DE2540543A1 - PHOTOGRAPHIC MATERIAL WITH AN IMPROVED NEUTRALIZING LAYER - Google Patents

Description

PAT CN T /. NWA !. -: ΠΙ

H. KINKELDBY W. STCCKMAlR

Ζ · ί t -! NG. ^ '' f- lC '\: <Γ Cr';

K. SCHUMANN P. hi. JAKOS Ci. BEZOLD

i> 't f-i.ti JUÄT Di; i; HFM

MUNICH

E. K. WEIL

DR. REP. QIC Wj

8 MUNICH 22

VAXlMiLlANGTRASSE 43

P 9570

■ 11. Sept 1975

LINDAU

Fuji Photo Film Co., Ltd.

Ho. 21O ₅ Hckanuffia, Minami Ashigara-Shi, Kanagavia, Japan

Photographic material having an improved neutralizing layer

The invention relates to a photographic material which is disclosed in is able to automatically neutralize an alkaline developing solution. The invention particularly relates to a Diffusion transfer photographic material having such an ability.

After a photographic light-sensitive layer has been subjected to an alkaline development treatment, must the alkali and other developing ingredients the photographic layer can be removed. For this purpose a number of treatments are including a neutralizing treatment with an acid bath and

609813/0958

TELEPHONE (ΟβΟ) 22 28

TELEX Ο5-3Θ30Ο

E-.1- £ G * 3AV A'S ΜΟΝΑΡΛΤ

a washing used.

Some attempts have been made to achieve that only the treatment with the alkaline developing bath is carried out v / ground and that one has to pay attention to the washing hairs who connect to the alkaline developing substrate, renounce so that the subsequent treatment can be ended automatically without manual assistance.

In one such known method, the photographic image is stabilized by adding a polymeric acid layer incorporated as a coated layer in a photographic material, the alkali remaining in the system after an appropriate time after development and other treatments neutralized and other salt-forming components extracted with the polymeric acid layer to prevent its precipitation and deposition in the photographic material (See U.S. Patent 3,362,819 and U.S. Patent 3,362,821). It is also known to use a polymer in the above process, which contains carboxyl groups, and to crosslink the polymeric acid layer with a multifunctional compound.

The polymeric acid layer must contain acid groups in an amount sufficient to remove the alkali that is in the system after the treatment remains to neutralize and return the system to neutrality. A polymeric acid layer, which contains acid groups in salt form after neutralization, but has very increased hydrophilic properties. Therefore, a polymeric acid layer having a high content of acid groups is hydrophilic as it is, and it is The layer swells strongly after neutralization, so that the strength as a film is not retained and this results a dissolution of the layer. The limitation in acid group content, mixing with other polymers or the introduction of hydrophobic residues in order to

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to lower businesses below a certain value disadvantageous because the film thickness must be increased to a certain level Amount of acid groups per unit area or because the rate of neutralization for the alkali lowers will. Attempts have been made to make a polynaer with a high content of acid groups water-resistant make by using a crosslinking agent. In general, however, satisfactory results are not obtained because the reaction of the crosslinking agent rait the carboxyl groups does not proceed quickly enough and the hardening gradually during progresses for a long time and thus continuous changes accompany the neutralization. Under these circumstances there is a need to develop a polymeric acid layer with satisfactory water resistance despite a high content of acid groups.

The present invention is therefore based on the object of providing a polymeric acid layer with a sufficiently high content to create acid groups, whereby the layer should be a thin layer and a high neutralization capacity or should have neutralization power density.

According to the invention, a polymeric acid layer is to be created which has sufficient water resistance even if the layer absorbs alkali after developing Has.

According to the invention, a polymeric acid layer is to be created that makes quick neutralization possible.

According to the invention, a polymeric acid layer is to be created that can be easily applied or coated.

According to the invention, a photographic film unit or a photographic film element is to be created, in particular

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in particular, a diffusion transfer film unit having a polymeric acid layer, which has a high neutralization ability, good water resistance and a high neutralization speed.

The invention relates to a photographic material containing a support and a polymeric acid layer thereon for neutralizing a photographic alkaline processing solution after treatment with the processing solution, the water resistance being improved and in which a polymeric acid which is more than 3% is used mmol / g of carboxyl groups and wherein about 1 % to about 40 % of the carboxyl groups are in the form of the salt thereof, and wherein the polymeric acid is reacted with a crosslinking agent which contains at least two functional groups in the same molecule, such as an aziridyl group, a glycidyl group, a precursor group thereof and / or mixtures thereof.

The invention relates to a sheet or plate material for use in a photographic product, wherein the material has a carrier and on top of it a polymeric acid layer contains to make the photographic alkaline processing solution after the processing with the processing solution is finished to neutralize, which is characterized in that the polymeric acid is about 3 mmol / g or more than about 3 mmol / g of carboxyl groups, and wherein about 1 mol% to about 40 mol% of the carboxyl groups in salt form of which are present, and has been reacted with a crosslinking agent which has at least two in the same molecule contains functional groups selected from the group which contains an aziridyl group, a glycidyl group, a Precursor group thereof and mixtures thereof.

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_ 5 -

The object of the invention is thus satisfactorily achieved with a polymeric acid which is prepared by reacting a polymeric acid having about 3 mmol / g or more carboxyl groups, about 1 to about AO % of the carboxyl groups being neutralized to form salt forms thereof, with a crosslinking agent which contains 2 or more groups selected from an aziridyl group, a glycidyl group, a precursor group thereof or a mixture thereof in the same molecule.

The attached figure shows the swollen amount of the crosslinked polymeric acid layer versus the immersion time in an alkaline aqueous solution in comparison with a comparative sample. In the present application, the following terms are used synonymously: leaf \ bow, rail, plates "and film material.

The polymeric acid used in the present invention can be selected from synthetic or synthetic natural polymers containing carboxyl groups in an amount of from about 3 to about 17 mmol / g. The carboxyl groups can be linked directly to the main chain of the polymer or to a side chain or branched chain be. Many polymers containing 7 to 17 mmol / g carboxyl groups are particularly useful in the present invention preferred because they can be dissolved in an aqueous solution for coating. Homopolymers or copolymers Vinyl monomers containing carboxyl groups are particularly useful in the present invention. Examples of vinyl monomers containing carboxyl groups include acrylic acid, methacrylic acid, maleic anhydride (and compounds derived from it such as maleic acid, half esters or half amides), cinnamic acid, crotonic acid, citraconic acid, p-carboxystyrene, vinyl cc-carboxymethyl ether and

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similar connections. Monomers - those for copolymerization used with the vinyl monomers mentioned above can include ethylenically unsaturated monomers such as ethylene, Vinyl acetate, styrene, alkyl vinyl ethers, acrylic esters, methacrylic esters, Acrylamide, methacrylamide, etc.

The polymeric acid used in the present invention must have a molecular weight sufficient to that a strong film is formed after the polymeric acid has been crosslinked. The appropriate molecular weight The range depends on the polymer used. A suitable molecular weight is generally in the range from 5,000 to 500,000 and is preferably from 10,000 to 200,000. Polymeric acids which can be used to advantage in the present invention have the following structural unit :

and / or - [- CH - CH -

COOH COOH

where R is a hydrogen atom or a methyl group, Specific examples of polymeric acids that can be used to advantage in the present invention can be given given below in the form of their structural units.

P 1

CH \ -

'J COOH

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2 5 4 O 5 A

P 2

2 " ^CH 2 ~ t ~ 0.25 ~ Π - ^CH

Γ J 0.75 COOH

—J-CH ₂ - CH-4— COOCH, - CH-

0.2 L COOH

0.8

P 4

- f-CH - CH ι ι

«- COOH COOH

CH ₀ - CH-

COOH

⁰ » ⁵

-I

0.5

I, I ? ^H ~ K?

COOH COOH

CH

OCOCH

0.5 CH - CH-

¹ J 0.5 COOH COOH

6 098 13/095

EJL

CIL · - CH

OCH,

0.5 '

CH-

COOH COOH

P 8

CH - CH- t t

COOH COOH 0.5

-J-CH ₂ -

CH

0.5

COOC ₄ H ₉ (n)

CH

COOH COOH 0.5

P 10

CH ₉ - CH

COOH

CH ₂ - CH -j- _Ot3 - (- CH- CH- OCH, COOH COOCH-

0.5

CHo -

CH-OCH-

0.5

CH - t

COOH

CH ι 0.5

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P 15

CH ₉ - CH

0.6

COOH CH

CH ₂ -C-

COOCH ₂ CH ₂ OH

0.4

P 14

-J-CH ₂ -

CH ι

COOH

0.65 CH ₀ - CH-

0.35

COOCH ₂ CH ₂ OH

P 1

CH K

t J

COOH CH,

CH ₉ - C

COOCH ₂ Ch ₂ OOCCH ₂ COCH ₃

0.2

P 16

~? ^H J 0.8 COOH

CH ₀ - CH

0.2

CONH.

P 17

CH t

COOH

0.7

C. - CH

Λ "\ CON

0.3

P 18

■ i

CHo -

CH OH

0.4

CH ₂ - CH OCH ₂ COOH

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It has been found that these polymeric acids can be cured quickly and effectively with a crosslinking agent containing an aziridyl group or a glycidyl group when the carboxyl groups contained in the polymeric acid ο are partly in the salt form thereof. This hardening accelerating effect is apparently observed when about 1 % of the carboxyl groups are in the salt form thereof, and it is particularly pronounced when about 5 to 30 % of the carboxyl groups are in the salt form thereof. In order to achieve the objects of the present invention, it is disadvantageous if more than about 40 %. of the groups are in the salt form thereof because the hardening is somewhat reduced and, in addition, the neutralization performance value is lowered due to a decrease in the free carboxyl groups available for neutralization. A wide variety of inorganic or organic bases can be used to form the carboxy Examples of bases that can be used to advantage in the present invention include alkali metal hydroxides, alkaline earth metal hydrides, alkali metal salts of weak acids, ammonium hydroxide, organic amines and precursors thereof, and the like compounds. Specific examples of bases are lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, borax, sodium phosphate, potassium phthalimide, sodium phenolate, ammonium hydroxide, tetramethylammonium hydroxide, butylamine, triethylamine, pyridine and piperidine They can be added to a polymeric acid solution prior to application of the solution to a support, or they can be applied to the layer from the outside after coating (e.g. from another layer adjacent to the layer).

Crosslinking agents used in the present invention

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have at least two functional groups selected from aziridyl groups in the same molecule. Glycidyl groups and precursor groups thereof such as epicblorohydrin and mixtures thereof. These functional groups can have various types of chemical compounds with one another be connected.

Examples of suitable cross-linking agent _f which can be used in the present invention are compounds represented by the general formulas (I) or (II) ϊ

CD

wherein R ^, R ₂ , R ₇ ? _{R 1} and -R 1 -, which can be the same or different, each denote a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, η denotes an integer from 2 to 6, and A 1 denotes an acyclic or cyclic group Containing nitrogen or oxygen atoms bound to the glycidyl group, the number of nitrogen or oxygen atoms present corresponding to η, for example polyvalent amines, polyhydric or polyhydric alcohols and derivatives thereof such as ethylene diamine, p-phenylene diamine, ethylene glycol, tetraethylene glycol, glycerol, sorbitol, Hydroquinone and similar compounds, or a 5- or 6-membered heterocyclic group, for example imidazoline, pyrazolidine, triazoline, piperazine, triazine and similar groups, in which the heterocyclic group can be bonded to a hetero atom such as S, N, O, etc.,

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or derivatives thereof or a nitrogen atom, a phosphate group, a sulfate group or similar groups, or

(U)

wherein Rg is a hydrogen atom or an alkyl group with 1 is up to 3 carbon atoms, η is an integer from 2 to 6 and Ap is an acyclic or cyclic group containing carbon, nitrogen, sulfur or phosphorus atoms bonded to the aziridyl group, where the number of these atoms present corresponds to η. The above acyclic and cyclic groups can be heteroatoms contain and the aziridyl groups associated with Ap can be the same or different.

The synthesis of these compounds is described, for example, by G.A. Buehler and D.E. Pearson, Survey of Organic Syntheses, Wiley-Interscience, p. 285 (1970), Nippon Kagakukaihen Jikken Kagaku Koza (Experimental Chemical Lecture, edited by the Japanese Chemical Society), Volume 17, Yukikagobutu no Hanno (1) (Reaction of Organic Compound (1)), Maruzen Volume 1, p. 282 (1957), H. Lee and K. Neville, Epoxy Resins, McGraw-Hill p. 3 (1957), Production and Application of Epoxy Resin, edited by Kakiuchi Kobunshi Kagaku Kankokai, p. 101 (1963) and by M. Budnowski, Kunststoffe, Volume 55, P. 641 (1965).

The crosslinking agents containing glycidyl groups are particular for the practice of the present invention

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useful. Those crosslinking agents which contain aziridyl groups often have a strong physiological effect on the human body and therefore special precautions should be taken be taken on to persons involved in the manufacture of photographic materials containing such compounds included, are concerned. Many types of compounds containing at least two glycidyl groups are known. Many of these types of connections are suitable for practicing the present invention. Particularly useful glycidyl compounds are given below:

G - 1

CH ₀ - CH - CH ₀ - O - (CH ₉ ) "- OCH ₀ - CH - CH

n ^ = 2, 3 »4 etc.

G - 2

O = P - (O - CH ₂ - CH G - 5

CH ₀ - CH - CH ₀ - 0 "OCH ₀ CH - CH

^ ² v% / ²

^X 2

OCH ₂ CH - CH ₂

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G - 4

- CH - CH ₅ )

G - 5

CH ₂ - CH - CH ₂ - "

N ⁺ - CH.

j .j

G - 6

CH ₂ - CH - CH ₂ - O - CH ₂ - CH ₂ - O - CH ₂ CH ₂ - CH - CH,

G - 7th

It

CH ₀ - CH - CH _n -

CH, t ^c CII

OH N - CH ₉ - CH - CH, CH ₂ OOCCH ₃

G - 8

CH. t.

- CH ₀ - N Έ - CH ₀ - C - CH

CH _x

CH ₉ -C- CH

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G - 9

CH, f

-CH- CH ₂ -N- CH ₂ CH, ι 3

- CHo - N - CH ₀ - CH

CH ₀ /

G - 10

OCH ₂ CH

0 - P - OCH ₀ t * -

OC ₂ H ₅

CH - CH ₀ - Cl t ^

OH

G ~ 11

Cl - CH ₀ - CH - CH ₀ - 0 - CH ₀ - CH - Cl

Oh
OH

G - 12

Cl - CH _{9 - CH - CH 0} - SO ₀ - CH ₉ - CH - CH 'Cl

OH OH

G - 13 CHo - CH

CH ₀ - 0 - (Z> 0 - CH ₀ - CH - CH ₀

G - 14

O =

P-OCH ₂ -CH

0CH ₀ - CH - CH c. \ / t

609 813/0958

O = P [~ O - (CH ₂ ) _η - OCH ₂ -

G - 16

Il

zip - ct J ₁ +.

- P (OCH ₂ - CH - CH ₂ ) ₂

-CH- CH ₂ ) ₂

0 - P (OCH "

In addition to the above compounds, multifunctional! - le low molecular weight glycidyl compounds as disclosed in US Pat. Nos. 3,047,394 and 3,091,537 of German Patent 1,113,807, den FR-PSs 1,231,056 and 1,270,785 and USSR-PS 151 described, and polymeric glycidyl compounds as in US Pat U.S. Patent 3,623,878 in the present invention be used. Many can in practicing the present invention known multifunctional aziridyl compounds can be used. Aziridyl compounds are particularly useful specified below:

A - 1

.CH,

CH,

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CH CH,

17 -

CH,

C.

'CH,

CH ₂ -

A - 3

A - 4

CH, - CH. 3 ι

CH.

CH,

CH,

- < ; N- C. * C ^ Il N N ^: C 1 .N CH ₂

.n:

- CH,

CH - CH,

"CH

N - CONH - (CH ₀ ) - NHCON

.CH,

CH

A - 5

CH

CH,

η- * is an integer from 2 to

CH

N - SO ₂ - (CH ₂ ) _n - SO ₂ -

Πλ is 2, 3, 4, 5, 6 etc. 1 3/0958

A - CH, - CH

J ι '

_N JP =; N

CH - CH,

N = P- - N.

XH

A -

It

-P-N =

A -

2 /

A - CH, CH,

0 ti

N-C-Ni

.CH,

CH,

A -

CH ₀ - CH

CH, CH,

Il

CH

CH,

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A - 11

CH

A - 12

ON
\ /

ti

P i

CH ₂ - CH

CH.

CH,

A - 13

813/0958

In addition to the compounds described above, multifunctional low molecular weight aziridinyl compounds used as described in US Pat. No. 2,950,197 »

2 964 404, 2 983 611, 3 392 024, 3 492 124, 3 549 378 and

3,575,705, in GB-PSs 797 321 and 918 950, in DT-PS 1 165 405 and in FR-PS 1 224 860, and furthermore polymeric aziridinyl compounds can be used v / ground as described in U.S. Patent 3,671,256.

The crosslinking agent can be incorporated into the polymeric acid layer or it can be incorporated into a layer that is adjacent to the polymeric acid layer is appropriate (for example in a control layer) and diffuse into the polymeric acid layer. The amount of wetting agent that is used is approximately 0.2 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the weight of the polymeric acid used.

According to the invention, the polymeric acid layer effectively and quickly neutralizes the alkali that remains in the system, and extracts other salt-forming components after the photographic processing is substantially completed. The polymeric acid layer can be incorporated into various photographic systems. Through training or incorporation of the polymeric acid layer can be an aftertreatment subsequent to the development, in particular washing, omitted, shortened or simplified. The photographic systems in which the present In the present invention, there are conventional silver halide light-sensitive materials and photographic ones Diffusion transfer materials.

The invention is particularly useful for diffusion transfer photographic systems. The polymeric acid layer can be incorporated into these systems in various arrangements. For example, the following arrangements are for

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the implementation of the present invention is advantageous:

(i) an arrangement in which a polymeric acid layer and an image-receiving layer can be applied successively to a first support, a syrup halide emulsion layer is applied to a second support and a treatment solution in layer form between the image-receiving layer and the silver halide emulsion layer spread as described in U.S. Patent 3,362,819;

(ii) an arrangement in which a polymeric acid layer and

• a silver halide emulsion layer on top of one another first support are applied and an image-receiving layer is applied to a second support, and a treatment solution in the form of a layer between the image-receiving layer and the silver halide emulsion layer spread as described in U.S. Patent 3,362,821;

(iii) an arrangement comprising a polymeric acid layer, an image receiving layer (and, if desired, a stripping layer or a light reflective layer) and a silver halide emulsion layer on a second support applied in succession, and a treating solution on the surface of the silver halide emulsion layer applied as described in U.S. Patents 3,594,164 and 3,594,165;

(iv) an arrangement in which a polymeric acid layer on a first support, an image receiving layer, and if applicable a stripping layer or a light reflective layer and a silver halide emulsion layer applied to a second support v / ground, and a treatment solution in layer form between the polymer Layer and emulsion layer, as described in Canadian Patent 928,559 and U.S. Patent 3 647 437 is described.

In the above embodiments, the polymeric acid layer is desirably isolated from the treating solution layer or separated, namely by a layer that regulates the rate of neutralization, or by a Control layer. This layer can prevent undesirable deterioration in photographic density,

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which is caused by a premature decrease in the pH of the system, caused by the influence of the acidic polymers Layer before the stages required for the formation of the photograph! See forms. How the development of the Si Ib eiiialogenidomul si cms layer and the formation of the diffusion transfer image, are essentially ceased, and they can delay the decrease in pH before the desired one Image formation essentially ceased int. Useful control layers include polymeric layers of gelatin, Polyvinyl alcohol, polyvinyl propyl ether, polyacrylamide, hydroxypropylmethyl cellulose, Isopropylcollulose, partially butyrated polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, Copolymers of ß-Hydroxyäthylniethacrylat with ethyl acrylate or similar compounds and a polymeric layer which increase the latitude of the treatment temperature can, as described in US Pat. No. 3,455,685, as well as a mixed polymer layer consisting of a continuous phase made of a hydrophobic polymer and a discontinuous one A hydrophilic polymer phase as described in US Pat. No. 3,785,815.

In the photosensitive elements used in the present invention, materials which can produce dye images be associated with the silver halide emulsions.

In the dye image-forming material used in the present invention can be used, it is a compound that occurs as a result of the development of an imagewise exposed silver halide emulsion a two-dimensional Distribution of diffusible according to the exposure

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Gives dyes. There are already different one dye image forming materials known to be used in the development of silver halide on the basis of various Systems can form diffusible dyes, examples of such systems are (i) a system in which the a change in their dye image-forming materials Diffusivity experience as a result of oxidation with silver halide, (ii) a system in which the one dye image forming materials react with an oxidation product, which has been oxidized by the silver halide to release diffusible dyes, and (iii) a system in which the oxidized, a dye image forming materials with an aid under-react Release of diffusion-prone dyes. With these In systems, oxidation with silver halide leads directly to the formation of diffusible dyes. aside from that there is (iv) a system in which limited amounts of developer compounds and a part of the developer connections that are not consumed during development can move into the image-receiving layer and is converted into dyes there, (v) a system, in which limited amounts of developer compounds are used and some of those not used in development Developer compounds react with the dye image-forming materials to form diffusible ones Dyes, (vi) a system in which a component which is associated with the oxidation product of the developing agent, z. B. a coupler, can react, is used in a limited amount and that after the reaction reactive constituents remaining after development migrate into the image-receiving layer and is converted into dyes, and (vii) a system in

6 0 9813/0958

the silver ions obtained from silver halide, which in the Development have not been consumed with the dye image-forming materials to be reacted under Formation of diffusible dyes. In these systems, the components that are used in the development and are not consumed in the reaction following the development, to produce images of diffusible dyes. In addition, there is (viii) a system in which, by developing silver halide grains a mordant is formed or destroyed around the silver halide grains to be fixed or released of diffusible dyes.

Thus the dye image-forming material of the present invention Can be used in diffusion transfer color photography, a complete dye structure residue or the dye structure residue can be present in the Development and the subsequent competitive level are formed. Alternatively, they can be used to form dyes The necessary components are allowed to migrate into the image-receiving layer together with the dyes formed thereon will.

The dye image-forming materials themselves that are used in diffusion transfer color photography according to the invention are useful during manufacture, storage and imagewise exposure of the photosensitive Materials non-diffusible. In terms of development and diffusion transfer, however, they can depend on different from the system of generating the dye image distribution Have types of diffusivity. In one system, for example, one is subject to a dye image

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forming material that is soluble and diffusible in the developing solution, a decrease in diffusivity as a result of development, and it is fixed while the undeveloped dye image-forming material is transferred to the image receiving layer. In another system, this sets a dye image forming Material that is nondiffusible even in the developer solution, a diffusible dye, or releases a diffusible dye precursor as a result of development.

According to the present invention, dye image-forming materials can be used based on various combinations of the development and conversion systems described above in dyes, the steps described above for the formation of the dye structure residue and the diffusivity be used. Particularly suitable dye image-forming materials are as follows:

(a) Dye developer

As disclosed in U.S. Patent 2,980,606, acts A dye developer is a compound that has both a dye structure residue and a silicon superhalide developing group contains in the same molecule. When this dye developer and an alkali on Image-wise exposed silver halide emulsions are applied, a reduction of the silver halide occurs at the same time and oxidation of the color developer. The oxidized dye developer has a developing solution a lower solubility and a lower diffusivity than the reduced form of the original

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Dye developer, and it will therefore be close to the reduced Silver halide fixed. In a preferred embodiment, the dye developer has at least a dissociable group which is the dye developer Practically insoluble in an acidic or neutral aqueous medium, but it is insoluble in the alkaline developer preparation makes soluble and diffusible. Such a dye developer can be converted into a photosensitive one Element, in particular incorporated into the silver halide emulsion layers or into layers adjacent thereto will. When the diffusion transfer of one photosensitive element with two or more photosensitive Units in which a silver halide emulsion and a dye developer with those opposite to the light-sensitive Wavelength range of the silver halide emulsion corresponding absorption properties combined is carried out on an image-receiving member, multi-colored positive images can be obtained by development treatment can be obtained. The light absorption of the dye developer is conveniently that which the reproduction of colors according to the principle of subtractive color photography, d. H. Yellow, purple, or blue-green images supplies. The remainder of the dye structure that is such Gives absorbency, can of azo dyes, anthraquinone dyes ^ phthalocyanine dyes, nitro dyes, Quinoline dyes, azomethine dyes, Indamine dyes, indoaniline dyes, indophenol dyes, Azine dyes and the like.

On the other hand, the silver halide developing group represents a group that is the silver halide struck by light can reduce, preferably such a group,

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which, as a result of oxidation, loses its ability to in alkaline solution to become soluble. Generally suitable a benaol-like developer group, d. H. one aromatic developer group which, after oxidation, forms a benzene-like structure (benzenoid structure). B-ine the preferred developing group is a hydroquinonyl group. Other suitable developer groups are an o-dihydroxyphenyl group, an o- and p-amino substituted hydroxyl group and the like. In preferred dye developers are the Dye Structure Eest and the Developer Group by a saturated aliphatic group, such as. B. an ethylene group, which prevents electronic conjugation, separated from each other. A 2-hydroquinonylethyl group and a 2-hydroquinonylpropyl group are particularly suitable. The dye structure residue and the developer group can have a coordination bond, as in the US patents 3,551,406, 3,563,739, 3,597,200 and 3,674 described, as well as connected to one another via a covalent bond. Besides, it is for some uses and some structures of the color diffusion transfer photographic materials advantageous to reduce the residual dye structure, thereby temporarily reducing it to convert into a colorless leuco form, as described in US Pat. No. 3,320,063, or the hydroxy or Acylate the amino group of the auxochromic residue, thereby temporarily reducing the absorption to the side of the shorter Shift wavelength, as in US patents 3 230 085 and 3 307 9 ^ 7. Dye developer with a dye structure residue containing a hydroxyl group in the ortho position to the azo bond are useful in that they have excellent absorption properties and excellent color image stability,

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as indicated in U.S. Patent 3,299,041. Other dye developers suitable for use in diffusion transfer color photography are described in U.S. Patents 2,983,605, 2,992,106, 3,04? 386, 3 0? 6 808, 3 076 820, 3 077 402 ,. 3 126 280, 3 131 061, 3 134-762, 3 134 765, 3 135 604, 3 136 605, 3 135 606, 3 135 734, 3 141 772, 3 142 565, 3 173 906, 3 183 090, 3246 985, 3,230,086, 3,309,199, 3,230,083, 3,239,339, 3,347,672, 3,347,673, 3,245,790, 3,230,082 and the like. Specific examples of dye developers that can be used in diffusion transfer color photographic materials are as follows:

4- fp - (/ S-Hydroquinonylethyl) phenylazoJ -3- (K-n-hexylcarbamoyl) -i-phenyl-5-pyrazolone,

2-fp - (/> - Hydroquinonylethyl) phenylazoJ -4-isopropoxy-i-naphthol, 1,4-bis-r _/ / 5- (hydroquinonyl-ct-methyl) -ethylaminoJ-5,8-dihydroxyanthraquinone.

C ₃ H ₇ O

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HIGH ₂ CH ₂

HIGH ₂ CH ₂

^> S0;

N = N — C — C — CH,

/ CN
O / CT \ /

OH

OH

HO

OH

CH,

CH ₂ HC-NHO ₂ S-

OH

OH - N

OH

N- Cu ~ N _V

L- ^ ^c

CH.

SO ₂ NH-CH-CH,

? 3

CH ₂ CHNHSO ₂

ΐ / V I '

N = (Γ C-N OH

OH

fs.

SO ₀ NHCH-CH.

OH

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In diffusion transfer color photography where a Dye developer as a dye image forming material it is beneficial to have an assistant developer association to use to speed up development. To this end, developer compounds such as z. 1-phenyl-3-pyrazolidone as described in U.S. Patent 3,039,869, hydroquinone derivatives, e.g. B. 4 -'-methylphenyl hydroquinone, t-butylhydroquinone and the like, or catechol derivatives as described in US Pat. No. 3,617,277, in a liquid developer preparation or in a light-sensitive element, in particular in a silver halide emulsion layer, a layer containing a dye developer, an intermediate layer or in a Covering protective layer can be incorporated. Also can to accelerate development and diffusion transfer, development in the presence of an onium compound, such as B. JN-Benzyl-e ^ -picolinium bromide, as in U.S. Patent 3 173 / ^ 86 described.

(b) A diffusible dye releasing coupler

It is a dye releasing coupler is a reactive, non-diffusible compound that interacts with the oxidation product of the developer compound can react and as a result of the coupling reaction is able to eliminate and release a dye, which is soluble and diffusible in the development treatment preparation. One type of one diffusible Dye-releasing coupler has a structure in which the coupling reaction center passes through a residue is replaced by the oxidized developing agent is eliminated. The electron conjugation system

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of the dye to be released can either start in the coupler can be incorporated, or it can be through the Coupling reaction are formed. In the first mentioned case, it is a "pre-formed type". Coupler this type-exhibit roughly the same spectral absorption on like the released dyes. The latter type is what is known as "instantly educated." Type ". Couplers of this type are in principle colorless and when they are colored their absorptions have none Relationship to the .Absorption of the released dye, and they are temporary. Typical examples of one Diffusible dye releasing couplers are such of the following general formulas:

(1) (Cp-I) -L- (Fr) ("preformed type") and

(2) (Cp-2) -L- (Bl) ("directly formed type"),

wherein Cp-1 is a structure active for the coupling reaction represents, in which the coupling position by a (Fr) -L residue and at least one Wicht coupling position by a Group which contains a hydrophobic group with 8 or more carbon atoms and is capable of diffusion resistance or ballast properties to the coupler molecule to give, wherein Cp-2 is a structure active in the coupling reaction in which the The coupling position is substituted by a (B1) -L radical and in which, if the coupler is in combination with a developer compound, which does not contain a water-solubilizing group is used, the Cp-2 group a water-solubilizing group Group in at least one non-coupling position on v / eist and (Fr) -L- and (Bl) -L-groups represent through the oxidized developing agent can be eliminated, wherein

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For a dye structure residue with an absorption im visible wavelength range and at least one water-solubilizing group and B1 mean a group which a hydrophobic group having 8 or more carbon atoms and makes the coupler molecule resistant to diffusion. "

Examples of structural residues that are reactive in the coupling reaction, which can be used as Cp-1 and Cp-2 are many functional groups known to be undergo an oxidative coupling reaction with an aromatic primary amine color developing agent. Examples these are phenols, anilines, cyclic or open-chain active methylene compounds and hydrazones. Specific Examples of particularly suitable reactive structural residues are those which are derived from acylamino-substituted phenols, i-hydroxy-2-naphthoic acid amides, N, N-dialkylanilines, i-Aryl-5-pyrazolones, the 3-position of which by a Alkyl, aryl, alkoxy, aryloxy, amino, acylamino, ureido or sulfonamido group is substituted, pyrazolobenzimidazoles, Pyrazolotriazoles, .- <. -Cyanoaeetophenonen and oC-Acylacetaniliden are derived.

Examples of the linking or bridging group L, whose Bond to the coupler structure residue is split by the oxidized developer compound, are an azo group, an azoxy group, a mercuryl group (-Hg-), an oxy group, a thio group, a dithio group, a triazolyl group, a diacylamino group, an acylsulfonamino group

ι
^ ' ^{an Acvl} oxy S ^ru -ppe, a SuIf ο ny 1 oxy group and

an alkylidene group. Among these are an oxy group, one

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Thio group, a dithio group, a diacylaraino group, a Acyloxy group and the like, which are eliminated as an anion, are particularly suitable, since the amount of the released diffusible dyes is great. The coupling position of the coupling structure of a fhenol or naphthol is preferably substituted by a group which has an oxy group, a thio group or a Diacyloxy group is associated with it. Also the coupling position of a pyrazolone is preferably substituted by an azo group, a thio group or an acyloxy group , and the coupling position of an acylacetaniline is through an oxy group, a thio group or a diacylamino group substituted.

Representative examples of dye structure residues for Fr are those of azo dyes, azomethine dyes ^ indoaniline dyes, Indophenol dyes, anthraquinone dyes, nitro dyes, azine dyes and the like derived residues.

Those contained in the residues represented by Cp-1 and B1 hydrophobic residues create a cohesive force between the coupler molecules in an aqueous medium and make the molecule in a hydrophilic colloid that makes up the photosensitive material, non-diffusible. as hydrophobic radicals can advantageously be a substituted or unsubstituted alkyl group, an alkenyl group, a Aralkyl group and an alkylaryl group having 8 or more carbon atoms be used. Examples of such groups are a lauryl, stearyl, oleyl, 3-n-pentadecylpheny.1-, 2,4-di-t-amylphenoxy group and the like. These hydrophobic residues are directly or via a divalsnte bond,

like ζ. B. an amino, ureido, zither, ester or sulfonamido bond to a fundamental coupling structure bound to form Cp-1. These hydrophobic residues also form with one another or together with an aryl group, a heterocyclic group or a similar group, which is bound to it directly or via one of the abovementioned divalent bonds, the B1 group.

Those contained in the residue represented by Cp-1 or Fr Water-solubilizing group is an acid group that essentially dissociates in a developing solution is or represents a precursor which provides such an acidic group on hydrolysis. Are particularly suitable acidic groups with a pKa no greater than about 11. Examples of such groups are a sulfo, sulfuric acid ester (o-iso-3H) -, carboxy, sulfonamido, diacylamino, Cyanosulfonamino, phenolic hydroxyl groups and like that.

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The diffusive dye releasing couplers of the general formula 1 are subject to cleavage of "in the reaction with an oxidized developer compound L-bond forming a non-diffusible Condensate between Cp-1 and the developer compound and a soluble dye containing the Fr structural residue. This soluble dye diffuses into the image receiving layer to form dye images.

The couplers of the general formula 2 releasing a diffusible dye are subject to the reaction with of an oxidized developing agent cleavage of the L-bond to form a soluble dye which is the oxidation coupling reaction product between Cp-2 and the developer bond, and a non-diffusible eliminated product derived from B1. This soluble dye diffuses into the Image receiving layer to form dye images.

Specific examples of a diffusible dye releasing coupler represented by Structural Formula 1 Types are the following:

oc- [4- (8-Acetamido-3,6-disulfo-1-hydroxy-2-naphthylazo) -phenyl] -a-pivalyl-4- (N-methyl-N-octadecylsulf amyl) acetanilide disodium salt;

1- (p-t-butylphenoxy>: yphenyl) -; 5- [a- (4- t-butylphenoxy) propionamido] -4- ^ -bromo - ^ - methylamino-5-sulfo-1 -anthra-9,10-quinalyl-azo) -5-pyrazoline;

1 -hydroxy-4- ^ 3 ~ O- (N-ethyl-N-ß-sulfoäthylamino) -2-methylphenylazo] phenylazo} -Ή- [8-C2,4-di-t-amylphenoxy) butyl] - 2-naphthamide sodium salt.

Specific examples of a diffusible dye releasing coupler des dm-ch represented structural formula 2 Types are the following:

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α- [4-methoxybenzoyl) -cx- (3-octadecylcarbamylphenylthio) -3,5-dicarboxyacetanilide;

α-Pivalyl-α-O-octadecylcarbamylph-nylthio) ^ - sulfo-acetanilide potassium salt;

1-Phenyl-3- (3,5 ~ dicarboxyanilino) -4- (3-octadecylcarbainylpheny 11 hio) - 5-pyrazolone;

1-phenyl-3- (3 ~ disulfobenzoylamino) -5 ~ (2-hydroxy-4 ~ n-pentadecylphenylazo) -5 ~ pyrazolone;

1- [4- (3,5 ~ dicarboxybenzamido) phenyl] -3-ethoxy-4- (3-octadecylcarbaBiylthio ) - 5-pyrazolone;

1-hydroxy-4- (3-octadecylcarbamylplienylthio) -N-ethyl ~ 3 ', 5' dicarboxy-2-naphthanilide;

1-Hydroxy-4- (n-octadecylsuccinimido) -N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide .

More specific examples of a diffusible Dye releasing couplers and their synthesis are described in British Patents 84-0731, 904 364, 1,085,631 and in U.S. Patents 3,476,563, 3,644,498, and 3,419 described.

The second type of diffusible dye releasing coupler is that in the substituent in the the dye residue contained in the position adjacent to the coupling reaction position is split off and in the case of an intramolecular Ring closure reaction with the substituent released, which occurs subsequent to the condensation reaction with the oxidized developing agent. Particularly suitable is in particular the reaction in which an aromatic amine developing agent is oxidatively attached to the 4-position of the phenol or aniline is coupled and then together with a suI-foiiamido group in the 3-position, which is the remainder of the dye structure contains, forms an azine ring with the release of a diffusible dye with a sulfonic acid group. Specific examples of couplers of this type are as follows:

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1-phenyl ^ -äthylcarbamoyl ^ - j ^ -methoxy ^ - [Nn-dodecyl-N- (i-hydroxy-4-chloro ~ 3-naphthyl)] sulfamylphenylazo I- 5-pyrazolone. 2- (β-octadecylcarbamoylethyl) -4- ^ 2- [4- (2-hydroxy-1-naphthylazo) phenylsulfonamido] anilinojphenol and the like.

Examples of primary aromatic amine developing agents to be used with; Advantage in combination with the one diffusible Dye-releasing couplers that can be used are:

p-aminophenol, p-phenylenediamine and derivatives thereof, in particular 2-chloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 4-amino-N, l · T-diethyl-3-methylaniline, Ν, Ν- Diethyl-p-phenylenediamine, N-ethyl-ß-methanesulfonamidoethyl-3-ynethyl - ^ - aniinoaniline, 4-amino-N-ethyl-N- (o-sulfobutyl) -aniline, 4-amino-U-ethyl- (ß -hydroxyathyI) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, ^ -amino-N-ethyl-N-Cβ-carboxyethyl) aniline, ^z ^ -> - amino-l I, N-bis (ß-hydroxyethyl) -3-methylaniline, 3-acetamido-4-amino-N, N- (ß-hydroxyethyl) aniline, 4-amino-N-ethyl-IT- (2,3- dihydroxypropyl) -3-methylaniline, 4-amino-N, N-diethyl-3- (3-hydroxypropoxy) aniline, 4-amino-N-ethyl-N- (ßhydroxyäthyl) -3-methoxyaniline and the salts of these anilines, such as for example the hydrochlorides, sulfates, oxalates, p-toluenesulfonates and similar salts. In addition, precursors of these developer compounds, such as the Schiff's bases of these anilines and phthalimides, can be used because they can be added to a photosensitive element.

Negative silver halide emulsion layers, which one Containing diffusible dye releasing couplers will result in negative diffusion transfer dye images upon development. On the other hand, direct-positive silver halide emulsion layers containing the diffusible dye releasing couplers are positive Diffusion transfer dye images. As a direct positive Emulsions may include those of the internal latent image type such as

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in U.S. Patents 2,592,250, 2,588,982, 3,22? 552 and the like, and fogged emulsions such as those described in British Patent Nos. 443 24-5, 462 730 and in U.S. Patents 2,005,837, 2,541,472, 3,367,778 and the like can be used.

Positive diffusion transfer dye images can be obtained Are provided by developing a layer adjacent to the negative silver halide emulsion layer and contains the diffusible dye releasing coupler and physical development elements, with a developer containing a solvent for silver halide. Process for generating reverse dye images using physical development such as that disclosed in British Patent 904-364 can also be used will. In addition, photosensitive elements provided contiguous with a silver halide negative emulsion layer with a compound (DIR compound) that reacts with an oxidation product of a developer compound a development inhibitor such as i-phenyl-5-mercaptotetrazole releases a layer with a diffusible one Contain dye releasing couplers and a spontaneously reducible metal salt, positive diffusion transfer dye images, as in U.S. Patents 3,227,551, 3,227,554, 3,364,022 and in German Offenlegungsschrift 2 032 711. According to the invention can a combination of these emulsions and the dye image-forming material can be used and it can appropriate ones depending on the intended end use Systems can be selected that provide negative and positive dye images.

(c) Reducers that release a diffusible dye

ti £ nsmitt_el.

In addition to the above-mentioned color

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substance developers and a diffusible dye • releasing couplers form a dye image Material used after oxidation during development by intramolecular reaction or by Implementation with an auxiliary compound contained in the solution releases a diffusible dye. In this type of dye imaging, it is advantageous that to oxidize the dye image-forming material using an auxiliary developing agent such as a Hydroquinone, a 5-pyrazolidone and the like. The oxidized, a dye image-forming material sets under the Exposure to a supplement agent such as hydrogen ions, Sulfite ions and the like present in a developer composition or in a photosensitive member, the diffusible dye free. Specific examples of dye image forming agents of this type are in U.S. Patents 3,585,026, J 698 897 and in US Pat German Offenlegungsschrift 2 242 762.

The dye image forming used in the present invention Material can be in a carrier, a hydrophilic colloid using various methods depending on the type of the dye image-forming material is dispersed will. For example, a diffusible, dye-releasing coupler or similar compounds with a dissociable group, for example a SuIfo- or carboxy group, can be added to a hydrophilic colloid solution after immersing it in water or an alkaline aqueous solution Solution have been resolved. When using a dye image generating materials that are weak in an aqueous medium and in an organic solvent are easily soluble, these are first dissolved in an organic solvent and then the resulting solution added to a hydrophilic colloid solution, followed by stirring or the like to make the solution in the form of fine particles to disperse. Examples of suitable solvents are

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Ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ß-butoxy-ß-ethoxyethyl acetate, dimethylformamide, dimethyl sulfoxide, 2-methoxyethanol, tri-n-butylphthalate and the like. Among these dispersion solvents, there may be those having a comparatively low vapor pressure have, evaporated on drying of the photographic layers or they can according to the US patents 2,322,027 and 2,801 I7I Process evaporated before application in the form of a layer will. Among the dispersion solvents, those which are easily soluble in water can be washed by washing removed with water by the process described in U.S. Patents 2,949,360 and 3,396,027 is.

In order to stabilize the dispersion of the dye-image-forming material and to accelerate the dye-image-forming step /, it is advisable to incorporate, together with the dye-image-forming material, a solvent in a photosensitive element which is practically insoluble in water and has a boiling point of no less at normal pressure than about 200C. Examples of solvents suitable for this purpose are fatty acid esters such as the triglycerides of higher fatty acids and dioctyl adipate, phthalic acid esters such as di-n-butyl phthalate, phosphoric acid esters such as tri-o-cresyl phosphate and tri-hexyl phosphate, amides such as Ν, Ν-diethyl laurylamide, Hydroxy compounds such as 2, ^z l-di-n-amylphenol and the like. It is also advantageous to use a polymer having an affinity for the solvent in order to stabilize the dispersion of the dye image-forming material and to accelerate the dye image-forming step together with the dye image-forming material incorporated into a photosensitive element. Suitable polymers for this purpose with an affinity for the solvent are shellac, phenol-formaldehyde condensates,

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Poly-n-butyl acrylate, n-butyl acrylate / acrylic acid copolymers, n-butyl acrylate / styrene-methacrylamide copolymers and the like. These polymers can be dissolved together with the dye image-forming material in an organic solvent and then in a hydrophilic solvent Colloid dispersed v / earth or they can be in the form of a hydrosol obtained by emulsion polymerization or the like. is added to a hydrophilic colloid dispersion of the dye image-forming material will.

In general, dispersing of the dye-image-forming agent can be used Material can be effectively carried out under the action of a large shear force. For example, is suitable a high speed rotary mixer, a colloid mill, a high pressure milk homogenizer, a pressure homogenizer, as described in British Patent 1,304, an ultrasonic emulsifying device and the like. By using surfactants as emulsifying aids the dispersion of the dye image forming material is markedly promoted. examples for Surfactants that are used to disperse the invention dye image forming material used are sodium triisopropylnaphthalene sulfonate, Sodium di-nonylnaphthalene sulfonate, Sodium p-dodecylbenzenesulfonate, dioctylsulfosuccinate sodium salt, Cetyl sulfate sodium salt and anionic surface active Means as advertised in Japanese Patent application Kr. 4293/64 are described. The combined use of these anionic surfactants Medium and higher fatty acid esters of anhydrohexitol result in a particularly good emulsifying power, as in the US patent ■ 3 676 141.

: In the silver halide emulsion used in the present invention is a colloidal dispersion of

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Silver chloride, silver bromide, silver chlorobromide, silver bromide iodide, silver chlorobromide iodide, silver iodide or a mixture thereof. The halide composition is selected depending on the desired end use of the light-sensitive material and the developing conditions. A silver bromide iodide emulsion or a silver chlorobromide iodide emulsion which contains from about 1 to about 10 mol% iodide and not more than about 30 mol% chloride and the remainder bromide is particularly advantageous. Useful silver halide grains have an average grain size of about 0.1 to about 2 microns . For some uses of the light-sensitive material, silver halides having a uniform grain size are preferred. The granules may have a cubic, an octahedral, or a mixed crystal shape. These silver halide emulsions may be prepared using conventional methods, such as are described by P. G-lafkides in "Chimie Photographique", 2. A _u fi _a ge, 1957, Paul Montel, Paris in Chapters 18 to 23, are prepared. That is, a soluble silver salt, such as silver nitrate, and a water-soluble halide, such as potassium bromide, are reacted with one another in the presence of a solution of a protective colloid such as gelatin and left in the presence of excess silver halide or a solvent for the silver halide such as ammonia one the crystals develop. A single jet or a double jet method or a double jet method with -pAg control can be used as the precipitation method. The soluble salts can be removed from the emulsion by washing, by dialysis of the emulsion solidified in the cold, by a combination of the addition of a sedimentation agent, such as an anionic polymer with sulfonic groups, sulfuric acid ester groups or carboxy groups or an anionic surfactant and the adjustment of the pH value or by the combined use of a

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Acylated protein, such as phthaloylated gelatin, as a protective colloid and adjustment of the pH value, whereby causing sedimentation to be achieved.

The silver halide emulsions which can be used in the present invention are preferably made by heat treatment chemically sensitized using a sensitizer, such as natural sensitizers, as they are contained in gelatin, a sulfur sensitizer, (e.g. Sodium thiosulfate, Ν, Ν, Ν'-trimethylthiourea and the like) as described in U.S. Patents 1,574,944, 1,623,499, 2,410,689, and the like, of a gold sensitizer (e.g. a thiocyanate complex salt or a thiosulfate complex salt of monovalent gold and the like) or a salt of a noble metal such as palladium, ruthenium, rhodium, platinum, and the like, as described in U.S. Patents 2,448,060, 2,399,083, 2,642,361 and the like, or a reduction sensitizer (e.g. tin dichloride, as described in U.S. Patent 2,487,850, or Hexamethylenetetramine). According to the invention, such Emulsions which have a tendency to form latent images on the surface of the silver halide grains, and those emulsions which have a tendency to form latent images inside the silver halide grains, such as see them in U.S. Patents 2,592,550, 3,206,313, and the like. are described.

The silver halide emulsions which can be used according to the invention can be prepared using additives such as, for example, 4-hydroxy-6-methyl-1, 3 _} 3a, 7- "betrazaindene, 5-nitrobenzimidazole, i-phenyl-5-mercaptotetrazole, 8- Chloromercuriquinoline, benzenesulfinic acid, pyrocatechol and the like. In addition, inorganic compounds such as cadmium salts, mercury salts, complex salts of metals of the platinum group, such as palldium chlorine are also suitable.

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complex salt and the like, for the stabilization of the light sensitive Materials of the Invention. Examples of such stabilizers are given in US patents 2 806 437, 2 444 605, 2 403 927, 3 266 877, 3 397 987 and the like. In addition, the silver halide emulsions which can be used in the invention sensitizing compounds, such as a polyethylene oxide compound, contain.

The silver halide emulsions used in the present invention can, if desired, have a photosensitivity, which has been expanded to include optical sensitizing dyes. Examples of suitable optical Sensitizing dyes are the cyanines, merocyanines, "the holopolar cyanines, styryls, hemicyanines, oxanols, Hemioxanols and the like. Specific examples of optical sensitizers are in the above book by P.Glafkides, in chapters 35 "to 41 and by M. Hamer in "The Cyanine Dyes and Related Compounds" (Interscience) and in US Patents 2,519,001, 2,666,761, 2,734-900, 2,739,964, 3,481,742, 3,672,898, and the like. For the practice of the invention Particularly suitable are the cyanines, in which a nuclear nitrogen atom is replaced by a hydroxy, carboxy or sulfo group-containing aliphatic group substit- '. as described, for example, in U.S. Patents 2,503,776, 3,459,553, and 3,177,210.

The. Used according to the invention, for the developer preparation permeable layers, such as the silver halide emulsion layer used in the present invention, which contain the the layer containing the dye image-forming material and the auxiliary layers (e.g. a protective layer, a Interlayer and the like), contain a hydrophilic polymer as a binder. Examples of suitable polymers

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are gelatin, casein, gelatin modified with an acylating agent or the like, with a vinyl polymer grafted gelatin, proteins such as albumin, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose and the like, polyvinyl alcohol, the partially hydrolyzed products of polyvinyl acetate, polyvinyl pyrrolidone, Non-electrolytes with a high molecular weight, such as polyacrylamide, polyacrylic acid, the partially hydrolyzed products of polyacrylamide, anionic synthetic Polymers, such as vinyl methyl ether / maleic acid copolymers, N-vinylimidazole / acrylic acid / acrylamide copolymers, synthetic polymeric amphoteric electrolytes, such as polyacrylamide, which are subjected to the Hofmann reaction has been. These hydrophilic polymers can be used alone or in combination. aside from that these hydrophilic polymer layers can have a latex-like appearance Polymer dispersion of hydrophobic monomers, such as, for example, alkyl acrylates, alkyl methacrylates and the like. These polymers, especially the polymers with functional groups, such as an amino, hydroxy or carboxy group, can using various Crosslinking agents are made insoluble without affecting the permeability for the developer preparation get lost. Examples of particularly suitable crosslinking agents are aldehyde compounds such as formaldehyde, Glyoxal, glutaraldehyde, succinaldehyde, mucochloric acid, 2,3-dihydroxy-1,4-dioxane, dimethylolurea, acrolein oligomers and the like; Aziridine compounds, such as triethylenephosphamide, as described in Published Japanese Patent Application No. 8790/62; Epoxy compounds, v / ie bis (2,3-epoxypropyl) methylpropylammoniufl-p-toluenesulfonate, 1,4-bis- (2 ', 3'-epoxypropyloxy) -butane, 1,3-diglycidyl-5- (v-acetoxy-ß-oxypropyl) isocyanurate, 1,4-bis- (2 ', 3'-epoxypropoxy) diethyl ether (as in the published Japanese Patent Application No. 7133/59

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described) and the like; active halogen compounds, e.g.

2 ^ -Dichlor-ö-oxytriazine sodium salt, 2,4-dichloro-6-methoxytriazine, 2-hydroxy ^ jö-dichloro-s-triazine sodium salt, sebacic acid bischloromethyl ester, N, Ή '-Bis- (α-chloroethylcarbamyl) piperazine and the like; active vinyl compounds such as divinyl sulfone, hexahydro-1,3,5-triacryl-s-triazinemethylene bisraaleiinide, 5-acetyl-1,3-diacryloyl- ¹ , 3, 5-hexa-hydrotriazine, N, N 1, N '-triacr3 ^ loyl-1, 3,5-hsxahydro-triazine and the like; Methyl compounds such as N-polymethylol carbon, hexamethylol melamine and the like; Ethylenimine compounds such as 2,4,6-triethylenimino-i, 3,5-triazine, bis-ß-ethyleniminoethylthioether and the like.; Methanesulfonate compounds such as 1,2-di- (methanesulfonyloxy) ethane, 1,4-di- (methanesulfonyloxy) butane, 1,5-di- (methanesulfonyloxy) pentane _{and the} like; compounds with a high molecular weight, such as dialdehyde, 3-hydroxy-5-chloro-s-triazinylgelatine and the like. Suitable examples of such compounds are disclosed in U.S. 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,

2 783 611, 2 725 294, 2 725 295, 3 100 704, 2 091 537,

3,321,313 and the like. These hydrophilic polymers can contain an agent that accelerates crosslinking, such as a carbonate or resorcinol, and the crosslinking agent.

The photographic layers used in the present invention can using various coating processes, for example by dip coating, by roller coating, by coating with an air knife, by drop coating as in the US patent

2 681 294 described by curtain coating (curtain coating), as in U.S. Patents 3,508,947 and

3,513,017 described, can be applied. For photosensitive For elements with a multilayer structure, it is particularly expedient to apply several layers at the same time using a multi-slit funnel,

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as in U.S. Patents 2,761,417, 2,761,418, 2,761,419 and 2,761,791.

To the application of the inventive photographic Layers can be made easier by the coating compound suitably a wide variety of surface-active agents included as a coating aid. examples for suitable coating aids are non-ionic surfactants such as saponin, p-nonylphencl, Ethylene oxide adducts, alkyl ethers of sugar, glycerol monoalkyl ethers and the like, anionic surfactants such as sodium dodecyl sulfate, sodium p-dodecylbenzenesulfonate, Dioctyl sulfosuccinate sodium salt and the like, and amphoteric surfactants such as the internal carboxymethyldimethyllaurylanmionium hydroxide salt "Deriphat 151", a product of General Mills, and that described in the US patent 3,441,413 in British Patent 1,159,825 iind in published Japanese patent application Betaine compounds described in Mr. 21 985/71.

To facilitate the application of the photographic layers used according to the invention, the coating compositions can contain various thickeners. In addition to those which increase the viscosity of the coating composition due to their own viscosity, such as, for example, polyacrylamide with a high molecular weight, anionic polymers such as cellulose sulfate, polypsulfostyrene potassium salt and acrylic polymers, as in US Pat. No. 3,655 ® 7 described, can be used, which thicken the coating composition due to the 7 / swelling effect with a polymer binder contained in the coating composition.

In the developer preparation used according to the invention is a liquid preparation which is used for developing a silver halide emulsion and for

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contains developer components necessary for the formation of a diffusion transfer dye image. The main solvent it contains water and in some cases, hydrophilic solvents such as methanol or Methylcellosolve, be present. The developer formulation contains alkali in an amount sufficient to maintain the pH to hold at a value which is necessary to achieve the development of the emulsion layer (s) and to neutralize the during the various stages of development and dye imaging acids formed is required. Sodium hydroxide, potassium hydroxide, a calcium hydroxide dispersion, Tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, and the like are used will. The developer preparation preferably has a pH of at room temperature (about 20 to 30 ° C.) no less than about 12. The developer preparation preferably contains a hydrophilic polymer, such as e.g. one with a high molecular weight, such as polyvinyl alcohol, Hydroxyäthyloellulose, the sodium salt of carboxymethyl cellulose or the like. These polymers impart the developer preparation has a viscosity at room temperature of not less than 1 poise, preferably of about 1000 poise, which not only ensures the even spread of the Preparation facilitated during development, but rather when the developer solution is concentrated as a result of the migration of the aqueous solvent into the photosensitive element and the image-receiving element in the course of development an inevitable film is formed, which serves to make the film unit uniform (evenly) after development z \ i do. In addition, this polymer film can serve to after completion of the production of the diffusion transfer dye bildes to control the further migration of the coloring constituents into the image-receiving layer, whereby a change in the image is prevented.

6 09813/0958

In some cases the developer preparation contains zv / corner wise a light absorbent such as carbon black and a desensitizer as described in U.S. Patent 3,579,333 to prevent the silver halide emulsion from being exposed to external light during development is veiled. The developer preparation also contains the "dye image-forming material used" specific development additives. Examples of such additives used together with a dye developer are auxiliary developer compounds, such as p-aminophenol, .4 · '-Methylpheny! hydroquinone, i-phenyl-3-pyrazolidone and the like, an onium development accelerator such as N-benzyl-a-picolinium bromide, an antifoggant, such as Benzotriazole, and examples of such additives, which in connection with the releasing a diffusible dye Couplers that can be used are developing agents, such as a primary aromatic color developing agent, an antioxidant such as a sulfite or ascorbic acid, an antifoggant such as a halide or 5-nitro-benzimidazole, a silver halide solvent, like thiosulfate or uracil.

The developer preparation used according to the invention is conveniently stored in a breakable container. Such a container is preferably made by folding a sheet of a liquid and air impermeable substance and sealing each edge to form a cavity in which the developer preparation is located, and the container is suitably shaped so that when the film unit passes the pressure application means, the container passes through the inside of the The hydraulic pressure generated in the container with the developer preparation breaks (tears) at a certain point, thereby releasing its content. As a substance for the production of the container, a polyethylene can expediently

terephthalate / polyvinyl alcohol / polyethylene laminate Lead foils / vinyl chloride / vinyl acetate copolymer laminate or the like can be used. This container is expediently permanently installed and extends transversely to a leading edge of the film unit, so that a discharge of the Contents of the container is achieved in practically one direction on the surface of the photosensitive element. Preferred examples of such containers are disclosed in U.S. Patents 2,543,181, 2,643,886, 2,653,732, 2,723,051, 3,056,491, 3,056,492; 3,152,515; and 3,173,580. These containers will be used in the practice of the invention used with advantage.

Supports used in the present invention are essentially planar materials that are not any notable dimensional changes under the influence of the treatment solution in the course of treatment suffer. Flexible supports are generally useful, although rigid supports such as glass can be used, depending on the purpose. Examples of suitable flexible supports are those generally used in photographic applications Materials are used, for example cellulose nitrate, cellulose acetate, polyvinyl acetate, polystyrene, Polycarbonate, polyethylene terephthalate, etc. and they can be used as a transparent carrier, as a colored carrier to which one has given a dye, as a light-reflecting support, to which a white pigment such as titanium dioxide has been added, or as a light-shielding support to which a light-absorbing compound such as carbon black has been added will. In addition, paper carriers, in particular barite-coated papers and papers, can have their surfaces coated were used to make them waterproof, for example with polyethylene, what

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depends on the purpose. Carriers that are impermeable to oxygen are like laminates in which a polyvinyl alcohol layer between polyethylene terephthalate layers is interposed, water vapor-permeable carrier, as in U.S. Patent 3,573,044 and supports having a light-shielding undercoat which is removed after treatment as disclosed in Published Japanese Patent Application 4,086/72 and Japanese Patent Applications OPI Nos. 10 020/74 and 10 021/74 can be used depending on the purpose for which the photographic Material is used. The carrier can, if desired a plasticizer such as phosphoric acid or a phthalic acid ester, an ultraviolet absorbing agent such as 2- (2-Hydroxy-4-tert-butylphenyl) -benzotriazole or an antioxidant such as a sterically hindered phenol. In order to maintain the adhesion between the support and the photographic layer containing a hydrophilic colloid, it is advantageous to provide an underlayer on the carrier or the surface of the carrier to a pretreatment subject to, for example, a glow discharge, an ultraviolet radiation, a flame treatment and similar. The thickness of the polymeric layer can be from about 3 to about 50 / U, and is preferably from 6 to 25 / u.

The polymeric acid layer can contain additional additives, for example Plasticizers such as glycerin, triacetin or polyethylene oxide, a developing agent scavenger or scavenger, as described in U.S. Patents 3,725,063, 3,730,713 and 3,743,504, a development inhibitor such as i-phenyl-5-mercaptotetrazole, or a color image stabilizer etc. included.

The polymeric acid layer of the present invention has the characteristic Characteristic that they have a high content of acid

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groups and has high water resistance. In general a polymeric acid layer with a high acid group content is naturally very hydrophilic; she becomes particular then even more hydrophilic when treated with an alkaline treatment solution. Under such conditions the polymeric acid swells strongly, so that its mechanical strength as a film is reduced and can be destroyed, In the present invention, the polymeric acid is effectively crosslinked, whereby a satisfactory mechanical Strength is retained even after the alkaline treatment. According to the invention it is possible that a polymer Acid having a high acid group content can be used as a photographic neutralizing layer.

The neutralizing layer of the polymeric acid having a high acid group content of the present invention; h "a neutralizing one Layer with high density of neutralization capacity is sufficiently effective with a thin film thickness, to neutralize a certain amount of alkali per unit area, those from the photographic alkaline processing solution originates. A thin film thickness gives several advantages. For example, one advantage is that that the coated material has a lower tendency to curl. It will also be economical Advantages achieved because a lower amount of polymeric acid is applied per unit area. The production takes place in an advantageous manner, since the coating is easier than with thicker materials.

The polymeric acid according to the invention is opposite to the treatment solution permeable, even when the 'polymeric acid is satisfactorily crosslinked to the desired degree, to achieve water resistance, and quickly neutralizes the treatment solution. In particular

the above characteristic feature occurs effectively,

6098 1 3/0958

when the polymeric acid layer is used in conjunction with a suitable control layer.

The polymeric acid layer of the invention is for photo-. Diffusion transfer graphic materials are useful, in particular for diffusion transfer photographic materials the delamination type, since it retains its satisfactory mechanical strength after the alkaline treatment maintains.

The invention enables the use of a polymeric acid having a high acid group content. Lots of such polymers Acids can be dissolved in aqueous solvents. By using aqueous solvents as solvents various advantages are obtained in coating. For example, at a coating stage in which a organic solvent is used, special manufacturing facilities are required to prevent accidents. The use of an organic solvent is also undesirable in terms of the safety of workers, their health and the environment protection. On the other hand, the coating stage requires where an aqueous solvent is used, these considerations and existing devices do not, usually used in the manufacture of photographic materials can be used. Used if an aqueous solvent is used, it is also possible to use a larger selection of carrier materials. For example, it is possible to apply the water-soluble polymeric acid on a plasticized cellulose triacetate film support which cannot be used satisfactorily when dealing with organic solvents coated.

The polymeric acid layer according to the invention undergoes a rapid crosslinking reaction after coating and the constant properties are retained. In contrast to

609813 / Ω9 KR

the crosslinking reaction proceeds "in the case of the known polymeric acid layers only at low speed until hardening and over a long period of time; this gives different Properties.

The polymeric acid layer according to the invention is water-resistant, but also hydrophilic and therefore has a uniform effect the components of the treatment solution together and can effectively capture the components of the treatment solution. Very good image stability, little photographic staining and good transparency are obtained in this way of the layers.

The following examples illustrate the invention without restricting it. Unless otherwise noted, all are Parts, percentages and the like in terms of weight.

example 1

80 ml of water is added to 20 g of a copolymer of vinyl methyl ether with maleic anhydride (in a molar ratio of approximately 1: 1; "Gantrez AN-139", manufactured by GAF, having an inherent viscosity in thienyl ethyl ether of approximately 1.2). The mixture is stirred for 6 hours while it is kept at 60 ^° C. in order to hydrolyze it (a polymer is formed which contains the structural unit P-7 described above and which contains 11.4 mmol / g of carboxyl groups), and thereby the copolymer dissolves. To this end, different, predetermined amounts of sodium hydroxide are added in order to achieve partial salt formation. 1 ml of an aqueous solution containing 40 mg of polyoxyethylene p-nonylphenyl ether (containing 9 oxyethylene units) is added to this mixture, and then 50 ml of methanol and 5 ml of methanol containing 0.40 g of 1,4-BiS- (Z ¹ 3'-epoxypropoxy) butane (by weight with the above-described structural formula G-1 wherein η = 4 group), added as a crosslinking agent. The resulting mass is coated onto a cellulose triacetate film support using a rod to produce a film thickness of 15 / rev on a dry basis. The film carrier used contains triphenyl phosphate as a plasticizer and is 130 / U thick and has an underlayer on one side that mainly contains gelatin.

The material thus obtained coated is held for 7 days at controlled conditions, namely at a temperature of 25 ° C and a relative humidity of 65%, and then immersed in an aqueous solution of 0,1η Natriumhydroxid'bei 25 ⁰ C. The swelling of the polymeric acid layer in the thickness direction is determined as a function of the immersion time.

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The device used to determine swell is of the type in which an element is periodic is brought into contact with the surface of the immersed film to determine the position of the film surface, while a constant temperature solution flows over the surface, and then the change in the position of the Element is read electrically using a solenoid. This device has a measurement accuracy of approximately 1 / u.

In the sample in which the crosslinking agent is not added and swelled in the sample into which the crosslinking agent had been added but where no salt formation occurred the polymeric acid layer very quickly, so that the strength of the polymeric acid layer as a film in the alkaline solution was not retained and the layer eventually dissolved and washed away. In this case it could swelling can only be measured at the beginning of immersion in the alkaline solution. On the other hand, the polymer swelled Acid layer that had been subjected to salt formation and into which the crosslinking agent was incorporated such a way that the swelling is about 90% of the saturated Swelling value reached after immersion for 1 minute in alkaline solution, the layer being the long-lasting Endured development with the alkaline solution. The swelling could thus be precisely determined.

The measured value for the swell ratio (expressed by the ratio of the thickness of the swollen film to the thickness of the dry film) after immersion for 4 minutes, when swelling almost reached its maximum is reported in Table I as a function of the degree of salt formation.

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Table I.

Maximum swelling ratio or swelling ratio at saturation of the polymeric acid layer (in 0,1η sodium hydroxide at 25 ⁰ C for 4 minutes)

Sample crosslinking no. medium, (%)
(Weight # / polymer)

1 0 2 2.0 3 2.0 4th 2.0 5 2.0 6th 2.0 7th 2.0 8th 2.0 9 2.0 10 2.0

Salt formation; Maximum source is released NaOHCIn)
(ml) Neutral relationship
station
Degree K Il 0 0 8.8 0 0 7.9 2.6 1.0 7.6 5.1 2.0 6.9 12.8 5.0 6.4 25.5 10.0 6.7 51.0 20.0 8.4 76.5 30.0 9.5 102.0 40.0 127.5 50.0

The sample 2 is continued at a temperature of 50 ° C and at a relative humidity of 40? q for 3 days and then swelling is determined in the same manner as described above. Despite the acceleration of the Crosslinking swells the sample to a great extent, so that the polymeric acid layer does not retain its strength as a film can and will eventually be extracted.

From the above results it can be seen that the polymeric acid which has been partially subjected to salt formation, easily reacts with the crosslinking agent, so that even if a small amount of the crosslinking agent is added becomes satisfactory in water resistance of the photographic film within a short time the coating is obtained. Furthermore, these results show that the acceleration of crosslinking by the

809813 / öS 58

Salt formation of a small part of the total carboxyl groups is significantly improved, so that the water resistance of the polymeric acid layer can be improved without reducing the neutralization capacity of the polymeric acid layer will.

Example 2

20 g of polyacrylic acid (which contains the above-mentioned structural unit P-1 and which contains 32 mmol / g of carboxyl groups and has an average molecular weight of about 70,000) are dissolved in 80 ml of water to which 13.9 ml of 1N potassium hydroxide is added as an aqueous solution dissolved to neutralize the 5% of the carboxyl groups to the salts. 1 ml of an aqueous solution containing 40 mg of polyoxyethylene-p-nonylphenyl ether (containing 9 oxyethylene units) is added to this mixture, and different, predetermined amounts of 1,4-bis- (2 ', 3'- epoxypropoxy) butane (with the structural formula G-1 described above, in which η denotes 4) was added as a crosslinking agent. -The resulting mass is coated on a transparent cellulose triacetate film base with a thickness of 30 / u, using a rod to produce a film thickness of 15 / u on a dry basis.

The materials coated in this way are left to stand for 14 days under controlled conditions at a temperature of 25 ^° C. and a relative humidity of 65% . The swelling ratio is then determined as described in Example 1 in a 0.1 η v / äßrigen solution of sodium hydroxide at 25 ⁰ C in the same manner and the results obtained are given in Table H.

The coated material, which had been kept for 14 days, was subjected to a heat treatment at a temperature of 50 ^° C. and a relative humidity of h0% for 3 days.

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11 O 12th 5 13th 5 14th VJl 15th VJl 16. VJl 17th VJl 18th 5

subjugated. The results treated with these Samples obtained are also given in Table II.

Table II

Maximum swelling ratio or swelling ratio at the saturation of the polymeric acid layer

(in 0.1η sodium hydroxide at 25 ⁰ C for 4 minutes)

Sample Neutralisa- crosslinking Mitt el Maxim ale s Quellve r häl tn ,. No. degree Xg) (weight / poly- after 7 days- after "the V / arm (%) mer) gene (%) mebehandl. (%)

0 0 dissolves 0 0 »i! «

0.1 0.5> '12> 12

0.2 1.0 11.9 10.8

0.3 1.5 8.1 7.2

0.4 2.0 6.3 5.8

0.6 3.0 5.5 5.1

0.8, 4.0 5.6 4.8

The coated films of these samples are flexible when dry and retain deformation, e.g. when bending with an acute angle.

Example 3

20 g of polyacrylic acid containing the above-described structural unit P-1 with an average molecular weight of about 50,000, are dissolved in 80 ml of water. To this are added 1 ml of an aqueous solution containing 40 mg of polyoxyethylene-p-nonylphenyl ether (which contains 9 oxyethylene units). There will be two or a pair of such solutions manufactured. One solution is kept as it is and that described in Table III is added to the other solution Base in an amount necessary to neutralize 10% of the polyacrylic acid. A crosslinking agent as described in Table III, in the same men-

609813/0958

gene is added to both solutions, and a cellulose triacetate film support having a thickness is made with both solutions of about 130 / u coated so that one film thickness of 15 / U on a dry basis.

The coated materials are 14 days at controlled conditions, ie, held at a temperature of 25 ⁰ C and a relative humidity of 65? A, and then the swelling ratio in an O, 1N aqueous solution of sodium hydroxide at 25 ° C in the same manner as described in Example 1 determined. The results obtained are shown in Table III.

Sample base no.

Table III Crosslinking Agents

Maximum

Compound added amount of swelling ratio (certain / polymer) nis

21
22nd LiOH G-1, n = 3
It 2.0
2.0 dissolves
5.7 23
24 Ba (OH) ₂ G-2
dd 1.0
1.0 dissolves
9.1 25th
26th NH ₄ OH G-3
dd 2.0
2.0 dissolves
8.0 27
28 Zn (OH) ₂ G-8
Il 1.0
1.0 dissolves
9.5 29
30th (CH ₃ ) ₄ N OH A-1
ti 1.0
1.0 ^s 6.6 31
32 (C ₂ H ₅ ) ₃ N A-2
It 1.0
1.0 10.5
6.0

The above results show that an accelerating effect on the crosslinking, due to the salt formation of the polymeric acid occurs with a wide variety of glycidyl compounds and aziridyl compounds.

609813/0958

Example -4

1 ml of an aqueous solution containing 50 mg of sodium p-dodecylbenzenesulfonate is added to 100 g of a 20% aqueous solution of a polymeric acid, as described in Table IV below. Sodium hydroxide is added in an amount which is necessary to neutralize 5% of the carboxyl groups of the polymeric acid. Then 5 ml of a methanol solution containing 0.40 g of 1,4-bis- (2 ', 3'-epoxypropoxy) -butane (compound G-1, where η means 4) is added as a crosslinking agent. The resulting mass is coated onto a cellulose triacetate film support with a thickness of 130 Ai , so that a film thickness of 15 / u on a dry basis is obtained.

These coated materials are kept for 7 days under regulated conditions at a temperature of 25 ^° C. and a relative humidity of 65%. The swelling is then determined in a 0.1 μm aqueous solution of sodium hydroxide in the same way as described in Example 1. The results obtained are shown in Table IV.

Table IV

sample polymer Maximum source ratio 12.3 5.2 No. Compound carboxyl group (mol / g) ratio {_%) 16.0 11.1 41 P-2 13.9 6.2 42 P-4 9.8 7.0 43 P-5 11.4 5.6 44 P-6 8.2 7.2 45 P-8 5.3 4.8 46 P-9 6.3 8.0 47 P-11 8.7 8.2 48 P-13 11.1 9.6 49 P-14 50 P-16

809-13 / 0958

The above results show that according to the invention a a wide variety of water-soluble polymers is effectively cured, resulting in improved water resistance. Of these samples, Sample Nos. 43, 48, and 49 yield flexible, dry, coated films that are at all have no tendency to break even when bent at an acute angle. So you own excellent mechanical properties.

Beisr) iel5

A mixture of 500 g of copolymer of vinyl methyl ether with maleic anhydride ("Gantrez AN-139", manufactured by GAF), 260 g of n-butyl alcohol, 1 g of phosphoric acid (85%) and 3 l of methyl ethyl ketone is stirred mechanically for 48 hours at 70 ° C. to prepare an n-butyl half ester of the above copolymer (containing 4.3 mmol / g of carboxyl groups).

To 100 g of a methyl ethyl ketone solution containing 20% by weight of n-butyl half ester of the copolymer of vinyl methyl ether with maleic anhydride, 0.30 g of 1,4-bis ~ (2 ·, 3'-epoxypropoxy) butane is added (G-1) as a crosslinking agent and then 4.3 g of triethylamine. With the resulting, transparent solution a polyethylene terephthalate film base is coated with a thickness of 100 / u to a film thickness of 21 / u Manufacture dry basis. A polymeric acid layer, sample (A), is thus created.

The same procedure as described above is repeated with the exception that no triethylamine is added. Man receives the comparison sample (B).

These samples are 14 days at controlled conditions, that is at a temperature of 25 ⁰ C and a relative humidity of 65%, preserved, and then the sources in a 0.1N v / äßrigen sodium hydroxide solution at 25 ° C in the same manner as in Example 1 described determined. The curves

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~ 63 -

Swell rate - immersion time are shown in the attached drawing. The sample (A) in which the polymeric acid partially was converted into the salt form according to the invention shows less swelling and improved water resistance compared with the comparative sample (B) because of the crosslinking is accelerated.

B e i s ρ i e 1 6

20 g of polyacrylic acid (which has the structural unit described above P-1 contains with an average molecular weight of approximately 70,000) are dissolved in 80 ml of water. 13.9 ml of a 1N aqueous potassium hydroxide solution are added to this and 1 ml of an aqueous solution containing 40 mg Polyoxyäthyleiip-nonylphenylather contains (contains 9 oxyethylene units). Then 0.40 g of 1,4-bis (2 ', 3' -epoxypropoxy) -butane are grounded (Compound G-1, "in which η means 4) was added as a crosslinking agent. The resulting mass becomes a white paper support coated, which was coated on both sides with polyethylene, so that you have a film thickness of 15 / U Preserves dry basis. A first layer is thereby formed.

A control layer of 65 mg / 100 cm of a copolymer of n-butyl acrylate with oc-hydroxyethyl methacrylate (monomer molar ratio: 0.80: 0.20; average molecular weight: approximately 50,000) and a fixer are placed on the above layer - or stain layer of 20 mg / 100 cm of poly-4-vinylpyridine (with an average molecular weight of 60,000) and 40 mg / 100 cm ^{2 of} polyvinyl alcohol (with an average molecular weight of approximately 70,000) applied one after the other to create an image To make a receiver sheet that can be used in diffusion transfer color photography. The curing of these two layers was done using hexamethylolamine.

609613/0958

Furthermore, were on a cellulose triacetate film support applied one after the other with a thickness of 130 / U: one

/ ρ

Layer which contained 14 mg / 100 cm 1-hydroxy-4-isopropoxy-2- [4- (ßhydroquinonylethyl) -phenylazo] -naphthalene, 20 mg / 100 cm, Ν-diethyllaurylamide and 24 mg / 100 cm ² gelatin, as the first layer; a layer that contains a green-sensitive silver bromoiodide emulsion in a coverage of 35 mg SiI-

p ρ

ber / 100 cm and gelatin in a coverage of 40 mg / 100 cm contained, as a second layer; and a protective layer that

ρ ρ

4 mg / 100 cm of 4'-methylhydroquinone and 15 mg / 100 cm of gelatin contained, as a third layer, to obtain a photosensitive sheet material, which in the diffusion transfer. supply color photography can be used. In this case, curing of these three layers was done using of 2-hydroxy ~ 4,6-dichloro-s-triazine sodium salt.

The photosensitive sheet material was exposed through an image and then an image receiving sheet was placed face-to-face. A developing compound A of the following Composition was spread between both sheets to give a liquid thickness of 60 / rev.

Viscous developing solution A water

Potassium hydroxide. Carboxymethyl cellulose N-benzyl-a-picolinium bromide

Benzotriazole

(Viscosity about 40,000 cP)

If the photosensitive sheet and the image-receiving sheet were separated 60 seconds after the developing solution was spread, a magenta print with smoother was obtained Surface and a photosensitive sheet to the surface of which the developing solution is adhered. If, on the other hand, an image receiving sheet is used which does not form partial salt the polymeric acid is produced, the polymeric acid layer and breaks when the two sheets are separated

609813 / 09B8

100 5 ml 12th 5 G 3, 6 " G 1, G 1, G

the transferred image adheres together with the developing solution layer on the photosensitive sheet.

Example 7

20 g of a copolymer of ethylene with maleic anhydride (monomer molar ratio approximately 1j1; average Molecular weight about 90,000) are dissolved in 80 ml v / water with heating. Then you give 44.4 ml of a 1N aqueous Add sodium hydroxide solution to cause partial salt formation. Then 5.0 g of formaldehyde-sodium bisulfite adduct are added and 0.8 g of triethylene phosphonamide (A-I). admitted. The resulting mass is on a transparent film carrier made of cellulose triacetate applied with a thickness of 180 / U, so that a film thickness of 20 / rev is obtained on a dry basis. A control system is applied to this layer one after the other.

layer containing 65 mg / 100 cm copolymer of butyl acrylate with ß-hydroxyethyl methacrylate (monomer molar ratio 0.80: 0.20; average molecular weight about 50,000), as a second layer and an image-receiving layer, the 35 mg / 100 cm of poly-4-vinylpyrrolidone, 15 mg / 100 cm of poly (2-methacrylethyltrimethylammonium methylsulfonate) and 80 mg of polyvinyl alcohol, applied as the third layer. The second layer and the third layer are cured using hexamethylol melamine. A light-reflecting layer, which contains 162 mg / 100 cm of titanium dioxide and 27 mg / 100 cm ^{2 of} gelatine, is successively applied to the above layers as the fourth layer; a layer containing 12 mg / 100 cm of a diffusible coupler which provides a blue-green dye, namely 1-hydroxy-4-octadecyloxy-N-ethyl-3 ', 5'-dicarboxyl-2-naphthanilide, 0.1 mg Contains silver / 100 cm ² colloidal silver sulfide and 27 mg / 100 cm ² gelatin, as a fifth layer; an emulsion layer containing 10 mg silver / 100 cm of a red-sensitive silver bromine

iodide emulsion, 9 mg / 100 cm of a coupler, the blue-green results, i.e. 1-hydroxy-N-dodecyl-2-naphthamide, and 19 mg /

Contains 100 cm gelatin, as the sixth layer; and a

609313/0958

Protective layer containing gelatin, applied at a thickness of 1 / U as the seventh layer, around a photographic To manufacture diffusion transfer color film. The hardening of the fourth layer up to the seventh layer takes place using 2-hydroxy-4 ~ chloro-6-s - triazinylated Gelatin prepared according to the procedure described in U.S. Patent 3,362,827. Of the Photographic film is exposed through an image from the side opposite the support and then with a Cellulose triacetate sheet covered with a thickness of 80 / u. Then, a treatment solution having the following composition is applied in a thickness of 100 / U between the film and streaked out on the sheet.

Viscous treatment solution B
water
Ascorbic acid

4-Amino-3-diethyl-N-ethyl-N ~ (ß-hydroxyethyl) aniline sulfate (Monohydrate)

6-nitrobenzimidazole nitrate

Sodium hydroxide

Sodium thio sulfate

Sodium carboxymethyl cellulose (viscosity approx 40,000 cP)

The appearance of the normal blue-green image was observed 90 seconds after the treatment solution was spread out. On the other hand, a sample in which the polymeric acid layer was not subjected to partial salt formation gave a partially distorted image. It is believed that this is due to the irregularity of the layer arrangement caused by excessive swelling of the polymeric acid layer.

100 8th ml 20th mg 2, G 15th 6th mg 4th 5 G 0, G 3, G

609813/0958

Claims (6)

Claims 1. Sheet or plate material for use in a photographic product, the material having a Carrier and thereon a polymeric acid layer contains to the photographic alkaline processing solution To neutralize termination of treatment with the treatment solution, characterized in that that the polymeric acid contains about 3 mmoles / g or more than about 3 mmoles / g of carboxyl groups, and wherein about 1 mol ~ # to about 40 mol / s of the carboxyl groups in salt form of which are present, and has been reacted with a crosslinking agent which has at least two in the same molecule contains functional groups selected from the group that contains: an aziridyl group, a glycidyl group, a precursor group thereof and mixtures thereof. 2. sheet or plate material according to claim 1, characterized characterized in that it further contains a polymeric layer which increases the rate of neutralization can regulate whether the polymeric acid layer is present between the support and the polymeric layer. 3. sheet or plate material according to at least one of claims 1 or 2, characterized in that that the polymeric layer delays the neutralizing effect of the polymeric acid layer until the treatment with the photographic alkaline processing solution im is essentially terminated. 4. Photographic sheet or plate material after Claim 1, characterized in that the polymeric acid has more than about 7 mmol / g of carboxyl groups contains. 609813/0958 5. sheet or plate material according to at least one of claims 1 to 4, characterized gekennzei chnet that about 5 to 30 mole percent of the carboxyl groups of the polymer Acid reacted with the crosslinking agent. 6. Photographic sheet or plate material according to at least one of claims 1 to 5, characterized in that the polymeric acid at least contains one of the following structural units: C. COOH CH - CH -
COOH COOH wherein R represents a hydrogen atom or a methyl group. 7. Photographic sheet material after at least one of claims 1 to 6, characterized in that the polymeric acid before the Crosslinking is water soluble. 8 · -: ... Sheet- _:. Or. Panel material according to at least one of claims 1 to 7 »characterized in that the crosslinking agent is selected from the group comprising compounds of the following formulas: CH ₉ - CH - CH ₉ - 0 - (CH ₉ ) _ - OCH ₉ - CH - CH / ι X / η = 2, 3 or 4 609 813/0958 O = P- (0 - CH ₀ - CH "- CH - ς / 0 "0CH ₀ CH - CH η t OCH ₀ CH - CH ₀ CH ₀ - CH - CH ⁺ NN ⁺ - CH ₂ - CH -CH ₂ I. 0 ^ 2CH, -ΓΑ- ™ -. CH CH, CH ₀ -C- CH ₀ n2 / 2 0 k j - CH ₂ - CH _x
ι ■> CH _x CH ₀ - 0 ■ C - CH ₀ D. 2 t
C _x -CH ₂
0 0 CH ₀ - CH - CH ₀ - 0 -M V 0 - CH ₀ - CH - CH ₀ 609813/0958 0 = P [- O - (CH _{2) n2} - OCH ₂ - CH ^ - ^ J ₂ CH 3 η ₂ = 2, 3 or 4 ^{1 line} CH ₅ ^ T "(T ^ CH ₂ CH ₂ - y9y diffusion transfer film inlet containing a photo-sensitive element, an image receiving element and an alkaline photographic processing element, wherein the unit contains a polymeric acid layer, characterized in that the polymeric acid layer a polymeric acid at about 3 mmol / g or more than about Contains 3 mmol / g of carboxyl groups and in which about 1 to about 40 mol% of the carboxyl groups in the form of a Salt thereof are present and reacted with a crosslinking agent, the crosslinking agent being in the same molecule contains at least two functional groups selected from the group comprising an aziridyl group, a glycidyl group, 6098 13/0958 contains a precursor group thereof and a mixture thereof. 10. Diffusion transfer photographic color film unit according to claim 9, characterized in that they have a photosensitive silver halide emulsion layer in combination with a compound that is a diffusible Dye provides an image-receiving layer which can accept the diffusible dye, the polymeric acid layer can neutralize the treatment solution to a pH value that gives a stable color image. 11. Diffuse transfer photographic film unit according to at least one of claims 9 or 10, characterized in that the polymeric acid layer present between the support and the image-receiving layer is and that the. Silver halide emulsion layer is provided on a second support and so that the unit is adapted is that a treatment solution in layer form zv / ischen d.er Image-receiving layer and the light-sensitive layer distributed can be. 12. Diffusion transfer photographic film unit according to at least one of claims 9 "to 11, characterized in that the polymeric acid layer is present between the support and the silver halide emulsion layer and that the image-receiving layer is on a second carrier is applied and that the unit is adapted so that a treatment solution in layer form between the image-receiving layer and the photosensitive layer can be spread. 13 «Diffusion transfer photographic film unit according to at least one of claims 9 to 12, characterized in that the polymeric acid layer, the The image-receiving layer and the emulsion layer are applied successively to the support. 609813/0958 14. Diffusion transfer photographic film unit according to at least one of claims 9 "to 13, characterized in that the polymeric acid layer on is applied to the support and the image-receiving layer and the silver halide emulsion layer is coated on a second support and that the unit is adapted so that a treatment solution in layer form between the porymeren Acid layer and the silver halide emulsion layer can be spread. 15 · Diffusion transfer photographic film unit according to at least one of claims 9 to 13, characterized in that it is a peelable layer contains between the image-receiving layer and the silver halide emulsion layer appropriate to separate both layers after treatment. 16. Diffusion transfer photographic film unit according to at least one of claims 9 to 14, characterized in that it is a peelable layer contains between the image-receiving layer and the silver halide emulsion layer appropriate to separate both layers after treatment. 17 »Diffusion Transfer Photographic Film Unit according to claim 13, characterized in that it contains an element containing a transparent support on which, in succession, an image-receiving layer, a light reflective layer and an emulsion layer were applied. 18. Photographer, see diffusion transfer film unit according to claim 14, characterized in that it contains an element containing a transparent "support, on which an image-receiving layer, a light-reflecting layer and an emulsion layer are applied in succession became. 6 09813/095 8