anthraquinone,

65) 1,4-bis (a-methyl-ß-hydroquinonylpropylaiiiino) ~ 5,8-aihydroxy-anthraquinone,

66) 1,4-bis- (a-methyl-ß-hydroquinonylpropylainino) -anthraquinone,

6?) 1,4-bis ~ hydroehinonylmethylamino-anthraehinone,

68) 1,4-bis (tt-niethyl-ß-hydroquinonylethylainino) ~ 6, 7-dichloro anthraquinone,

69) 1,4-bis ~ (a ~ methyl-2 ^T , 5'-dihydroxybenzylamino) ~ anthraquinone,

70) 1, ^ - BiS'-fa-methyl-ß-hydroquinonylethylainino) -5 ₅ 8 ~ bis sulfoncmidoanthraquinone,

71) 1,4-bis (α-ynethyl-B-hydroquinoylethylamino) -5 "-hydroxy-8 amino-anth3? a quinone »

72) 1,4-bis (ß-hydroquinonylethylamino) anthraquinone,

73) 1,4-bis-Z3- (3 ', 4' »dihydroxypheny1)» ethylamino7-5,8-di ™ hydroxyphenyl) ethylamino-dili3'-drox3ranthra quinone j

209830/1003 BAD ORlGlMAL

74) 1,4-Bie-ZS- (3 ^I , 5 ^f -dihydroxyphenyl) -äthylamino7-anthraquinone,

75) 1 ^ -Bis-ia-ethyl-ß-hydroquinonylethylamino) anthraquinone,

76) 1,4-bis (2 ', 5'-dihydroxyanilino) anthraquinone,

77) 1,4-bis-ß- (homogentisamido) ~ ethylainino-anthraquinone,

78) 1,4-bis-homogentisamido-anthraquinone,

79) 1,4-bis (2 ', 5'-dihydroxyanilino) anthraquinone,

80) 1,4-bis- / ß- (2 ', 5'-dihydroxyphenyl) -propylaiain ^ -anthraquinone,

81) 1,4-Bis-Zi ', 5'-bis- (2 », 5» -dihydroxypheny1) -3'-penty 3J-aminoanthra ehinon,

82) N-monobenzoyl-1,4-bis- / ß- (3 ', 4'-dihydroxyphenyl) ~ ethylaminoj-anthraquinone,

83) IT-monobenzoyl-1,4 ~ bis / ß- (2 ·, 5'-dihydroxyphenyl) ™ ethylamino7-anthraehinone,

84) 1,4-Dian] ino "; iT-ß-2 '^' - dihydroxyph ^ yl-a-methyl-ethyl) -2,3-anthrachi / ion-dicarboxamide,

85) 1-Amino-4-hydroxy-ir-ß-2 ', 5 ' -dihydroxypheny1-a-methylethyl) -2,3-anthraquinone-dicarboxamide,

86) 1-Hydroxy-4-Zi ^l »5 ^t -bis- (2", 5 "-dihydroxyphenyl) -3" -pentyl7-amino-anthraehinone,

87) 1-Amino-4-anilino-2-hydroquinonylsulfamylanthrac; hinon

88) 1-aminoethylamino-4-hydroquinonylcarbaniylniethy laroinoäthylamino-anthraquinone,

89) Sodium 1 "amino-4- / p- (N-hydroquinonylcarbamyliDethylainino) -phenylamino7-2-anthraquinone sulfonate,

90) 1- (a-HydroxyiDethylpropylaiDino) ~ 4 ~ (ot-niethyl-ß-hydroquinonylethylamino) -anthraquinone,

91) 1- (a-Hydroxymethyl-propylamino) -4 ~ (<methyl-ß-hydroquinonyl-methylamino) -5,8-dihydroxyanthraquinone,

92) 1-Hydroxy-4 ~ (2 ', 5' ~ dihydroxyanilino) -anthracbinone,

93) 1 ~ hydroxy-4- (ct-methyl-hydroquinonylethylamino) -antbrachinon,

94) i-Ca-methyl-ß-hydroquinonylethylamino) -4- (α-ethyl ~ ßhydroquinonylethylamino) anthra chinone,

95) 1 - (ä-Methy1-ß-hydroquinony läthy lamino) -4- (a ~ äthy 1-ßhydroquinonyläthylamino) ~ 5,8-dihydroxyanthraquinone,

96) 1- (a-Hydroxymethyl-propylamino) -4 ~ ( ot-me thy1-ß-hydroquinonylethylamino) -5-hydroxyanthraquinone,

97) 1 ~ (a-Hydroxymethylpropylamino) -4-Zß- (4'-methyl-2 ', 5'-dihydroxyphenyl) -a-n] ethy1-ethylamino) 7-anthraquinone,

98) 1-ethylamino-4 ~ Zß ~ (3 '»4'-dihydroxyphenyl) -äthylamino7-anthraquinone,

99) 1-chloro-4- (ß-hydroquinonylethylamino) anthraquinone,

100) 1 ~ Hydroxy-4-Zß- (3 ', 4 ^l -dihydroxyphenyl) ~ äthylami.no_7 · - anthraquinone,

101) 1- (ß-Hydroxyäthylamino) -4- (ß-hydroquinonyläthylainino) -anthraquinone, '

102) 1- (ß-Hydroxyäthylamino) -4 - (<x-methy1-ß-hydroquinony1-äthylamino) -5 »8-dihydroxyanthraohinon,

103) 1-methylamino-4- (ß-aydroquinonylethylaraino) -anthraquinone,

104) 1-ß-Hydroxyäthy lamino-4- (a-me thy 1-ß-hydroquinony 1-äthy 1-amino) -anthraquinone,

105) 1-ß-Aminoäthylamino-4-ß- (homogentisamido) -äthylaminoanthraohinon,

106) 1,5-bis ~ hydroquinonylmethylainino - anthra quinone,

107) 1,5-Bls- / B- (3 *, 4'-dihydroxyphenyl ^ äthylaminoT-anthraquinone,

108) 1,5-bis ~ (ß-bydroquinonylethylamino) anthraquinone,

109) 1, S-Bis-Ca-methyl-ß-hydroehinonyl-ethylamino) -anthraquinone,

110). 1,5-bis-hoinogentisamido ~ 4, 8-dihydroxy-anthraquinone,

111) 1, S-bis-homogentiaamido-anthraquinone,

112) 1,5-bis (IT-methyl-hoinogentisaiiiido) -55 8 »dimetbylamino-anthraquinone,

113) 1-Cblor ~ 5 ~ (ß-bydrocbinonylätbylam.tno) -antbrachinon,

114) 1 - / ß "{ 3 ^r j 4'-Dibydroxypbeny1) -ätbyIamino7 ~ antbraclinon.

115) 1 »8-bis- ^ ß- (3 ', 4'-dibydroxypbenyl) -äthylamino7-antlaracbinon,

116) 1,8-bis ~ (β-bydrocbinonylätbylaniino) -antbracbinoii, ■

117) 4, .8-bis- (2 ^f _J 5 ^t -dihydroxyanilino) -antbracbinon,

118) 4- (2 ', 5 ^t -dibydroxyanilino) ~ 8 ~ cblor - antbi: acbinon,

119) 1- / p- (ß-Hydroquinonylethyl) -phenylamino7-anthrac> iinon,

120) 1- / ß- (3 ', 4 * -dibydroxypbenyl) -ä-fchyIamino7-anthracbinon,

121) 1-Homogeneously isainido ~ 5 ~ amino-4 ₅ 8-diby dr oxyantbra cbinon.

It is "known" that the sensitizing dyes used in the context of the invention can be used for the spectral sensitization of conventional halide emulsions. Also, the application ¹ dei useful in EaIl of sensitizing dyes are Anthraehinonfarbstoffentwicklungsmitteln / specified in the Japanese Patent Publication 392 '1965th

209830/1003 BAD ORIGINAL

The sensitizing dyes disclosed in the above Japanese Patent Publication have a carboxyalkyl group or SuIfoalky! group, whereby the employed Alkylene chain is an n-alkylene chain, and if a Anthraquinone dye developing agent is used the sensitizing dye according to the patent shows higher sensitization suitability than a sensitizing dye having an alkyl group, but becomes sufficient Sensitivity without using a very large amount of the sensitizing dye based on silver halide, not achieved, this being due to one due to the presence of the paraffin developing agent Disensitizing effect can be caused. Palis, however, utilizes multilayer color photographic materials a large amount of the sensitizing dye it are produced, there is a problem that the sensitizing dye in the red-sensitive emulsion layer of the color photographic material into the other photosensitive Silver halide layers, for example blue-sensitive light-sensitive emulsion layers or green-sensitive light-sensitive emulsion layers diffused and these layers spectrally eensitized. In particular, diffuse alkyl-containing sensitizing dyes having a carboxyl group or sulfo group easily and show a tendency to spectral sensitization of other silver halide emulsion layers.

On the other hand, it was surprisingly found that when using the combination of sensitizing dyes according to the invention, a red-sensitive emulsion layer having a high sensitivity is obtained and the sensitization of the other emulsion layers is remarkably reduced.

209830/1003

Moreover, it is from the Japanese patent publication 4933/1968 and the German patent specification 1 929 037 known that the combination, which in the Sensitizing dyes used in the context of the invention produces good results in a system that contains a color coupler dispersion, however, it was found within the scope of the invention that if the combination the sensitizing dyes in a system containing the dye developing agent according to the invention is used, the effect of combining the sensitizing dyes is unexpectedly higher than that of the case its application in a coupler dispersion system.

In the case of using a combination of sensitizing dyes and dye developing agents, the sensitivity of the red sensitive emulsion, usually considerably due to the merging of the sensitizing dyes and the dye developing agent is reduced, the theoretical reason for these phenomena has not yet been clarified, but this reduction in Sensitivity may be due to the leather sensitizing effect due to the dye developing agent, however, when the combination of the specific sensitizing dyes according to the invention is used, the above can be reduced and a photographic emulsion having high red sensitivity is obtained.

The use ratio of the sensitizing dyes. of the general formula I to the sensitizing dyes of the general formula II is not particularly limited but preferably 9: 1 to 1: 9. The ratio can vary according to the purpose of the application and the combination will. - "- ~

The sensitizing dyes according to the invention can to the photographic emulsion according to any known one

Process in the field of photographic manufacture Emulsions are added. Usually the sensitizing dye can be used in photographic Emulsion incorporated as a solution in a solvent such as water / water, methanol, ethanol or methyl cellosolve will. In this pail, ultrasonic waves can be applied to the system to help dissolve the sensitizing dye improve it in the solvent. The amount of sensitizing dye used can can be varied according to the properties of the silver halide emulsion and the results desired. In general the optimum amount of sensitizing dyes for best sensitivity is in the range of 0.005 to 0.3 g per gram mole of silver halide.

Purely the silver halide emulsions which can be used in the context of the invention can silver halides such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide can be used, however, the Application of silver iodobromide particularly effective.

In the context of the description of the present invention an ordinary gelatin-silver halide emulsion is used, however, some or all of the gelatin may be due to a resinous material or a cellulose derivative which does not have bad influences on the photosensitive material.

The "photographic emulsions" used in the invention may contain ordinary additives such as chemical additives. Sensitizers, anti-fogging agents, stabilizers, Hardeners, wetting agents, plasticizing agents promoters, air mist prevention agents, and the like, and they are applied to suitable supports, such as glass plates, cellulose derivative films, plastic resin films, synthetic papers, barite-coated papers and

20983071003

applied polyolefin coated papers.

The image pickup element used in the context of the invention is composed of a support and an image receiving layer with alkali permeability and is used for dyeing suitable with the dye developing agent in alkaline solution. That is, the image pickup element is made of a carrier with a coating thereon of at least one image-receiving layer which is permeable to alkali and can be colored. The image-receiving layer may contain or contain a chemical suitable for etching has a mechanism for fixing the color developing agent that has not been oxidized. The materials for the image receiving layer and the structure of the image receiving layer are in Japanese Patent Nos. 8274/1963, 8449/1963, and 29,756/1961, and U.S. Patents 3 003 872., 3 043 689, 3 065 074, 3 148 061, 3 239 337, 3 353 056 and 3 362 819.

In some cases the dyeable layer consists of an alkaline treatment mass that is left on the support in the case of the separation of the photosensitive material is suitable.

The carrier for the image pickup element consists of a gate from a synthetic paper, a barjrt-coated paper, a polyolefin-coated paper, however Other supports, for example G-Ia splat th, cellulose derivative films can also be used or synthetic resin films can be used.

The following examples serve to further illustrate the invention without limiting it.

5 g of the cyan dye developing agent 5,8-dihydroxy 4-bis - / ^ ß-hydrochinyl-a-methyl -) - ethylamino7-anthraquinone

209830/1003
BAD ORIGfNAL

It

were in a mixture of 10 ecm N-n-butylacetanilide ■ and dissolved 20 ecm of methanol and then the solution obtained by emulsification in 50 ecm of a 10 ^ aqueous Gelatin solution, the 3 ecm 5 $ sodium sodium dodecylbene sol * sulfonate contained, dispersed. The emulsion was with 2 ecm of a 2 $ aqueous solution of 2-hydroxy-4,6 ~ dichloro-S-triazine mixed and then water to the emulsion added to obtain a total volume of 100 ecm. The emulsion was imbibed onto triacetyl cellulose film to a dry thickness of 5 microns.

2.0 g of 4'-methylphenyl hydroquinone were dissolved in a mixture of 2 ecm of Nn-But ^ laeetaiiilid and 4 cc of ethyl acetate and the solution was emulsified by emulsification in 20 ecm of a 10% aqueous gelatin solution with the addition of 1 ecm of a 5% - dispersed aqueous ITatriuin-n-dodecylbenzenesulfonst solution. 20 g of the emulsion prepared in this way and the sensitizing dye or the combination of the sensitizing dyes, as entered in the table below, were added to a silver jodbro? Aid emulsion containing 5-3 g gelatin and 3.6 χ 10 "" ² Hol silver per 100 g of emulsion ·; · να ~ set and then the silver halide emulsion weighed out on the carrier layer produced in accordance with the invention to a dry thickness of 2.5 microns. 100 ecm of a 3% aqueous gelatin solution with a content of 1 cm of a 2 50% aqueous solution of 2-I3ydro.xy-'4,6-dichloro-S-trissin on a dry temperature of 0 was applied to the silver halide emulsion layer , 8 microns pulled up.

The photosensitive substance obtained in the above manner pilin was durcli e.int5n optical wedge with a continuous Varying the density exposed, in an alk.vlische Treatment solution with the following composition immersed-and then in contact with a lUlaau.C-

209830/1003
BATH ORIGINAL

Receipt sheet with the structure given below. After 2 minutes, the photosensitive film was separated from the image receiving sheet, leaving a positive Dye transfer image of the dye developing sachet was obtained, the intensely exposed parts of the photosensitive film having a lower density, while the parts corresponding to the less exposed areas have a higher density on the image receiving sheet had.

Composition of the alkaline treatment solution

Hydroxyäthylcellulosc of high viscosity 3.5 g

KTaOH 4.0 ρ

Benzotriazole 2.0 g

1-phenethyl-2- picolinium bromide 2.0 g

Water 100 ecm

Structure 'dee Bilda ufi ^ fomebogens

A gelatin layer, which is a mixture of a mordant, Poly-4 ~ vinylpyridine and 1-phenyl-5-raercaptotetrazo! became one on a baryta-coated paper Absorbs dry thickness of 10 microns.

When the reflection density of the on the image pickup sheet obtained color image was determined by means of a densitometer ^ and the amount of exposure in the areas where the reflection density was 1.0 was determined the results listed in Tables I and II are obtained.

20983Ö / 1003

Table I. Sensitive
speed + Red sensitivity
chance ++ Yersuchs-
No. Sensitizing
dye S.
(ml / 100 g emulsion) 85 100 1 1-6 (2) 100 100 2 . "(4) 93.3 87 3 " (8th) 51.3 46.8 4th II - 10 (2) 74 63.1 VJl (4) 69.1 63.1 6th (8th) 240 151 7th II - 6 (2) II - 10 (2) 263 158 8th ". (2)» (4) 246 155 9 "(4)" (4)

The experimental numbers 1 to 6 are comparison samples.

The density of the sensitizing dye solution was 1 × 10 ^-3 mol / liter.

+) The sensitivity is as a relative value of the reciprocal Amount of the loan amount necessary to achieve D = 1.0 E.

++) The red sensitivity is the sensitivity of only the red sensitive layer. The red-sensitive Emulsion was applied to a triacetyl cellulose film for formation the sample is drawn up and the sample is and white development. A No. 7 Fuji filter was used as a red filter.

209830n, 0, p3

BATH ORIGINAL Table II

Experimental sensitizing dye Ur. (ml / 100 g emulsion)

Sensitivity -4-

10 I - I - 2 (2) (2) 11 Il It (4) (4) 12th Il Il (8th) (4) 13th II - 5 (2) 14th It (4) 15th It (8th) 16 2 (2) II - 5th 17th (2) It 18th (4) It 19th I - I - 3 (2) (2) 20th Il It (4) U) 21st Il t! (8th) (4) 22nd II - 6th (2) 23 It (4) 24 It (8th) 25th 3 (2) II - 6 26th (4) Il 27 (4) It

85 100.

93.3, 70.8

135 112 158

219 162

95 _s 100 93.3 95.5 97.6

91.1

145 174 166

Trial numbers 10 through 15 and 19 through 24 are Comparison tests »

+) The sensitivity is sis relative value of the reciprocal Amount of the amount of helium required to achieve D - 1.0 E specified.

Example 2

2 g of the ·! Yellow dye detaching agent 1 "phenyl-3-ΤΊ- * n-hoxy-1 ~ carbo7.yamido- ^ 1 ~ / p- (2 '» b' ■ "d.ihy0.x ^< oxyphenethyl) -xshonylazo7-5-pyro '/, olon were in a C'Cifliych from 2 cora (Pri> ~

20983 0/1003 BAD

cresyl phosphate and 5 coin cyclohexanone dissolved with heating. The solution was dispersed by emulsification in 50 ecm of a 10% aqueous gelatin solution with a content of 2 ecm of a 2 % aqueous solution of 2-hydroxy-4,6-dichloro-'S-triazine. The emulsion was drawn down on triacetyl cellulose film to a dry thickness of 4 microns. A red-sensitive iodobromide emulsion with a content of 4.8 g of gelatin and 3.5 × 10 mol of silver per 100 g of was applied to the emulsion layer

^ Emulsion, which-added the sensitizing dye or containing a combination of sensitizing dyes drawn down to a dry thickness of 2 microns.

1 g of 4'-methylphenyl hydroquinone was dissolved in a mixture of 2 ecm NjN-Biätb / yllaurylamid and 4 ecm ethyl acetate and then this solution by emulsification in 20 ecm. a 10% aqueous gelatin solution with a content of 1 ecm of a 5% v / aesaric solution of sodium n-dcdecylbenzenesulfonate. After adding 2 ecm of a 2% aqueous mucochloric acid solution to the emulsion and further addition of water to a total volume of 50 ecm, the emulsion was applied to the above red-sensitive silver halide emulsion sheet

W weighed out to a dry thickness of 0.8 microns.

By treating the photosensitive sheet thus prepared as in Example 1, a Transfer image of the "ear material developing agent" to the Image acquisition sheet received. The exposure meiigo for one-. Reflection density of 1.0 is shown in Table III.

209830/100 3

Table III Sensitivity + Experimental Sensitizing dye ITr. (ial / 100 g ~ Emulsiöh) 89 28 I - 9 (2) 100 29 "(4) 93.5 30th " (8th) 64.5 31 II - 9 (2) 79.4 32 «04) 74.1 33 * (8th) 224 34 1-9 (2) II - 9 (2) 240 35 "(2)» (4) 219 36 «■ (4) ■» (4)

+) The value of the sensitivity is the same as in Table I. The samples with the test numbers 28 to 33 are comparison samples.

. Example J5

3 g of the magenta peat developing rice 4 ~ Iso ~ propoxy-2- £ p (ß-hydroehinonylethyl) -phenylazq7 "-1" -naphthol were in a mixture of 6 ecm Ν, ΪΤ-diethyllaürylamid and 10 ecm of ethyl acetate dissolved and the solution by emulsification in 50 ecm of a 10% aqueous gelatin solution with a content of 2 ecm of a 5% aqueous Solution of iiatrium ~ n * -dodecylbenzenesulfonate dispersed. Addition of 2 ecm of a 2% aqueous mucochloric acid solution to the Eaiulsion and subsequent addition of water to a total volume of 100 ecm was the Emulsion on a triethyl cellulose film to a dry strength pulled up from 5 microns. That way formed emulsion layer was a rotompfindllcho SiI-

209830/1003 BAD

2185594

berjodbromidemulsion with a content of 5.3 g of gelatin and 3.7 x 1O ~ ² mole of silver per 100 g of the emulsion to which the sensitizing dye or the combination of transmitter sibilisierfarbstoffe, according to the following table was added to a dry thickness of · Mounted 2 microns.

1.3g Pheny! Hydroquinone were in a mixture of 2 ecm FjN diethyllaurylamide and 4 ecm ethyl acetate dissolved and the. Solution by emulsification in 20 ecm of a 10 day aqueous gelatin solution with a content of 1 ecm a 5 $ aqueous solution of sodium n-dodecylbenzenesulfonate dispersed, compartment addition of 2 ecm a 2 days aqueous mucochloric acid solution and further addition of water to a total volume of 50 ecm was the Emulsion coated on the red sensitive silver halide emulsion layer to a dry thickness of 0.8 microns.

By treating the photosensitive film obtained as in Example 1, a transfer image was obtained Color developing agent was obtained on the image receiving sheet. The exposure amount for a reflection density of 1.0 results from the following table.

Table IV Sensitive-
no fc + Sensitive to red
only
the red sensitive
ch en layer ++ (U) Experimental
No. Sensitize
dye
(ml / 100 g emulsion) (a) 83.1 77.5 . 9'3.3 100 37 I - 6 (2) 100 100 81.2 38 ¹¹ (4) 74.1 70.7 37.0 39 " (8th) 41.7 41.7 63.1 40 II - 10 (2) 42.7 66.0 59.0 41 (4) 29.5 53.5 123 42 (8th) 229 126 126 43 I - 6 (2) II - 10 (2) 257 126 126 44 »(2)" (4) 251 123 45 "(4)". (4) 209830/1

ORIGINAL

+) The sensitivity is. in the same way as given in Table I. The samples with the test numbers 37 to 42 are comparison samples.

++) Results by treating a by pulling up the red sensitive emulsion on a triacetyl cellulose film produced sample with black and white development * The Puji-Pilter ITr, 7 was used as a red filter.

a) without coupler. b) with the addition of a coupler

In the experiments in the table above, the same red-sensitive emulsion as in the example was used in the case of the procedure without a coupler. In the package of a coupler additive in the preparation of the emulsion containing the magenta color developing agent, the emulsion was prepared using 13 g of 1- (2 ', 6 ^I -dichloro ~ 4 ^f - ■ methoxy) -3 ~ Z ^ "~ (2 " ^t , 4 ^l " -di-tert-amy! phenoxy) -butylamido} phenylureida7-5-pyrazolone instead of (learning magenta dye developing agent prepared and the emulsion to the same red-sensitive silver halide emulsion as in the example in an amount of 20 g / 100 g emulsion trains- 'give.

Example 4

A multilayer type photographic picture was made by successive mounting of the photographic emulsion layers given below on a triacetyl cellulose film, which is denoted by the reference number 10 in Pig.2. In Pig * 2 of the enclosed ■ The drawing is schematic: the sliding structure of the on top of this Way illustrated photosensitive pilms.

2 0 9 8 3 0/1003 0RK3INAL "^:;

1) Cyan developer layer (reference number 9 of Pig. 2):

10 g of 1,4-bis (a-methyl-.beta.-hydrochinonyläthylamino) -anthraehinon were dissolved in a mixture of 10 cc of N, K-diethyllaurylamide and 20 cc of ethyl acetate, dissolved by heating at 6O ⁰ C for 20 minutes. The solution prepared was dispersed by emulsification in 100 ecm of a 10% gelatin solution containing 5 ecm of a 5% aqueous sodium decyrbenzenesulfonate solution. . After adding 4 ecm of a 2 -strength aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine to the emulsion and further addition of water to a total volume of 200 ecm, the emulsion was on the PiIm to a dry strength of 6, 0 microns soaked up.

2) Red-sensitive emulsion layer (reference number 8 of Pig. 2):

A rotempfindIiehe silver iodobromide emulsion containing 5.8 g of gelatin and 3.8 χ 10 ~ ² moles of silver per 100 g of the emulsion was coated on the emulsion layer to a Trockenstärke'von 5.2 microns. "

3) Intermediate layer (reference number 7 in Pig. 2):

1g phenylhydroquinone was in a mixture of 1 ecm ΪΤ, Ν-diethyllaurylaiaid and 4 ecm cyclohexane dissolved, the solution in 30 ecm of a 10 $ aqueous gelatin solution with a content of 2 ecm of a 5 $ aqueous solution of sodium n-dodecylbenzenesulfonate with an iron alloy dispersed and 30 g of the emulsion were added to 100 ecm of a 5 O ~ aqueous gelatin solution and the mixture applied to the red sensitive layer to a dry thickness of 3.2 microns.

4) Magenta dye developing layer (reference number 6 of the Pig, 2): '

7 g of 4- * ethoxy-2- / p- (ß-h3fdroxyethyl) -pheiiylaso7 "™ 1-" nnplrthol

209830/1003
BAD QRfQlNAi

were in a mixture of 7 ecm Ν, ΪΓ-diethyllaurylamide and 14 ecm ethyl acetate dissolved with heating and the solution by emulsification in 100, ecm of a 10 $ aqueous Gelatin solution with a content of 7 ecm of a 5 $ aqueous solution of FatriurQ-n-dodecylbenzenesulfonate dispersed. After adding 4 ecm of a 2-day aqueous solution of hydroxy-4,6-dichloro-S-triazine to the emulsion and further addition of water to a total? With a volume of 200 ecm, the emulsion was drawn onto the intermediate layer to a dry thickness of 4.0 microns.

5) Green-sensitive emulsion layer (reference number 5 in FIG. 2):

The sensitizing dye or a combination of the sensitizing dyes as shown in the following table were, per 100 g of emulsion was added to a Silberjodbroinidemulsion with a content of 6.5 g gelatin and 3.5 x 10 ^-2 mole of silver and then the silver halide emulsion on the Magentafarbstoffentwicklungsffiitteischicht to a Applied dry thickness of 3.1 microns.

6) Intermediate layer (reference number 4 in FIG. 2) s

The same coating composition as in 3) was applied to the green-sensitive emulsion layer to a dry thickness drawn from 2.8 microns.

7) yellow dye developing agent layer (ref the pig. 2):

5 g of 1-phenyl-3-Nn-butyl-carboxyamido-4-Zp- (2 ⁸ , 5 ¹ -dihydroxyplienethyl) -phenylazo7-5-pyrazolone were dissolved in a mixture of 5 ecm, ΙΤ-methyl laurylamide and 14 ecm ethyl acetate and the solution produced by emulsification in 100 ecm of a 10% aqueous gelatin solution with a content of 5 ecm of a 5% aqueous solution

BATH ORIGINAL

dispersed by sodium dodecylbenzenesulfonate. After addition -of 4 ecm 2-hydroxy ~ 4,6-dichloro-S-triazine for Emulsion and further addition of water to a total volume of 200 ecm was the emulsion on the intermediate layer grown to a dry thickness of 3.4 microns.

8) Emulsion layer sensitive to blue stain (reference number 2 of 2):

A blue-sensitive silver iodobromide emulsion having a öehalt of 5.3 g of gelatin and 3.6 χ 10 ~ ² moles of silver per 100 g of the .Emulsion was coated on the yellow färbst of fentwicklungsmittelschicht to a dry thickness of 2.5 microns mounted.

9) Protective layer (reference number 1 of Pig. 2):

3g Pheny! Hydroquinone were in a mixture of 3 ecm M ", N-diethyllaurylamide and 10 ecm cyclohexane dissolved and the solution by emulsification in 30 ecm of a 10 $ grade aqueous gelatin solution with a content of 2 ecm of a 5 $ aqueous solution of liatrium dodecylbenzenesulfonate dispersed. 30 g of the emulsion obtained were mixed with 100 ecm of a 5 $ aqueous gelatin solution and the "Mixture drawn onto the blue-sensitive emulsion layer to a thickness of 1.5 microns.

-The entire surface of the manufactured in this way color photographic film became uniform with blue light and exposed to green light and then the color photographic film was continuous behind an optical wedge varied density with red light. The color photographic PiIm exposed in this way was with the treated with the same alkaline treatment solution as in Example 1 and then in contact with an image receiving sheet

BAD ORIGINAL 2 0 9830/1003

2185594

as in Example 1 for 2 minutes. When eggs Image recording sheet removed from the photographic PiIm was separated, became a positive transfer dye image of the cyan dye developing agent with a reverse Pigment density to the amount of exposure received on the image acquisition sheet. The density on the image receiving sheet was determined using a densitometer and the amount of exposure required for a density of 1.0 is given in Table Y.

Table V 5 emulsion) Sensitivity + Experimental Sensitizing dye 6 (4) Mr. (ml / 100 t (8th) 100 46 • j- _ (4) 83 47 ti (8th) 67.5 48 II - II - 8 (2) 64.5 49 ti "(4) 219 50 1-6 (2) "(4) 240 51 "(2) 234 52 "(4)

+) The sensitivity was determined as in Table I.

The samples with the search numbers 46 to 49 are "Comparative samples. It can be seen from Tables I to Y that the photosensitive films according to the invention, containing the combinations of sensitizing dyes, compared to the usual known ones photosensitive materials produced excellent photographic effects.

20 9 8 30/1003

Claims (1)

Claim ■ Red-sensitive silver halide photographic emulsion, containing a paraffin developing agent for photographic light-sensitive materials for the diffusion transfer process, characterized by the content of at least one sensitizing dye corresponding to the following general formula I and at least one sensitizing dye of the following general formula II; R ₁ - N - C = CH - C = CH - C = N " ₊ - R ₂ (-O _n-1 I) in which Z is a non-metal atom group necessary for the formation of a naphthothiazole ring or naphthoselenazole ring, Z _{1 is} a non-metal atom group necessary for the formation of a haphthothiazole ring, a benzothiazole ring, a naphthoselenazole ring or a benzoselenazole ring, R is a hydrogen alkylene group or a lower group ₁ and Rp an alkyl group or a substituted alkyl group, where at least one of the radicals R ₁ or R «represents an alkyl group with a hydroxyalkyl group or a carboxyl group or an alkyl group containing a sulfo group, X an anion and η the numbers 1 or 2, where, if the dye is an intramolecular salt, η denotes the fourth 1 R ^ τ Έ - C = CH - C = CH - C - N ₊ - R ₅ ( ^x "") _m --j ^TI ) where Z «and Z ^, which are the same or different can, one to form a benzothiazole ring or Benzoselenazclringes notv / endiß'e NJ ohtmetallatoiagruppioruns 209830/1003 R * is a hydrogen atom, a lower alkyl group or an aryl group, R, and Rc have the same meaning as R.J and Rp in general formula I have and at least one of the radicals R * or Rj- is an alkyl group with a hydroxyalkyl group or carboxyl group or an alkyl group containing a sulfo group, X is an anion and m has the same meaning as η in the general formula I has. 2098 JU / I ÜÜ.J Blank page