DE2324794A1 - COLOR PHOTOGRAPHIC MATERIALS - Google Patents

Description

Color photographic materials

The invention "relates generally to color photography Materials and particularly relates to color photographic Materials suitable for recording sound images.

As a long-term image recording system of color photography Materials used for cinema projection or television generally become optical Recording system or a magnetic recording system applied. The color photographic materials according to the invention represent optical recording systeresis represent.

309848/0982

According to the invention, a color photographic material becomes specified which one for optical sound recording systems is suitable and has a photographic layer, which is suitable for the formation of silver images,

- those with no bleaching in the color photographic material remain in the lead stage after color development.

The layer contains a bleach inhibitor with at least two ethylene groups.

The reproduction of noises, or sounds, through a

■ optical recording system in color photography Playback films, color photographic reversal films, color photographs see reverse play films and the like that usually in the field of cinema projection or in television systems are used by converting the in the color films as a pattern of varying density or areas of recorded sound signals into optical signals, converting the optical signals into electrical signals Signals by means of a light acceptor and then Conversion of the electrical signals into sound or noise signals carried out. With the sound reproduction system Phctoelectric cells with different spectral properties are used as light acceptors. the The photoelectric cell generally used for this purpose is the so-called S-1 type photoelectric cell with a maximum spectral sensitivity of about 800 mu in the infrared range (see, for example, Adrin Cornwell Clyne, "Color Cinematography", 593 (1951)).

On the other hand are the usual 'farbphotographi rule materials for the subtractive color process Main absorptions caused by coupling of the oxidation product a developer such as p-phenylenediamine and the color coupler formed colors all in the visible range, which does not match the spectral properties of the used

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BAD OBlQtNAl.

232Ü794

photoelectric walking ropes collapses. That's why if the optical noise recording only with the coupled Dye images is carried out, the Gjräurc habgabe very weak, so the application of such dye images for optical noise recording for the Px-sxis is unsuitable.

Therefore, reproduction of sounds or noises is usually carried out in color photographic materials Treatment of photographic materials with a treatment, polygamy silver image or silver sulfide image in the G-eräusclispur forms, and utilization of the densities of the Silver images or silver sulfide images performed in the infrared range for the reproduction of sounds or noises. In this case the infrared densities (transmission densities) usually en two 1.0 to. about 1.6.

The sound trail in photographic reproduction films for example, according to that in "Journal of the Society of Motion Picture and Television Engineers", volume 77, page 1154- (1968) specified method will. In this method, the color images in the image parts and the sound images or the pattern in the Sound recording parts are formed simultaneously in the color development in the color developing bath. In the first fixer the unexposed silver halide is removed and in the bleach bath that formed in the development stage becomes developed Gilber rehalogenated. Then, in the sound development stage, a viscous sound developer becomes selective applied to the noise traces and only the silver halide on the noise traces is in Transferred silver images. In the second fixing bath, the silver halide is fixed and removed in the image parts, and the dyes of the image parts are stabilized in the stabilizing bath. The densities of the silver images in the infrared

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rich of the sound traces formed in this way used to reproduce the sound.

As mentioned above, in forming the sound track in color photographic 1 ^'1 Unen the formation of silver images or silver sulfide images required, ie, the formation of such images is also required to form the dye image in the image parts. As stated above, the reason for the formation of this sound trail composed of yellow or silver sulfide is that the spectral sensitivity properties of the "photoelectric cells used to reproduce the sound have a sensitivity maximum in the infrared range, while the colored images formed in the color photographic materials in the color development step have none have sufficient density in this region of long wavelengths.

One object of the invention therefore consists in color photographic Materials that do not require a specific treatment step, such as the above conventional procedures to form a sound trail.

Another object of the invention is a method for forming sound images without the need for it is, specific 3 levels of treatment as with the usual Procedure to apply ..

The above objects of the invention are achieved when, on a color photographic material, a Layer formed for the formation of silver images xvird, which in the color photographic material without bleaching in the bleaching step nor the color development due to the Presence of a bleach inhibitor with at least two Gxyäthylengruppen remains.

In general, a fa.rbph.0t03raphisch.es material from a carrier with several Lchichich-

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th of photographic cilber halide emulsions, each in a different sensitivity range. are sensitized. If such a color photographic material is exposed imagewise and then is subjected to color development, dye images become and silver images formed. The silver images are then oxidized in a bleaching process and continue to be the oxidized purple images from the color photographic material removed by a fixing treatment, thereby obtaining a color photograph consisting of the dye image will.

The color photographic material according to the invention has a layer for forming the silver image, which is not removed by such a bleaching step and results Color photographs of dye pictures and silver pictures with normal color development. The silver images are conveniently used as a sound trail for a color photograph material used.

It was found that when a silver picture developed with a compound with at least two Cxyäthylengruppen is contacted in the molecule, the silver remains unbleachable. Such connections are made below referred to as "bleach inhibitor".

According to one embodiment of the invention, the color photographic material has a first one on a support Silver halide emulsion layer, one of which is responsible for the formation of a yellow dye on reaction with the oxidation product a color developing agent suitable coupler having a sensitivity to a first visible Area contains a second silver halide emulsion layer, one for forming a magenta dye in the reaction with the oxidation product of a

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Color developing agent contains geiegnetec coupler with a sensitivity for a second visible range, a third emulsion layer which contains a coupler for the formation of the cyan dye by reaction with the oxidation product of a color developing agent suitable coupler with a sensitivity for the third visible range, and a fourth silver halide emulsion layer which contains a Contains bleach inhibitor and for visible _? sensitive to ultraviolet or infrared areas. '.. _f

If any of the above color photographic materials are exposed to an "original" and is then color developed, a yellow dye image and a silver image are in the first silver halide emulsion layer, a magenta dye image and a silver image in of the second silver halide emulsion layer, a cyan dye image and a silver image in the third silver halide emulsion layer and a silver image in the fourth Silver halide emulsion layer is formed. So if that thus developed color photographic material is subjected to the bleaching treatment, the in the first, second and third silver halide emulsion layers are bleached, while that in the fourth silver halide emulsion layer remains unbleached due to the action of the inhibitor contained in the emulsion layer. Through this becomes a color photograph with dye images and silver / sound images obtain.

The fourth silver halide emulsion layer can have sensitivity to all visible, ultraviolet or have infrared areas. If, however, the sensitive area of the fourth SiIb is susceptible to failure

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sensitive area of the first silver emulsion layer, the second silver halide emulsion layer, or the third silver halide emulsion segment doubles, it is favorable to the sensitivity of the former ε-ε to one Value below 1/4, preferably below 1/6 of the sensitivity to humiliate all of the latter.

In the color photographic materials according to the invention, the silver halide emulsion layer constitutes the contains the bleach inhibitor, at least one in addition to the blue-sensitive silver halide layer, the green-sensitive Silver halide emulsion G layer or the red-sensitive silver halide emulsion layer for formation a layer formed of an ordinary color photographic material. In a preferred embodiment the color photographic materials according to the invention are a blue-sensitive silver halide emulsion, containing a yellow dye forming coupler, a red sensitive silver halide emulsion layer, containing a cyan dye forming coupler, a green-sensitive silver halide emulsion layer which contains a magenta dye forming coupler, and a green-sensitive silver halide emulsion layer, containing the bleach inhibitor is formed on a support in the above order.

As already stated, the bleach inhibitor contained in the layer can be sensitive to all ultraviolet, visible or infrared areas. Therefore, the above form of training is only one preferred embodiment of the invention.

In this case, the green-sensitive silver halide emulsion layer, containing a Msgenta dye-forming coupler, are absorbed after the green-sensitive silver halide emulsion G layer containing the

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Contains bleach inhibitor, on the red-sensitive silver halide emulsion layer, which contains the coupler forming the cyan dye is absorbed. In any case can also use the silver halide emulsion containing the bleach inhibitor contains spectral sensitivities for all ultraviolet, visible or infrared ranges have * In this embodiment, only the Order of the green-sensitive emulsion layer that contains the Ilagenta coupler, and the green-sensitive one Emulsion layer containing the bleach inhibitor different from the one described above. Execution form.

In a further preferred embodiment of the invention, the light-sensitive silver halide demulsion layers, which contain dye-forming couplers on the support in a different order be designed as specified above. For example, a red-sensitive emulsion layer containing a cyan dye forming coupler, a green-sensitive emulsion layer that has one Magenta dye forming. Contains coupler, a yellow one Filter layer containing colloidal silver (Carey Lea type) or a yellow dye (e.g. tartrazine and dyes according to US-Potentschrift 2,527,583) contains, a blue-sensitive emulsion layer containing a yellow dye-forming coupler, and a silver halide emulsion containing the bleach inhibitor contains, formed on the carrier in this order.

The soundtrack image recording layer of the photographic. Materials is for recording purposes only of the sound or noise trail image. Latent images of the image recording must not be formed in the layer

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xverden. The selective exposure of the sound recording of the Image recording layer can be achieved by application different photographic sensitivities or spectral sensitivities of the silver halide of these Layers are effected. For example, the for Sirber halogen emulsion layer for sound and recording be sensitized to a radiation to which the image recording layers are at least partially insensitive are, for example infrared radiation, or for the range of relatively minimal sensitivity be sensitized between two imaging layers of adjacent spectral sensitivity, for example. assign the area between the green and the red sensitive layer. On the other hand, the sound recording layer less sensitive or slower than the image recording layer of the corresponding spectral Be sensitivity.

Examples of bleach inhibitors suitable for practical use, which are used in the context of the invention are given below:

Compound 1. HO (GH ₂ GH ₂ O) _n H (molecular weight about 1000)

Compound 2. HO (GH ₂ CH ₂ O) _n H (molecular weight about 6000)

Compound J. HO (CH ₂ CH ₉ K) _n H (molecular weight about 11,000)

Compound 4. HO (GH ₂ CII ₂ G) _n H (molecular weight about 20,000)

Compound 5. C ₅

Compound 6. C ₇

Compound 7. 'C ₁

Connection 8. ' C ₁

Compound 9- C ₁

Compound 10. C ₂

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link

11. C ₉ H ₁₉ COO (CH ₂ CH ₂ O) ₂₁ T CC ₉ H ₁₉ ,

O ti

Compound 12. C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₉ -C ₁₁ H ₂₃ ,

Connection 13..

Connection <\ ΐ ± ₉

Connection 15 «

Connection ης.

Connection 17.

Connection 18 · Connection. ^ g,

Connection 20.

Connection 21.

Connection 22. "

Connection 23 «

Connection 24.

Connection 25.

Connection 26.

0 1t

C ₁₇ H ₃₅ COO (CH ₂ CK ₂ O) ₉ -C ₁₇ H ₃₅ ,

C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ^ CC ₁₇ H ₃₅ ,

0 dd

C ₁₇ H ₃₃ COO (CH ₂ CH ₂ O) ₂₃ CC ₁₇ H ₃₃ , C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₂ H,

C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₄₀ H, ^C 14 ^H 29 ^{0 (CH} 2 ^CH 2 ⁰⁾ 15 ^{H 'C} 16 ^H 33 ^{O (CH} 2 ^CH 2 ^O) 2O ^H' G ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₈ H,

C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₅₀ H, C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₀ H ₉

C ₂₂ H ₄₅ O (CH ₂ CH ₂ O) ₁₅ H, C ₂₂ H ₄₅ O (CH ₂ CH ₂ O) ₅₀ H,

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V erb in duns 2 ?. ^CH 3

Connection 28.

Connection 29.

Connection 30.

Verb in dung 31 »

Connection 32.

Connection 33.

Connection 34.

Connection 35.

(CH ₂ CH ₂ O) ₅₀ H,

(CH ₂ CH ₂ O) ₅₀ H, H ₉ OO

(CH ₂ CH ₂ O) ₅₀ H, ^ i ₁₁ (t)

(CH ₂ CH ₂ O) ₅₀ II.

0 (CH ₂ CH ₂ O) ₂₇ H.

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-A ⁰ I-

Compound 36. CH ₅ O (CH ₂ CH ₂ O) ₁₂ H, Compound 37. C ₂ H ₅ O (CH ₂ CH ₂ O) ₆ H ₁

Connection 38 <connection connection

^N (GH ₂ CH ₂ O) _q H

■ (CH ₂ CH ₂ O) _p H

^G 14 ^H 29 ~ ^N \

^X (CH ₂ CH ₂ O) _q H

O) _q H

link

¹ N.

( CH ₂ CH ₂ O) _p ff (CH ₂ CH ₂ O) H

Connection ρ + q = 30,

P + Q. = 5,

"P ₊ q = 20,

ρ + q = 30.

Ve vb in dung

Compound 44. ^ j-CH- CH ₂

2, η = 5, m «22
η '= 400

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Connection i \ ^

. -J-CH -

m = 15 η = 400

Connection 46.

0- £ CH _o CH _o 0j-H

Compound 47

CH, -0-

K N OCH

Connection 43 m + η =

" ^CH

CH

link

0 = P-0- £ GII ₂ CI! ₂ 0} £ -

50,

(^ ₁₂ II ₂₅

link

0 Il CH

=

a + b + C =

O ₁₇ H ₃₃ -O- (CH ₂ CH ₂ OJ ₂ PO- (CH ₂ CH ₂ O) ^ ₁₇ H ₃₃

ONa a + b =

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CH ₃

Connection 51.
Connection 52.

ρ + q = 10

CHpCOO

Connection .55. H0 ~ f CH ₀ CH ₀ O) - (- CH ₀ -CH-C- (CH ₀ CH ₀ O) ₀ H

-CH, -. 3

. a + c = 4

b = 30

Compound 54. HO- ^ CH ₀ CH ₀ O) (CH ₀ -CH-O), (CH ₀ CH ₀ O) ^ H

2 2- 'a 2 | ^y D 2 2c

¹ y

CH,

a + c "=

"F =

Compound 55.

CH ₀ CH-CH-CH ₀ -OCC..H

₀ C

O · ■ O

0-4CHpCHpO

a + b + c =

-. (CHpCHpO ^ H

Compound 56. C ₁₁ Hp ₅ CON _f "■

(CHpCH ₂ O3- * H ρ + q = 10

Compound 57, C ₁₇ H ₅₅ CON

- (CH

ρ + q = 30

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Connection 58.

Compound 59. C ₁₇ H ₅₅ COoJfCII ₂ -CH-CH ₂ -OJ ₂ ^ CH ₂ -CH-CH ₂ OH

OH OH

Compound 60.

Connection 61.

Cl

ONa

^ci

ONa

Compound 62. Cl-

The amount of in the color photographic according to the invention Materials used in bleach inhibitor mainly depends on the properties of the bleach inhibitor itself, but is generally in

-7 4

Range from about 1 χ 10 -4 g to 1 χ 10 g, preferably 1 χ 10 -4 to 1 χ 10 -4 g per half of silver in the silver halide emulsion layer.

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The amount of bleach inhibitor can be adjusted according to the ilalogenide composition and the grain size of the in the silver halide used in the layer.

The thickness of the soundtrack recording layer can vary widely, but "is generally about 0.5 "to about 5 hikron, preferably 0.5 to 3 hikron. '

The swinging ingredients of the bleach inhibitor containing sound trail recording layer according to of the invention are a silver halide, a hydrophilic colloid and the lead inhibitor. If desired, can a coupler can also be added to this. All of the usual silver halide emulsions used in imaging layers can in the soundtrack recording layer in accordance with the discovery. she can silver chloride, silver bromide, silver chlorobromide, Silver bromoiodide, silver chlorobromoiodide or mixtures thereof contain. You can get off a negative development emulsion odex 'a veiled direct positive emulsion exist. Gelatin or all conventional photographic hydrophilic colloids can be used as a carrier for the silver halide can be used in the sound or noise trace recording layer. '

The soundtrack recording layer may also be others Additives such as sensitizing dyes, hardeners for contain the hydrophilic colloid or coating aid. The choice of these and other additives and the method of incorporating them into the silver halide emulsion Soundtrack recording layer can be freely selected by those skilled in the art which the emulsion- in view of create the special end use.

As for the color photographic materials according to Carriers preferably used in the invention are -example-

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v / other cellulose ester films such as cellulose nitrate films, cellulose acetate films and the like, polyester films such as polyethylene terephthalate films and the like, Polyvinylchloridfilrae, Polystyrene films, polycarbonate films, and the like. The carriers can be freely selected by the experts.

All known photographic hydrophilic colloids can be used as binders for the silver halide emulsion layers be used. For example, gelatin, albumin, gum arabic, agar-agar, cellulose derivatives, such as alkyl esters of carboxycellulose, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose and synthetic resins, such as polyvinyl alcohol and polyvinyl pyrrolidone are preferred. These hydrophilic colloids are preferably also called Binder for layers other than the emulsion layers used in photographic materials, for example as protective layers, filter layers, intermediate layers, Antihalation layers, base layers, back layers and the like. *

That see for the different layers of color photography Material according to the invention used hydrophilic colloid is suitably by a hardening agent, for example an aldehyde as a hardening agent, a methylol as a hardening agent, a 1,4-dioxane as a hardening agent, an aziridine curing agent, an isooxazole curing agent, a carbodiimide curing agent active halogen as a curing agent or an active vinyl compound cured as a curing agent. Typical examples of such hardeners are given in US patents 3 232 764, 3 288 775, 2 732 303, 3 635 718, 3 232 763, * 2 732 316, 2 586 168, 3 103 437, 3 017 280, 2 983 611,

2 725 294, 2 725 295, 3 100 704, 3 091 537, 3 321 313 and

3,543,292 and British patents 974,723, 1 167 207 and 994 869 are given.

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According to the invention, all can usually be the field of the photographer! e silver halide emulsions used, for example silver bromide emulsions, silver iodobromide emulsions, Silver chloroiodobromide emulsions, SiI berchlorobromide emulsions and syllable rc hl orideiauls ionen used will.

In the imaging layers, the preferred average grain size of the silver halide is about 0.05 to about 1.5 microns, preferably about 0.05 to about

1 micron.

In the sound recording layer, the preferred average grain size of the silver halide is about 0.15 "to about 0.6 microns, preferably about 0.05" to about 0.4 microns.

The weight ratio of silver halide to The binder is suitably in the range from about 0.2 to about 20 (silver halide / 3inder), preferably about 0.3 "to about 5 in. of the image recording and soundtrack recording layers. These values are not limiting. However, excellent results are obtained when work is carried out in accordance with these guidelines.

Also the so-called converted silver halide grains described in US Pat. No. J 622 318 and the British Patent 635 84-1 effective-be used in the context of the invention.

The Sirberhalogenidemulsionen used in the farbphotographisehen materials according to the invention can, by chemically active gelatin or sulfur compounds according to US-patent publications in Λ 574,944 ,. 1 623 499 and 2 410 689 are sensitized. You can also use noble metal salts, for example palladium or gold salts according to the US patents

2 448 060, 2 399 083 and 2 642 36I.

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You can also use a reducing agent, such as tin (J.l) salts according to the Ub patent document 2 487 850 be sensitized or by Polyalkylene derivatives are sensitized. You can also sensitized with cyanine or ileocyanine dyes v / earth, -v / ie in the UC-Potentschriften 2 5 ^ 9 001, 2,666,761, 2,734,900, 2,739,964 and 3,481,742 are given.

The silver halide emulsions used according to the invention can use a stabilizer such as mercury compounds, azaindenes and the like., plasticizing such as Glycerin and the like, and liberation aids, such as saponin, Polyethylene glycol monolauryl ether and the like. Contain. In addition, they can contain antistatic agents, ultraviolet-absorbing agents, fluorescent whitening agents and the like., included.

According to the invention, all open-chain, the yellow dye-forming iletomethylene color coupler can be used effectively. Typical examples of such couplers forming the yellow dye are benzoylacetanilide color couplers, Pivalylscetanilide color couplers and the like Materials.

As color couplers forming the magenta dye for example Iyraζölon color couplers, Indnzolon color couplers and the like, effectively used in the Ealrinien of the invention.

Furthermore, as color couplers forming the cyan dye, for example phenolic color couplers, naphtholic ones Color couplers and the like effective in the invention used.

Each of the couplers listed above may have a group which can be split off or released upon coupling contained on the active carbon atom in the coupling position. It is preferred that the invention

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- - 20 -

Color couplers used with non-diffusing properties is equipped by means of a ballast group in the molecule of the color coupler.

The terms "group that can be released during coupling", "ballast group" or "non-diffusing property" are in the linn, as they are usually used in color couplers are used, applied and their meaning is the. Familiar to professionals.

A large number of such couplers are known, but color couplers which are particularly favorable are those color couplers which form yellow images with an absorption maximum in the wavelength range from 4-20 to 460 μm on reaction with the oxidation products of the color developing agent. Color couplers which form magenta dyes with an absorption era maximum in the wavelength range from 520 to 57Ö mjii in the reaction with the oxidation product of a color developing agent / and those color couplers which form cyan dyes with the absorption maximum in the wavelength range from 63O to 710 mja during the reaction "Form with the oxidation product of a color developing agent.

Examples of nondiffusible couplers that can be incorporated into the image receiving oil halide emulsion layers photographic. Materials can be incorporated, are in US Patents 1,108,028, 2,186,849, 2 206 142, 2 343 702, 2 367 531, 2 569 489, 2 423 730, 2 436 I30, 2 474 293, 2 600 788, 2 689 793, 2 728 658,

2 742 832, 2 808 329, 2 998 314, 3 046 129, 3 062 653,

3 265 5O6, 3 311 476, 3 408 194, 3 419 390, 3 419-391, 3 458 3.15, 3 476 563, 3 516 831 and 3 617 291 and the British Patent 1,183,515.

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These color couplers are incorporated into the hydrophilic colloids for the photographic materials according to any one well-known processes incorporated »they can sample wines in the hydrophilic colloids as a solution in a high-boiling organic solvent such as dibutyl phthalate, Tricresyl phosphate, and the like, are and can be incorporated if desired a low-boiling organic solvent, such as ethyl acetate, tetrahydrofuran and the like., Correspondingly of the! ^ patent specification 2,522,027. If the Color coupler an acidic group, "for example a carboxyl group or has a sulphonic acid group, it will be hydrophilic colloid introduced as an aqueous alkaline solution .

In the sound track formation according to the invention, it is advantageous if the developed bilber has the highest possible density with the lowest possible kenge of drawn silver. Therefore, it is favorable to incorporate in the sound tracking layer a compound having the effect of accelerating development with high density. Examples of compounds having such action are compounds which result in a coupling reaction with the Gxidationsprodukt of Farbent- · wicklungsnittels, ie coupler. The term "coupler" in this case denotes a color coupler used for the usual color photographic materials and a coupler (colorless coupler) which does not form a colored dye. Of these couplers, particularly preferred are those couplers which slightly diffuse when immersed in an alkaline developer and accumulate on the surfaces or near the surfaces of the developed silver as an unreacted coupler or a coupling product.

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Such compounds are believed to have an effect of protecting the silver image from exposure to the bleach and the reduction of lead sensitivity to have. As examples of couplers having such properties couplers with diffusion-resistant groups are listed, including, for example, in coupler A the group

pie tion -GH ₀ GH ^{&quot; y} delivers this effect. The groups

preferably contain about 6 to about 12 carbon atoms and are directly or via a bridging group, for example an iither, ester or an amide bond with linked to the coupler molecule. Couplers other than the above may have the desired diffusion resistance property by choosing the degree of dissociation of the couplers in an alkali and the hydrophilic ones Property of the same. Examples of couplers with such properties which are suitable for use in practice are given below:

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Coupler A:

COCH ₂ CONH

COOCH ₂ ^

.C ₁ . IL

Dome a? 3;

COCH ₂ CCl-IH

Coupler C:

// y-COCH ₂ CONH "^ /

Coupler D: ft y- COCH ₂ CONH

Coupler E: Coupler "F:

COCH ₂ CONH _ / \

0C _r H, _x 6

CH

COCH ₂ CONH CH,

Coupler Coupler H:

COCH ₂ CONH-

CH,

CH, COCH _o CONH 3

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"Coupler I:

Coupler 'J:

CH _x COCH ₀ COITH

Coupler K:, COCH ₂ CONH CH ₅ COCH ₂ COHH

^0G 10 ^H 21

Coupler 1ϊ

COCH ₂ CONH

Cl

^C 10 ^H 21

. OCH-

Coupler M:

COCH ₂ CONH

CON ⁰ A ₇

Coupler ^ *

CH ₂ COCH

Coupler "0:

Coupler- ? · ■

OH

COCH ₂ COOC ₁₂ H ₂₅

CONH (CH ₂ ) ₇ Ü (

.Coupler Q:

OH ^. _ ^, ("CH ₂ )

CONH (CHp) ,, OCHpCH

C ₂ H ₅

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Coupler. R: OH coupler * S:

Küppier T: OH

CO NH (CH ₂ ) ₆ CH ₃

Coupler * TJ: OH

CO NH (CH ₂ ) "CH

Coupler '

(CHg) ₃ CH _{3 coupler} -. ν /: OH

CON

CON

(CHg) ₅ CH

■ Coupler X:

C0

NCH ₀ CH ₀ CONH 2

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These couplers can be incorporated into the sound track forming layer in the same way as in the case of the introduction of the previously described color couplers' introduced; will.

Since these couplers are used to accelerate silver image formation, the amount can vary widely ieren. The amount of the coupler is generally about

- -5 - 1-2

2 χ 10. "to about 5 x 10 MoL, preferably 5 -X 10 to

—I
5 x 10 moles per mole of silver in the silver halide emulsion.

The infrared couplers given in the description of Japanese Patent Application 94-265 / 1971 can also be used in the color photographic materials according to the invention. The infrared couplers form a dye with the absorption maximum at a wavelength range longer than 725 ηψ- through a coupling reaction with the oxidation product of the color developing agent. When the density of the dye formed in this way is used, the density of the silver image of the optical sound track can be reduced according to the invention, ie the amount of silver to be enumerated can be reduced.

In the usual sound recording, essentially exploited the infrared density of the silver image in the sound track, since photocells in the projectors with a Sensitivity in the infrared range can be used. The infrared densities are usually 1.0 to 1.6 in the Sound track. If an infrared coupler in the emulsion layer is incorporated in accordance with the invention, an infrared dye is formed after development. These Infrared dye density contributes to the soundtrack density together with the silver picture in the sound track.

The color photographic material according to the invention can be imagewise and tonally in any desired way

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exposed and then developed according to any customary colors . treated v / earth. The main stages of color treatment are color development, bleaching and fixing. If necessary, an underwater wash can be carried out between these stages. After fixing, the color photographic material is washed and dried, but it is preferable if the color photographic material is treated in a stabilizing bath before drying.

As those skilled in the art know, the photographic processing temperatures are typically between about 20 ° C. or less to 60 ° C. or higher. Temp era doors of ^ twn JO ⁰ C or higher are suitable for low-speed treatment procedures. Treatment times at each treatment stage can vary widely depending on the treatment temperature, but are usually a few seconds to a few minutes or more.

Typical examples of useful methods of treatment can be found in the Journal of the Society of! Lotion Picture and Television Engineers, Volume 61, pages 667-701 (1953) and in the British Journal of Photography, pages 122 to 123, 126 (1960).

Usable color developers include aqueous alkaline ones Solutions that contain a color developing agent. as Color developing agents preferentially ground all color-forming developing agents from the primary aromatic Amine type, for example phenylenediamines, v / ie N, N-diethylp-phenyl en dia min, li-lthyl-li-hydroxyethyl-p-phenyleneamine, N-ethyl-K-hydro; iyäthyl-2-methyl-p-phenylenediamine, R- £ N-methanesulfonamidethyl-3-methyl-4-amnoaniline, N, N-diethyl-2-methyl.p-phenylenediamine, as well as the sulfates,

309848/0982

. - 28 -

Hydrochlorides, or sulphites thereof and similar materials, used, for which on C.E.K.'Mees and T.H. James, The Theory of the Photographic Process, pp. 294- "through 295 (The-Macmillan Co. 1966) and U.S. patents 2,592,364 and 2,193,015.

The color developer can also contain additives such as are commonly used in the field, for example alkali sulfites, carbonates, bisulfites, -Bromides, -iodides, benzyl alcohol and the like.

All bleaching solutions, the known bleaching agents, such as ferricyanide z. B. potassium ferricyanide or sodium ferricyanide, Bichromates, such as potassium dichromate or sodium dichromate and the like can be used in the present invention. Also, all fixing solutions that are ' contain known fixatives, e.g. sodium thiosulphate, Potassium thiocyanide and the like can be used will.

In addition, the bleaching stage and the fixing stage can also be used run in a bath. This was "with the usual procedures that required sound development, not possible. By using a blix bath instead of the The bleaching bath and the fixing bath according to the invention can be the treatment stages for the photographic materials can be further simplified according to the invention and also, the treatment time can be shortened.

The solvents used in the known blix solutions for syllable epidemics, all can also be used in the blix solutions for the treatment of color photographic materials according to the invention. as Examples of such solvents for silver halides be water-soluble thiosulfates, such as ITodium thiosulfate, Potassium thiosulfate, ammonium thiosulfate and the like, water-

309848/0982

soluble thiocyanides such as sodium thiocyanide, potassium thiocyanide, amraonium thioeyanide and the like; water-soluble organodiol oxidants having an oxygen atom or sulfur atom such as J-thia-1,5-pentanediol, 3,6 ~ dithia-1,8-octanediol, 9 ~ ^C; xa-3> 6, i2,15-'betra-thia ~ '1,17-heptadecanediol and the like, water-soluble sulfur-containing dibasic acids or water-soluble salts thereof such as ethylene bisthioglycolic acid, sodium salt thereof and the like, and imidazolidine thiones such as methylimidazolidine thione and .

The oxidizing agents previously used in the blix solutions for silver can all - also in the blix solutions used in accordance with the invention. Examples of such Oxidizing agents are water-soluble ferricyanide, such as sodium ferricyanide, potassium ferricyanide, ammonium ferricyanide and the like, water-soluble quinones such as quinone, chloroquinone, methylquinone and the like, water-soluble Iron (III) salts, such as iron (III) chloride, iron (III) sulfide, Iron (IU) thiocyanide, iron (III) oxalate and the like., water-soluble cobalt (III) salts, such as cobalt (III) chloride, Cobalt ammonium nitrate and the like. Also polyvalent cations of water-soluble organic acids or alkali complex salts of water-soluble organic acids can preferably be used as oxidizing agents. To the Organic acids include the compounds of Pormelny

HCOC-E ₁ -XR ₂ -C OGH or

HOOO-R _x -Ir-E ₄ -OOOH

HOOC-R _x -IT-B .. -COOH 3 4-

where X is a hydrocarbon group ^ an oxygen atom, a sulfur atom or a group = NRgj Iti> ßp '^ v ^ u

309848/0982

Rc is an unsubstituted or substituted hydrocarbon group and Rg is a hydrogen atom or an unsubstituted one or substituted hydrocarbon group.

Specific examples of the organic acids include malonic acid, tartaric acid, ethylmalonic acid, malic acid, Fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, Nitrotriacetic acid, ethylenediaminetetraacetic acid, Aminotriacetic acid, ethylenedithioglycolic acid, Dithioglycolic acid and similar compounds.

Specific examples- of polyvalent cations are the iron (III) ion, the cobaltClII) ion and the copper (II) '·; ion.

An iron-sodium complex salt of ethylenediaminetetraacetic acid is particularly useful as a bleach.

In the blix baths according to the invention, the additives used for ordinary blix solutions can be advantageous can be used. Examples of such additives are sodium sulfate, potassium bromide, potassium iodide, sodium iodide, Polyalkylene oxide, 2-mercaptoimidazole, 3-mercapto-1,2, ^ 1— triazole, dithioglycol, thiourea, ethylene thiourea, Hydroxylamine salts, p-aminophenol, ascorbic acid, semicarbazide, hydrazine and the like *

Specific practical examples of blix solutions for treating the color photographic materials according to the invention are given below:

Bleach (monohydrate) below Sodium. 5 g Boric acid 5 g Sodium sulfite 5 g Fixation device 1 below

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The solution is adjusted to a pH of 6.0 and the volume adjusted to 1.0 liter by adding water.

Various bleach and fiber combinations for Blixbjider are listed below:

Blixbad bleach fixer

(a) Iron (III) sulfate + ITodium thiosulfate (0.05 hol) disodium ethy- (0.6 mol) lendiamine tetracetate

(0.1 Hol)

(b) lTatriuT7i-iron (III) -ethylene-sodium thiosulphate diamine tetraacetic acid (0.6 hol)

(0.1 Hol)

(c) Eisen (Hl) -salz der ITi- as well trilotriacetic acid

(0.1 Hol)

(d) Iron (111) salt of ΪΤ- as well as Hydroi ⁱ oxy & .thyläthy3.endi-

cmin triacetic acid
(0.1 Hol)

(e) ITatriUKi-iron (III) -ethylene-potassium thiocyanide dianine tetraacetic acid - (0.6 Hol)

(0.1 Hol)

(f) sodium iron (II) ethylene potassium thiocyanide diamine tetraacetic acid (0.5 Hol)

(0.1 hol) liatrium thiosulfate

(0.5 Hol)

(g) Katriun iron. (IIl) ethylene thiourea (5g)

diamine tetraacetic acid,. _T. '. ,,. _Ί ".

in λ \\ r, - \\ ITatriuEithiosulfat

^C0 ' ^{1 Iloi;} (0.6 Hol)

Typical bleaching agents are detailed in the Journal of the Society of Hotion Picture and Television Engineers 61_, page 66? to 701 and the Uo patent font 189 452,

the typical fixatives in L.F.A. Hason, photo

303848/0982

graphic processing chemistry, pages 197-188,! Focal Press (1966) and

typical blix solutions in the German patents 866 605 and 966 410, in British Journal of Photography, pages 122 to 12 * and 126 (1066) and in. U.S. Patent 3,582 J22. These references also describe the generally used conditions.

In developing the color photographic material according to the invention in a color developer which is a color developing agent contains, the silver image necessary for recording a sound image is simultaneously with the yellow, hagenta and cyan pigments to form formed of color images. Of course, too Silver images are formed in the color image parts, however these silver images are lightly bleached in the bleach bath or blix bath listed above. However, the in the emulsion layer containing the bleach inhibitor, formed silver images not in the 'bleach bath or flower bath bleached and remain as a silver image.

Since a sound image (3iberbild) 'by application only an ordinary development process becomes an additional development stage for the formation of a silver image for sound recording, as in previous processes, unnecessary according to the invention, so that the entire process steps are greatly simplified when the color photographic material according to the invention is used. I. E. , by application of the color photographic material according to the invention the so-called silver tone development becomes unnecessary as with the usual systems.

According to the invention, a sound track is also made

309848/0982

Silver images recovered. Therefore, the advantage occurs in the case according to the application of the color photographic materials of the invention that the sound track is not through a Reduction in density accompanied by exposure to light, heat or moisture is common is observed in recording tapes composed of an organic dye with an absorption in the infrared region are made.

If a color photographic material has a yellow filter layer, containing yellow colloidal silver, or an antihalation layer containing black colloidal Silver contains, has, v / ground these colloidal silver materials re-halogenated in the bleaching stage and the halogenated silver materials will continue in the sound development developed. Therefore, the usual sound development is inapplicable in this case. Since according to the present Invention of this additional sound * development is unnecessary, it becomes possible to also see color photography Apply materials containing colloidal silver.

The following examples serve to further illustrate the invention on the basis of preferred specific embodiments .

example 1

The opposite surface of a cellulose acetate film backing to the surface with the antihalation layer containing Buss was coated with a primer layer and on top of the primer layer was a "coating" drawn up containing a silver iodobromide emulsion with a Content of 1.2 mol ^ iodide and 0.05 mol of silver and one Contained yellow coupler, i.e. H. a dispersion, which by dispersing a- (2-methylbenzoyl) -3- / a- (2,4-di-tert.-

309848/0982

amylpheno>: y) -acetamidq7-acet3nilide of the formula

COCH ₂ CONH

NHCOCH ₂ ON ^ Λ

made in a mixture of diallyl phthalate and ithyl acetate to form the blue sensitive layer. A gelatin interlayer was placed on top of the blue-sensitive layer formed and on this layer ■ a coating mass was applied, - the 100 g silver chlorobromide emulsion. . (G, C6 Hol silver) with a content of JO mol% ßromide and a cyan coupler, namely 1-hydroxy-4-chloro-IT-hexanedecyl-n-C2-cyanoethyl) -2-naphthamide the formula

^C 16 ^H 33

contained as a dispersion in a mixture of dibutyl phthalate and ethyl acetate, the silver halide emulsion spectrally in such a way that it had the sensitization maximum at about 685 phr with a sensitizing dye of the formula

30984870982

θ, C-CH = CH-C = CH-CH = C

was sensitized so that the ret sensitive layer was formed. A gelatine intermediate layer was formed on the red-sensitive layer and a coating wet was also applied to the layer which contained a silver chloroboramide emulsion (0.06 Hol Gilber) with a content of 55% Bronxd and a dispersion of the magenta couplers, 1- (2,6-dichloro-4-methylphenyl) -5 ⁱ - {3- ^ ä- (2,4-di-tert-aiaylphenoxy) -butylamido_7-benzamidoJ -5-pyrazolone of the formula

Ct) C ₁ -H

H ₂ C-CO

COIiH-C = N

309848/0982

and 1- (2, ^, 6-triclilorphenyl) -3- £ 3- ^ ä- (2,4-di-tert-arylamylphenoxy) -butylamidec ^ 7-benzsmidoj ~ 5-pyrazolone. the Pormel

CONH-C =

entMelt, vrobei this SilTDerhalogonidemulsiori spectrally in the way that they ^m xhr Gensibilisationsmaximum at about 555 V · had one through. "üensibilisierfarbstoff the Ponael

o \ r ^ .0

® ' C-CH = C-CH = C ^

SO ^ H. N

309848/0982,

had been sensitized, so that the green-sensitive Layer was formed.

A dispersion of liquid Farsffin in an aqueous gelatin solution was then drawn onto the green-sensitive layer to form a protective layer. The color photographic reproduction film formed in this manner itfurde ^a ^ - ^s sample I, respectively.

A color reproduction photographic film was also made prepared in the same manner as above, but with a soundtrack formation layer between the green-sensitive layer and the protective layer of the sample by applying a coating composition containing a silver chlorobromide emulsion (C, 06 mol silver) with a content of 80 Holyö bromide and a dispersion of 6.45 g des above coupler Λ in 1.3 ml of dibutyl phthalate, 1.5 S the above compound 42 as a bleach inhibitor and those used in the green-sensitive layer of Sample I. Containing sensitizing dye. This film is referred to as Sample I.I.

A color reproducing photographic film was also made prepared in the same way as in the case of the preparation of Sample II, except that the dispersion of the Coupler A has been omitted. This film is used as a sample III designated.

Furthermore, a color photographic reproduction film was made prepared in the same manner as in the case of the preparation of Sample II, except that the compound and the dispersion of Coupler A have been omitted. The film is referred to as Sample IV.

The amount of silver drawn up in the soundtrack "formation" layers of samples II to IV was 1.5 g / m and the narrowing of the other components present therein were the following:

309848/0982

Amount in the coating

Yellow pushes
Cyan layer

Magent3-layer

Soundtrack

educational

layer

Silver coupler gelatin

(Binder)

1.2g / m ² 1.2g / m ² 3, Gg / m ² O, 8 ₃ / m ² 1.5g / m ² 1, Sg / m ²

Λ , 1g / m ² 1.5s / m ² 3, Og / m ²

1.5g / m ² 1, Og / m ² 2, Og / m ²

strength

3.0

Menpren of sensitizing dyes

Cyan layer
Magenta layer '

Kl an g tracing layer

25 mg / mole silver 250 mg / mole silver

180 mg / mole silver

Ratio of the two magenta couplers = l / l on the weight based. '

Each of Samples I, II, III, and IV prepared in this way was gradually applied to a tungsten lamp

⁰ ) through an ultraviolet absorption filter, which

Light with wavelengths longer than about 400 em let through,

a .Yellow filter, - the light with wavelengths longer than about 500 mu let through and exposed a silver wedge. The intensity was 100,000 lux for 1/100 of a second. The filters used for exposure were those commonly used to expose color transfer films be used.

Each of the samples I, II, III and IV exposed in this way were prepared according to the methods given below . or B treated. The densities of the infrared range of the films (narrow band, peak at about 800 mu.

309848/0982

which is usually used to determine; the soundtrack density is used) was made using a Ütatur S-58 filter using a Macbeth TD-206-A type densitometer certainly. The results are in the following Table I listed.

Procedure A

3 negotiation level

Opening band laundry color wrapping

temperature 10 Time 15th Seconds II Seconds I! 2o Minutes and 15th üekun den I! 1 Cekun den 11 40 minute I! 3 Seconds t! 1 Minutes Il 15th minute m temperature 15th Seconds 27 ° C 2 Seconds 11 5 Minutes ti 10 Seconds ti customers.

First fixation laundry bleaching laundry Kl an gen tv / i c Irlun g Laundry Second fixation Laundry stabilization

The compositions of the above treatment The treatment baths used were the following:

Pretreatment solution: water sodium carbonate (monohydrate) Sodium sulfate (anhydrous) v / ater

800 ml 10.0 g

50.0 s

1 liter

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Color developer: "Water

Sodium hexametaphosphate Sodium sulfate anhydrous

2-amine o-5- \ diethylainin otoluene hydrochloride Sodium carbonate (monohydrate) Potassium bromide water too

First fixing solution and second fixing solution ,Water

Na triutnthio sulfate (5-hydrate) Anhydrous sodium sulfate glacial acetic acid boric acid potassium alum

Water to bleach solution:

V / ater

Ka liumbromi d Ka 1 i UEib i c h.r oraD t Potassium alum Natriura acetate (trihydrate) Glacial acetic acid

Water to Kl an g en tv.d c kler:

(Liquid A) water

Anhydrous ITodium sulfite N-methyl-o-aminophenol sulfate Sodium hydroxide Hydroquinone

232A79A , 0 g 800 nl liter 2 , 0 g ml 4th , 0 Ξ S. , 0 g , 0 g 25.0 g , 0 g , 0 g 1 '0 g' 600 liter 240 Hurry 15th , C- g 12th ■■ 0 g 6th , 0 g 15 · , 0 g η »0 g ' 800 liter 20th ml 5, ₍ 0 g 40. .0 g 3, 0 g 10, 0 g 1 600 40, 40, 40, 40,

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(Liquid B) water tragacanth gum Denatured alcohol (liquid C) ethylenediamine (? 0 %)

ml 10 ml 20 ml

The liquid A was mixed with the liquid B. and just before use, the liquid C became a total volume together with water to the mixture of 1.0 liter was added.

Stabilizing bath: Procedure B 800 ml water 10 ml Formalin (37 %) Polyethylene glycol (molecular weight 5 ml 400), 40% aqueous solution * 1 liter Water too

Treatment level

Pre-bath wash dye development

Laundry First fixation Laundry bleaching laundry Second fixation laundry Stabili si erun? S

temperature

Time

27 ⁰ C 10 seconds H 15 seconds Il 5 minutes
20 seconds It 15 seconds Il 1 minute 1". 40 seconds Il 3 minutes Il 1 minute Il 2 minutes Il 5 minutes Il 10 seconds

309848/0982

• The compositions of the above procedure Treatment baths used were the same as in the above procedure A.

Table I.

Sample I PI III IV

Procedure AB A B A B AB

density ⁰ * " ¹ > 95 ^G ' ^GA - ² '73 1 * 83 2.69 0.63 2.30-0.04

From the values in Table I it can be seen that Sufficient infrared density for samples I and IV was not obtained without applying sound development, while a high infrared density at an ordinary one Color development and no sound development was obtained in Samples II and III, which was color photographic Materials according to the invention that contain a bleach inhibitor A particularly high infrared density was obtained in Sample II.

Example 2

A color photographic playback film was made in prepared in the same manner as in the case of preparing Sample II in Example 1, except that a black Antihalation layer, the colloidal silver and gelatin contained, on the G-Rundierschicht according to Example 1 instead the formation of the antihalation layer containing carbon black on the back surface of the support became. The film is referred to as Sample V.

309848/0982

The amounts of coating for this layer were:

colloidal gelatin starch oilber

Antihalation ^ 2

Layer C, 5 g / V ¹ "2 g / m 2 h.

The sample was exposed in the same manner as in Example 1 and subjected to the process B according to Example 1, except that the pre-bath -were omitted and the immediately subsequent wash, whereupon the infrared density of the developed l ⁽¹ ilme in the same manner as was determined in Example 1. The results given in Table II were obtained.

Table II

Sample V

Procedure B

Infrared density 1.88

As can be seen, the same good results as in Example 1 were obtained with the color photographic material according to of the invention with an antihalation layer, the colloidal Contains silver.

Example 3

Each of Samples I, II, III, IV and V of Examples 1 and 2 was exposed as in Example 1 and then after treated by Method G below and the infrared density determined as in Example i. The results are summarized in Table III.

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Treatment level

Pre-bath laundry]?

Laundry blix treatment laundry stabilization

Procedure C Time temperature 10 seconds 27 ° G 15 seconds Tl 5 minutes and
• 20 seconds It - • 15 seconds Il 4 minutes Il 2 minutes Il 10 seconds Il

The composition of the blix bath was as follows:

Sodium iron (IIl) ethylenediaminetetraacetic acid sodium carbonate (monohydrate) borax

Sodium thiosulfate Water to ν

34.0 g 11.0 g 45.0 g

140.0 g

1 liter

The compositions of the treatment baths other than the blix bath were the same as in Method A above - -

Table III

sample I. II III IV V procedure 0 C. C. C. C. Infrared-
density 0.06 1.95 0.72 0.10 1.82

09848 / 098.2

From the values in Table III it can be seen that Samples II, III and V, the color photographic materials according to the invention, gave a high infrared density even when in the blix bath without application a sound development were treated, while sample I, which is in color photographic material from common type, and the sample IV with a sound track formation layer, however, which does not contain a bleach inhibitor, gave only low infrared densities.

Example- 4

A Farbphotographi shear playback film was in the prepared in the same manner as in the case of preparing Sample II in Example 1, except that 5.5 g of the above was prepared Coupler P instead of coupler A and 1.5 S of the above compound 44 instead of the * compound used. The film is referred to as Sample VI. Sample VI was made in the same manner as in Examples 1 and 3 exposed, developed and the infrared density certainly. The results are summarized in Table IV.

Table IV

Sample VI

Procedure B C.

Infrared density 1.85 1.90

As can be seen from the above values, a high infrared density was obtained in Sample VI which a color photographic material according to the invention

309848/0982

represents. Even if the sample is in an ordinary Bleach bath, - the potassium dichromate as an oxidizing agent for Containing silver, a high infrared density was similarly obtained.

Example 5 *

Color photographic films were made in the same manner produced as in Example 1 and Example 4, except that the position of the green-sensitive layer and the position the layer forming the sound track was replaced in each case. These films were recorded as samples VII and Samples VIII designated. These films were exposed, treated, and infrared density in the same manner as in Example 4 measured. The results are shown in Table V. ■ ·

Table V

sample B. VII C. 2 VIII B. C. procedure 1.90 1.93 ", 03 1 , 95 Infrared
density

As mentioned above, in the case of color photography, a high infrared density was achieved without applying sound development Film obtained according to the invention, where the sound track formation layer under the green-sensitive Emulsion layer was formed.

309848/0982

Example 6

Color photographic pilms were prepared in the same manner as in Example 5, except that 1.5 g of each of the above compounds 10, 40, 4 ^, 45, 51 and 59 in place of the compounds 42 or 44 and 2.7 g of the above coupler K in place used by coupler A or coupler P. The elm tree are referred to as samples IX, X, XI, XII ₁ XIII and XIV. These samples were exposed and treated as in Example 4, and the infrared density was determined. The results are summarized in Table VI. It can be seen from the values that a high infrared density was obtained in each lall.

Table Vl

sample

IX

XI

XII

X III

Anti-bleaching agents

procedure

^{2 '20}

² ' ^{? 0 1} > ⁸⁶

^{2 '20 2} ' ^{20 1} > 99

sample

XIV

Anti-bleaching agents

59

Procedure B

Infrared, _fi o density ^{1 '88}

309848/0982

. Example 7

Color photographic I'llme were prepared as in Example 6, except that 1.5% of the above compound 42 were used as ¹ bleach suppressant and 2.7% of the above-mentioned Coupler JF and 2.6 g of Coupler Q were each used as a coupler. The i'ilme are referred to as samples XV and XVI. The samples were exposed, treated, and the infrared density determined as in Example 4. The results are shown in Table VI. As can be seen from the table, a high infrared density was obtained in each line.

'·, Table VII Sample XV XVI

Coupler 1? B. C. Q B. C. procedure 2.20 1.98 1.88 1 ^ 76 In f rs red
density

Example 8

Samples II, III and V were exposed and treated as in Example 4 and the infrared densities were determined. To determine the change in density of the recording tape during storage, the samples were kept under the conditions of 60 ° C. and 70 % relative for 14 days The percentages of density changed before and after storage are shown in Table VIII.

309848/0 982

Table VIII

Sample II III V__

Procedure BC BC BC

Changed

infrared- ^{2 d} * " ¹⁰ ° 100 100 99 103

density

As is clear from the above table, even when the xarb photographic films according to of the invention under severe temperature and fire conditions stored viurae, a decrease in infrared density not observed.

The invention has been described above on the basis of preferred embodiments without being limited thereto is.

309848/0982

Claims (12)

Claims 1. Color photographic material consisting of a carrier with at least one "on it" blue-sensitive oilberhalogenidernuisionsschicht, which ^ contains a yellow dye-forming coupler, at least one red-sensitive emulsion layer which contains a cyan dye-forming coupler, at least one green-sensitive emulsion layer, which contains a magenta dye forming coupler, and at least one silver halide emulsion layer, the one bleach inhibitor with at least two hydroxyethylene groups contains. - 2. color photographic material according to claim 1, characterized in that the silver halide emulsion layer containing the bleach inhibitor is abutted the green-sensitive emulsion layer is formed. 3- color photographic material according to claim 1, characterized in that the silver halide emulsion layer, which contains the bleaching heamstoff, butting against an intermediate layer adjacent to the green-sensitive Emulsion layer is formed. 4-. Color photographic material according to claim 1, characterized in that the kilber halide emulsion layer- ^ containing the bleach inhibitor, adjacent is formed into the blue-sensitive emulsion layer. 5 'color photographic material according to claim 1, characterized in that the silver halide emulsion layer, which contains the bleach inhibitor, butting against an intermediate layer adjacent to the blue-sensitive Emulsion layer is formed. 6. A color photographic material according to claim 1 309848/0982 "to 5j characterized in that the silver halide emulsion layer, containing the bleach inhibitor further contains a coupler. 7-Parbphoto-Traphisehes material according to claim 1 "to 6, characterized in that the Lilberhalogenideiaul si one layer that contains the bleach inhibitor, one Sensitivity lower than 1/4 of the sensitivity the bilber halide emulsion layers to form the Has dye images. 8. Color photographic material still claim 1 to 7 »characterized in that the color photographic Material from a color photogx-aphic reproduction film (print filT.) exists. 9. Fax photographic material according to claim 1 to 8, characterized in that the bleach inhibitor -7 4 in an amount of 1 χ 10 'to 1 χ 10 g per hol of silver in the bilber halide emulsion layer containing the bleach inhibitor contains, is present. 10. Facsimile photographic material according to claim 1 till 9? characterized in that the lead inhibitor in an amount of 1 χ 10 to 1 χ 10 ^ g per hol of silver in the silver halide emulsion layer containing the bleach inhibitor contains, is present. 11. Vex-driving for the formation of dye images and imaging in a color photographic material according to claim 1 to 10, characterized in that the color photographic material an exposure, color development, Is subjected to bleaching and fixing. 12. The method according to claim 11, characterized in that that the bleaching and the fixation are carried out in a single bath system four den. 309848/0982 JBAD ORIGINAL