DE2249471A1 - PHOTOGRAPHIC, LIGHT SENSITIVE SILVER HALOGENIDE ELEMENT - Google Patents

Description

The invention is concerned with photosensitive materials such as photographic films and photographic ones Papers and relates in particular to a photographic photosensitive element which, by addition of an N-long-chain amidoalkyl-quaternary ammonium carboxylic acid / 'betaine derivative to a photographic emulsion as coating aid for the hydrophilic colloidal Coating mass which is on a carrier, for example synthetic films and papers, or as a means of improving electrical discharge and the adhesion properties of the. Surface of a base film or the surface layer of the coated photographic emulsion.

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On the basis of the invention, N-long-chain amidoalkyl quaternaries Ammonium carboxylic acid / betaine derivatives as superior coating aids for the formation of photographic, photosensitive elements and the elements made in this way.

In general, cellulose esters, synthetic high molecular materials such as polystyrene, polycarbonate and polyethylene terephthalate, glass, paper or paper coated with a poly-oc-olefin as a base for photographic, photosensitive elements applied. A silver halide photographic emulsion layer is provided on this support either applied directly or applied over an undercoat layer.

With numerous types of photosensitive materials becomes a layer for protecting the surface of the photographic emulsion layer thereon for prevention of adhering the surface of the photosensitive material to the same or different kind of photosensitive materials and the damage to the surface of the photosensitive material due to applied by pressure.

Other than the above layers are often made of gelatin, other hydrophilic colloids or vinyl polymer latex formed L "coating layers containing various additives, such as dyes, antistatic agents, hardeners, couplers and antihalation agents, for example Antihalation layers, intermediate layers, Filter layers, antistatic layers or the like, present on the support of a photographic film.

As indicated above, the usual, photographic light-sensitive materials have numerous layers and therefore it is necessary that the The above-specified coating composition has a uniform shape

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a thin layer without any coating difficulties, for example, rejection at the time of production of the photographic, light-sensitive material can be applied. '

In the production of photographic ·, light-sensitive materials of the type described above, there are numerous cases in which different types of photographic emulsions or other coating compositions containing gelatin are applied simultaneously as multiple layers, for example if different ¹ borrowed photographic Emulsions are continuously applied to a support to form the three photographic emulsion layers in the manufacture of a color photographic photosensitive material »'

If gelatin or another colloidal mass is applied to a colloidal gelatin layer ^ is it is very difficult to obtain the required coating properties compared to the case where get a colloidal Gelatin mass is applied directly to a carrier, especially if an undercoat in a moist one and cold state immediately after its application is. ·

As an example for the iJberzügsverfahrenstüfen im Case of making phot ο graphic, photosensitive Difficult problems caused by materials, let us list the difficulties where a mordant dye is dispersed in a gelatin solution. put colloidal dispersion uniformly on a door bracket must be applied and a layer of a colloidal dispersion as an antihalation layer or filter layer in the photographic, photosensitive material is applied.

Im'diesem case it is very difficult to have a ^uniform: to get Liehe dispersion of Beizfarbstoffes and these raise so that no bubbling Odoi ^-1 rejection

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takes place and a diffusion of the dye from the applied mordant dye layer in the adjacent photographic Emulsion layer is prevented.

In terms of surface properties one A photographic surface layer is often applied Formation of haze due to the wiping of the surface of the emulsion and the back surface in the case where a number of printing papers are stacked and if one emulsion surface "another different one Substance touches, for example a "$ ßchuk thimble, which is used to roll up the graphic paper is used.

Further occurs in the case where the emulsion surface of the photographic light-sensitive material is dried by placing the emulsion surface against the surface of a cloth tape of the ferrotype, the problem that the emulsion surface at the The surface of the cloth tape sticks and this not only results in spots on the emulsion surface or a Damage to the same, but it also results in a disturbance in the smooth processing, so that a Set lowering of the operational efficiency in drying the photographic light-sensitive materials.

To overcome the difficulties or To avoid disadvantages, various types of surfactants have been used as coating additives for various Coating compounds for photographic, light-sensitive Materials or to improve the surface properties of the surface layer of the photographies Materials used. In particular, saponin has been widely used as a coating aid in the used in photographic industry.

Saponin showed the disadvantage of a slight BIa-

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sen formation, shows remarkable fluctuations in terms of the quality because saponin is a natural product is and has poor properties as a coating additive.

Various other synthetic surfactants have their own different difficulties the coating properties and the surface properties of the various photographic compositions or photographic layers and consequently their range of use is very limited.

Therefore, a large number of different Types of surfactants selected and used according to specific uses.

In general, it is difficult to uniformly apply a "" coating composition to a support without some coating aid, if an antistatic agent is applied with a low surface activity.

However, if a common, known coating additive, for example the sodium salt of N-alkyltaurine, sodium alkylbenzenesulfonate, Polyoxyethylene alkyl ethers or the. listed in British Patent 1,159-825 Amidoalkyl quaternary ammonium sulfonic acid betaines are used together with an antistatic agent, v / ground the antistatic properties of this system in bad in numerous cases, as can be seen from the following examples.

In view of the foregoing, a first object of the invention is to avoid the. Disadvantages of the prior art discussed above and in the achievement of improved photographic, photosensitive compositions with regard to the coating properties, such as anti-repellency, in the case where a gelatin containing solution or another hydrophilic, colloidal solution ^ which is difficult to apply uniformly to a carrier.

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are on the support "for example a synthetic film or paper or a photographic Layer to be applied.

Another object of the invention consists in measures through which a photographic emulsion or other hydrophilic colloidal wet on a support with high Speed can be applied without a Blistering, rejection, or other coating disorders occur.

A third object of the invention consists in measures through the a second and a third gelatin-containing layer lightly onto a first gelatin-containing, photographic layer can be applied if each coating step is carried out with separate coating machines when the upper layers are applied simultaneously to a lower layer to form multiple layers a backing and even if the top layers are in order on a bottom layer to Formation of multiple layers applied to a support will.

A fourth object of the invention is a photographic, light-sensitive material having a improved photographic, antistatic layer for coating without damaging the antistatic properties, even when certain types of antistatic agents are used.

Another object of the invention is a photographic light-sensitive material in which a haze due to the contact friction between the photographic emulsion surface and the same or different types of substances will.

Furthermore, there is an object of the invention in mass

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took, reducing the stickiness of the surface of a photograph! see, photosensitive material should be avoided can.

Nature, principle, details and usefulness of the Invention will become apparent from the following detailed description, which begins with general considerations and with specific examples closes the preferred one Represent embodiments of the invention. ·

In the context of the invention it was found that the The foregoing various objects of the invention can be achieved if, a long chain amidoalkyl quaternary ammonium carboxylic acid / be-taine derivative according to the following general formula for the various photographic Coating compounds are added:

+ τ

ECOlTHCCH ₂ ) _n - N -

L - ⁺ CH - (CH) -COO "

where E is a saturated or unsaturated hydrocarbon group, for example an alkyl, alkenyl group and the like, with 7 to 21 carbon atoms, R. and E ₂ alkyl radicals, - hydroxyalkyl radicals and polyalkylene oxide chains, each with a content of 1 to 18 carbon atoms, For example, from ethylene oxide, propylene oxide and the like., E, and H ₁ , a hydrogen atom or alkyl radicals with 1 to M carbon atoms, η a whole. Number of 2 or more, ', more preferably 2 to 10, and χ denotes the numbers 0 or 1.

Typical examples of long-chain amidoalkylquaternaryammoniumcarboxylic acid ^ betainderivate, which can be used according to the invention, are given below:

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Connection - ή ■:

Pre-connection - 2:

Connection - Jt Connection - 4:

Connection - 5:

Pre-connection - 6; Connection - 7:

J - OM ₁

03 ».

WgOU) OQ '

■. ■ ff: ■.

C ₁₇ H ₅₅ COHH (CHg) ₃ «^ M. ÖÄ _$

- ⁺ N - CH ₅ CH ₂ COO "

L '«

H ₉

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Connection - 8:

f 5

CH ₂ CHCOO "

Connection ~ 9:

₁ 7H ₅₅ CONH (CH

CH ₂ CH ₂ OH - ⁺ N --CH ₅ CH ₀ OH .CH ₂ COO "

Connection - 10

- ⁺ N - C ₇ Hq j 3

CH ₂ COO "

Compound - ΛΛ : C ₂₁ H ₄₇ COlTH (CH ₂ ) ^ - ⁺ Έ - "GH,

Connection - 12:

CH ₂ COO "

C ₁₁ -H ₂₅ CQNH (CH ₂ ) ₅ - ⁺ Έ - (CH ₂ CH ₂ O) H

CH ₂ COO

where ρ + q =>.

A process for the preparation of the j ^ midoalkyl-quaternary ammonium carboxylic acid / betaine derivatives according to the invention is described below.

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Her s tell ungsbeispiel (Compound - 3)

+ H ₂ H (CH ₂ ) JT> C ₁ CH ₇₁ CGNH (CILp. AN <f

^{N J} CH ₇

Connection A
C, .H ₇ CONH (CHp) -, N (CH.) Ρ + ClCHpCOONa

.CCNH (CHp) ₇₁ N

CH ₂ COO

256 g (1 KoI) palmitic acid and 122.4 g (1.2 mol ·) 3-dimethylaminopropylamine were ström in a Ko-gas ^; a ^ temperature of 180 ° C heated for 6 hours and refluxed. The water and the excess amine formed in the process were removed from the system.

After the reaction, unreacted palmitic acid and amine were distilled off under reduced pressure and thereby a pale, yellowish-white solid was obtained. These raw crystals were recrystallized twice with the 2 ^^ ΪΆθίι & Ώ. Purified quantity of methanol and 190 g of Compound A were obtained in the form of small white crystals.

Then, 170 g (0.5 mol) of the thereby obtained Compound A in about 250 ml of ethanol to form a Solution solved. An aqueous solution was added to the resulting solution ITatriu-imonochloracetat-solution added which by dissolving 57 g (0.6 Hol) ClCHgCÖONa in 24 al Water had been made, added and #as system

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The product obtained is kept at reflux for 5 hours would be cooled ^ washed with petroleum ether $ concentrated and dried *

Änse'hliessehd ethanol was added to your receipt rush product and the mixture under heating geloVst "· Insoluble ITa tri by chi ο chloride were ij as a 'by-product and the ^1" Ofeeiisehtiss to Natriiimnionochloräcetat obtained by heating filtered off from the system * spell würdö the ethanol is distilled off and the product dried, with 210 g of small ₄ white iris stalls being obtained *

The product obtained consisted of the iTerbindühg - 5 * It is soluble in water or alcohol and the surface is flaky an ifoigen ^ aqueous solution of the compound 31 dyh / cm »

The other compounds according to the invention can be produced in the same way as above using the appropriate materials _4, although the production process for the connections is not limited to the method described above «

The surface active agent used according to the invention Means can be in an amount of 0.01 big j? ° g d ° .i kg of * p'hötQgi? aphis'chen tibernungssmasse are zugefeetzt and im in general, 0 ^ 1 to 5 g of the surfactant, n agent cheap, . ■. .

■ It is beneficial if the addition of the surface-active Kittelfe running in EOrni a solution, which by dissolving the surfactant in water> methanol or other miscible with water Solvents is produced »

The particularly favorable property features, which are obtained with the addition of the surface-active agents according to the invention , lie in the fact that an extremely uniformly drawn-up element is not only applied at the usual speed when it is applied.

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even with high-speed enrobing (more than 50 m / min.) Can be obtained. Furthermore, the Effects of the antistatic agent used to achieve antistatic properties for the coated Filtn is added, does not deteriorate and problems, such as friction, fogging or sticking of the printing paper or the sensitive materials can be avoided.

Even if there is a large amount of these surfactants Agent added to the photographic emulsion may not cause yellowing or other adverse effects Influences on the photographic properties, in the case of the use of polyoxyethylene as non-ionic Apparent surfactants appear, cannot be observed.

Even if the surfactants according to the Invention together with other anionic, cationic, non-ionic or amphoteric surfactants when applied, there will be no problems. In this pail these surfactants can be the same or to different layers of the photographic, light » sensitive material than to the layer to which the. added surfactants according to the invention was admitted.

Surface-active agents other than those according to the invention which are used in conjunction herewith can, for example, are in "Kaimen Kassizai No Gosei To Bono Oyο (Synthesis of Surface Active Agent and The Application Therefor) "(1964 edition) by Ryohei Oda and Kazuhiro Teramura, published by Maki öhoten, stated. '■■,' ■

The surface-active agents according to the invention can be added to the various hydrophilic colloidal substances

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draw compounds generally used in the photographic art uses earth and / or non-aqueous coatings added to ground.

Typical hydrophilic colloids or binders are, for example, gelatin, colloidal albumin, polysaccharides, Cellulose derivatives and colloids of synthetic polymers, such as polyvinyl alcohol and polyacrylamide. Since the hydrophilic colloid or the binder is of secondary importance with regard to the object of the present invention, all hydrophilic colloids such as generally used in the photographic art can be used in accordance with the invention.

Furthermore, the coating properties of non-aqueous coating compositions, which have a hydrophobic Binder, for example a water-insoluble polymer, such as polyalkyl acrylates, polyalkyl methacrylates and the like *, in an organic solvent such as methanol, ethanol, acetone, ethylene chloride and the like. ,, Contained, according to the Invention can be improved, whether they are used alone or as a mixture. The non-aqueous Coating compositions to which the compounds according to the invention can be added are very valuable when applied to the surface of photographic supports v / ground to give them antistatic properties.

The surface-active agents according to the invention can be used with all known silver halide emulsions of the different compositions used $ which chemically with sulfur, selenium, polyalkylene oxides or Compounds containing such materials as an ingredient can be sensitized. The emulsions can with a sensitizing dye, for example be spectrally sensitized to a cyanine dye or merocyanine dye.

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The coating compositions provided with the surface-active agent according to the invention for the colloidal Various photographic hardeners, for example, inorganic hardeners such as chrome alum or chrome acetate as used in the art known, or organic curing agents such as formaldehyde, Contain mucochloric acid, active halogen compounds, active vinyl compounds or ethyleneimine compounds.

The surfactants according to the invention containing photographic light-sensitive elements can also contain various emulsion stabilizers, such as azaindenes and phenylmecaptotetrazole, which are well known, antifoggants and other various additives used in the manufacture of photographic, photosensitive elements, are required, contain, for example surface treatment agents such as silicones, fluorine-containing compounds or esters of fatty acids and various color couplers, dyes, plasticizers or the like, as used in sensitive elements for dyed Light can be used.

The following specific examples illustrate preferred ones Embodiments of the invention and the results obtained therewith. These examples are for Explanation without limiting the invention.

Example 1

A series of emulsions were added by adding the compounds according to the invention or comparative compounds as a coating additive to 1 kg of a sensitive photographic negative emulsion containing 7% by weight of gelatin and 8 % of silver iodobromide in the ratio given in Table I. If nothing else

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7249471

is indicated, the percentages are also given below based on weight.

Each emulsion thus prepared was coated on a triacetyl cellulose support as previously had received an underclass.

Immediately after the work hardening of the emulsion layer, a mass for a surface protective layer was applied to it, which had been prepared by adding 200 days of gaponin to 1 kg of an aqueous gelatin solution of 2.5 % , and the comet number and for the surface protective layer obtained determines the critical speed. '

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Table I.

Coating additive

Connection 1
Connection 5

Sodium dodecylbenzenesulfonate
(Comparison)

Polyoxyethylene nonylphenyl ether
In = 10)
(Comparison)

Without

Amount added (ßj to 1 kg of emulsion

0.125

0.125

0.125

0.125

Comet number *
(Number / m2)

O
O
O

20th

Critical speed * * (m / min.)

more than JO more than JO less than 5

20 - 50

20th

* Comet: The term denotes a speckle-like one

thin coated part formed by narrowing the coating mass.

** Critical speed: Maximum speed at

who uniformly applied a gelatin solution for the protective layer to the emulsion layer becomes what is the critical speed for the protective layer

It can be seen from Table I that when the compound according to the invention was used, the critical one Speed was high and no comet was observed.

On the other hand, in the case of using liatriun ~ dodecylbenzenesulfonate as a typical anionic surfactant, the critical rate was low, and in the case of using polyoxyethylene nonylphenyl ethers (n - 10), although the critical rate was high, the comet number increased.

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In the application of the invention bond -did not have an adverse impact on the photographic properties of the photographic 'photosensitive' Material, such as fog or sensitivity, observed.

Example 1 thus shows that the surface properties of the layer which contains the compound according to the invention are improved and that the layer (gelatin layer) which is applied to the surface can be applied without rejection.

Example 2

First, a photographic emulsion was prepared by adding 5 ml of a 4% aqueous saponin solution as tjberzugszusatz to 1 kg of a sensitive emulsion for Eöntgenphotographie that 9% of gelatin and 9 ° / ° of silver halide contained prepared.

Then a mass for the surface protective layer was made by adding 100 ml of an 10% aqueous saponin solution as an antistatic agent and 10 ml of a 2.5% iS ^eri -i aqueous solution of the compound - 1 according to the invention as a coating additive to 1 kg a follow, made aqueous gelatin solution.

The photographic emulsion and the coating composition were had been simultaneously coated previously on a triacetyl cellulose support on which a subbing layer is applied so that dried films yes accordance with a thickness of 5 £ or Λ the multilayer coating traversing s were formed. The layers applied in this way were left to work harden and then dried.

Another mass for a protective coating was made made in a similar manner as above, however

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the compound according to the invention was added as an overlay not added. There were other compositions for use as a surface protective layer in the same manner as above produced, but three types of known coating additives instead of the compounds according to the invention were used.

These coating compositions and the above photographic Emulsion were coated on the carrier and in the dried in the same manner as above. The results regarding the "coating properties of the applied The film surface area and the effects of the added antistatic agent are shown in Table II.

Table II O Unavailable coating
additive O Unavailable Connection 1 Added rejection number * Static Ilar-
Quantity (g) (number / m ^) ken **
to 1 kg of the
Protective layer 1 Note 1 ihe s
Appear Connection 2 0.25 O Considerable
Appear Comparison
connection I 0.25 3 Considerable
Appear Comparison
connection II 0.25 Minor up
step Comparison
connection III 0.25 Without (single
lich saponin) 0.25 -

Comparison compound I

C _Λ "II, ₇ CCHCH _o CE _o S0_Ha * (yy ι cd 'j

CH-,

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^C - | 2 ^H 25

CH ₇

1 5

Comparative compound III

U.CONH (CH ₀
pi d

) iH

CH

CH ₀ CH ₀ CH ₀ SO d cd

* Rejection Number: The Rejection Number is calculated by

the number of rejections, per square unit of the coating counted xverden.

** Static Marks: An unexposed PiIm is applied to a

Put the rubber sheet and the PiIm with pressed a rubber roller to achieve a certain friction. Then the film is peeled off and developed using the developing agent specified below;

B-methyl p-aminophenol sulfate Uodium sulfite. (Anhydrous) hydroquinone

Sodium carbonate (monohydrate) potassium bromide

Water too

4 g 60 g 10 g 53 g 25 g

1 1

Connection ID was the number of static Marks appearing on the obtained film were determined.

It follows from Table ^ II that-the connection According to the invention, not only an excellent coating additive represents, but also does not deteriorate and even improve the antistatic properties quite well, even in your case where an anti-static gown with a low surface activity, v: ie Caponin, is used together. In addition, there were no unfavorable ones Effects on the photographic properties

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due to the addition of the compound according to the invention on.

On the other hand, it was found that '. The,

connection III has a tendency to increase dung showed.

Example 3

A photographic emulsion was made by adding

5 ml of a 4% aqueous saponin solution as a coating additive to 1 kg of a silver iodobronide enmlsion which contained a coupler together with dibutyl phthalate had been. The emulsion had a dried film thickness of 3 & A mass of 50 parts of gelatin,

6 parts of a dye and 5 parts of a mordant diluted with water so that the gelatin content was 1.6% by weight. The compound-1 according to the invention and the comparative coating additives I, II, III and IV in an amount of 2.5% and 7> 5 % based on the weight of the gelatin were added to separate portions of the resulting solution, so that separate coating compositions were obtained . Each coating composition was based on the above. applied photographic emulsion layer and determined the wetting conditions and the repellency number; the results are given in Table III.

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Added
(Wt. ° / o
bond / g
tine Table III Rejection number _p
(Number / 100 nr) Wetting
range C%) Coating
additive • 2.5 lot
Ver
GeIa- O 100 Connection 1 ■ 2.5 O 100 Connection 5 2.5 83 73 Comparison
connection I 7.5 75 '75 - Comparison
connection I 2.5 33 71 Comparison
connection .11 7.5 35 80 Comparison
link. II 2.5 50 - χ 87 Comparison
connection III . 7.5 33 95 Comparison
connection III 2.5 53 · . . ⁸ 5- Comparative
.connection IV 7.5 24- ^Λ 91 Comparison
connection IV >

* Wetting Area: The extent of wetting of a photographic with the "coating composition wetted emulsion layer in comparison "to a value of 100 (fully 'wetted Area (width of the base) of the emulsion layer) indicated by the relative percentage.

dye

ITC-C-GE-CH = CQ-GH-,
3 ii ι ι Π ■ 3

SO-, Κ
's

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Pickling agents

CH,

(η * 800)

Comparative coating additive (I)

-80-, well

Comparative coating additive (II)

Comparative coating additive (III)

Comparative coating additive (IV)

Saponin
^{C i} 2 ^H 25 ^{NHCH 2 CH} 2 ^MHCI ^ ^CH 2 ^IiHGH 2 ^C00Na

CH ₂ -

Cl '

It can be seen from Table III that the coating compositions to which the comparison compounds (I) to (IV) had been added, showed a higher repellency number and an unfavorable wetting. In particular, beneficiaries the comparative compound (I) the diffusion of the dye into the adjacent photographic emulsion layer, whereby the sensitivity of the neighboring photographi * - emulsion layer was lowered, while the comparative compound (IV) underwent dye coagulation Caused the formation of a yellow precipitate.

On the other hand, none of the above occurred Cons on and it became a uniformly wounded one

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Film obtained J if the compounds according to the invention were applied.

Example 4

An antistatic composition with the following composition was applied to a polyethylene terephthalate film support with a thickness of 0.1 mm and dried (dried film thickness 0.2 a).

Antist atic m ases.

OK solution of the. Connection - 5

according to the invention in methanol 1 g.

5% solution of cellulose triacetate ■ (Methylene chloride,: 'methanol * = 92: 8) 12 g

Phenol · - '2 g

Tetrachloroethane 8 g

Ethylene chloride 85 g

Methanol 5g

A ρ ho to graphic silver halide emulsion vjurde then on the opposite surface of the support thus coated with the antistatic composition applied. The emulsion was then dried.

In the thus prepared photographic Film was the surface resistance of the back surface of the slime, determined at 30% EH, 8 10 Ω. , This result is low compared to the surface resistance (8 10 ohms) of an untreated film and it this results in an excellent antistatic effect.

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Example 5

A photographic emulsion was prepared by adding 25 ml of a 2% methanol solution of the compound according to the invention, a color sensitizer, antifoggant, fluorescent curing agent, hardening agent and a matting agent in the usual amounts in the art to 1 kg of a silver halide photographic emulsion containing 5 % silver chlorobromide containing 1% silver bromide and 6% gelatin, including 50 mol.

The photographic produced in this way Emulsion was applied to a photographic baryta paper with a weight of 85 g / m in the manner that the amount of silver chlorobromide was 2.5 g / m 2. The emulsion was dried and the photographic Received paper.

As a comparative sample, another photographic paper was prepared as above, but that of the invention Compound omitted from the emulsion.

These samples were exposed after exposure photographic pair of an ordinary developing and subjected to fixing treatment.

Then each treated photograph was made! See paper using an MD-2 type dryer for copying for photographic paper (product of Japou Kabushiki Kaisha) at a temperature of 80 to 95 ° C during dried up to 80 seconds in such a way that the Eaiulsionsoberflache of the photographic paper in close Was in contact with the cloth belt of the dryer.

Here, the photographic paper containing the in accordance with the invention contained, without sticking to

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the cloth tape dried, -during - .. the ρ ho to graphic papers of the comparison sample when drying on the cloth tape
glued on. . ■

' Example 6

A number of photographic emulsions were made by adding a compound according to the invention or a. Comparative compound, as indicated in Table IV, prepared in the amounts indicated there. Furthermore were
a color sensitizer, antifoggant, fluorescent whitening agent, hardening agent and matting agent in the amounts usually employed for 1 kg of one
photographic silver bromide emulsion, polyglot 5% silver bromide and 15 % gelatin ^ contained, added.

Each photographic emulsion prepared in this way was coated on a photographic baryta paper (150 g / m 2 weight) in such a way that the amount of SiI overbromide was 5 · s / ^m ; The emulsion was then dried and the photographic paper obtained.

Each photographic paper obtained was used in the
treated in the same manner as in Example 5. Then became
using any treated photographic paper
the same dryer as in Example 5 at 80 to 95 ° C for 80 to 180 seconds in such a way that the emulsion surface of the photographic paper in
close contact with the cloth belt of the dryer, stood ..

After drying the photographic papers, it was used determines the adhesion between the cloth tape and the photographic paper; the results are given in Table IV.

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> 6 -

Table VI liability additive Amount added
Cg) / 1 kg of
emulsion No sticking Connection - 3
straight the he
finding 0.5 It Connection - 3
according to the He
finding ■ 1.0 ti Connection - 6
according to the He
finding 0.5 It Connection - 6
straight the he
finding 1.0 Adhere Comparison ver
binding 1 0.5 Il Comparison ver
binding I .1.0 Il Comparison ver
binding II 1.0 Il Comparison ver
binding ΪΙ1 1.0

Comparison compound I: saponin

"II: sodium dodecyl sulfate

"III: sucrose monolaurin ester

It can be seen from Table IV that no adhesion was observed and favorable drying properties were achieved could be used if the compounds according to the invention were used.

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Example 7 . ■

A number of emulsions are eliminated by adding one. Compound according to the invention or a comparison compound, as can be seen from Table V, produced in the plenums indicated there. Furthermore, a sensitizing dye, an antifoggant, a fluorescent whitening agent, hardening agent, and matting agent in the amounts usually used were added to 1 kg of a photographic silver halide emulsion containing 7.5% gelatin and 7.5 % silver chlorobromide including 30 mol% silver bromide added.

Any photographic material produced in this way Emulsion was applied to photographic baryta paper

(Paper weight 55 s / ^m) i ⁿ such a way that the applied

The amount of silver chlorobromide was 2 g / m · The emulsion Then dried and a photographic paper obtained. . - 'Each photographic paper obtained was the The following specified Abibungsschleier test in the unexposed Subject to condition, those listed in Table V. Results were obtained ..

Learn V de ^ s E eibunp; sschleie rtests:

A stainless steel needle with a point end of hemispherical shape (diameter 3 mm) vmrde with 10 g, 50 g, 100 g, 200 g, JOO g, '400 g and 500 g' weighted. The end of the score the Hadel xfurde in contact with the emulsion surface of each sample to be examined, and the point end of the needle at a speed of 10 cm / sec. guided over the emulsion in contact with it. -

"Then I vmrde iode treated in this way Prqbe one Subjected to customary development and application treatment and at the same time the extent of the

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- ■ 28

bearing the weighting occurring lieibimgsocftle.ierfoild.ung examined.

Table V ■. ■■,.

Compound Amount added Weight (g) _f

(gj / 1 kg of the άι # / effefct

emulsion

Connection * according to the invention

Compound according to the invention

Compound vegetable of the invention _v

Compound according to the invention

Comparison compound I

Comparison compound I

Comparison compound II

Comparison connection II

Comparison compound HI

Comparative compound III

Settlement pre-binding IV

Comparison link IV

Without

0.5 1.0

0.5 1.0

0.5 1.0

0.5 1.0

0.5 1.0

dung occurred,

400 ■ /

300 ti 500 50 'ineffective 50 \ <· ■ "". '', 50 Il · 50 . it 50
100 '' * '.
¹ ■ · i
■ slightly 50 50 · 50 ¹ It

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Comparison compound I: sodium dodecyrbenzenesulfonate

"II: saponin

"III: sucrose monolaurin ester

"IV:. Sodium Dodecyl Sulphate

It is found from Table V that the frictional fogging prevention effect in the photographic. Papers containing the compounds according to the invention, remarkable compared to those was, di.e did not contain a compound according to the invention or the above comparison compounds contained..

From this and the preceding examples it can be seen that the compounds according to the invention have extremely favorable properties compared to the known compounds.

In the foregoing, the invention has been described on the basis of preferred embodiments without being subordinate to this is limited.

309816/1165

Claims (1)

2249Λ71 Claims A photosensitive silver halide photographic element comprised of a support which is a photographic emulsion and a compound represented by the following general formula f. HC ONII (CH ₂ ) _n ⁺ NR ₂ CH - (CH) - COO I j ^x where R is a saturated or unsaturated hydrocarbon group with 7 to 21 carbon atoms, E and Ep are alkyl groups, hydroxyalkyl groups or polyalkylene oxide chains each with 1 to 18 carbon atoms, E ₇ and IL are hydrogen or alkyl groups with 1 to 4 carbon atoms, η is an integer of 2 or more and χ the numbers G or 1 means "; .. _; has. 2. Photosensitive silver halide photographic element according to claim 1, characterized in that the compound has the following formula: CH. τ. CHpCOO 3 · Light sensitive, photographic silver halide element according to claim 1, characterized in that the compound has the following formula: 309816/1 165 GH ₂ COQ ' 4-. Photosensitive3 sirper halide photographic element according to spoke 1, characterized in that the compound has the following formula: • - f? CH ₂ GOO " 5. Silver halide photographic photosensitive element according to claim 1, characterized in that the compound has the following formula; CrH ΟΟΝΗ (ΟΠρ) ρ - H- OH ClI _n OGH OHpOH CH CH ₂ COO " 6. Silver halide photographic photosensitive element according to claim 1, characterized in that the compound has the following formula: .. C ₁₇ H ₃₅ GONH (GH ₂ ) - N 'C CH-, I ³ N - CH . CH COO7 7 · Light sensitive, photographic silver halide element according to claim 1, characterized in that 3098 16/1165 224 9-71 the compound has the following formula: 9H ₇ . CH ₂ COO 8. Photosensitive photographic silver halide learning ent according to claim 1, characterized in that the compound has the following formula: ) ₅ - ^ - C ₄ H ₉ CH ₂ CH ₂ COO " 9 · Silver halide photographic photosensitive element according to claim 1, characterized in that the compound has the following formula: C..H ₀ ^ CONH (CH ₀ ) _o - ⁺ K - CH, CH ₂ CHCOO CII 10. Photosensitive, photographic silver halide element according to claim 1, characterized in that the compound has the following formula: CII ₀ CH ₀ OH C. _r7 II _y7 CG! IH (CH _o ). - ⁺ 1J - CH ₀ CH ₀ OH ^CH ₂ COÜ ~ 3 0 9 8 16/1165 2249Λ71 "11. Silver halide photographic photosensitive element according to claim 1, characterized in that the compound has the following formula: / p 9
C ₇ H ₁₅ COHE (CH ₂ ) ₂ - ⁺ N - C ₃ II ₉ CH ₂ COO 12. Silver halide photographic photosensitive element according to claim 1, characterized in that the compound has the following formula: CIL, CH ₂ COO 13. Photosensitive, photographic silver halide secondary according to claim 1, characterized in that the compound has the following formula: (CH ₀ CH ₀ O) H. J ^P ) _z - ⁺ H - (CH ₀ CH ₀ O) JE ₂ CH ₂ O) _q CH ₂ COO where ρ plus q have the value 5. 14. Silver halide photographic photosensitive element according to claim 1 to 13> characterized in that that the emulsion contains a hydrophilic colloid. 15. Yellow halide photographic photosensitive element according to claim 14, characterized in that "The hydrophilic colloid contains gelatin. 16. Photosensitive photographic silver halide element according to claim 14 or 15, characterized 3 0 9 8 16/1185 draws that the connection; is contained in the emulsion. 17 · Light-sensitive, photographic silver halide · material according to claims 1 to 1J? » characterized, that the compound in an antistatic layer on the surface of the support opposite to the emulsion layer is included. 18. Photosensitive silver halide photographic solvent according to claim 1 to 15 »characterized in that that the element comprises a multilayer color photographic element and the compound is in at least one hydrophilic colloid-containing layer of the element is available. 19- Light-sensitive, photographic silver halide element according to claims 1 to 18, characterized in that the compound is contained in a layer applied to the support in an amount of from 1 to 50 6 J ^e 1 kg of the photographic coating composition which forms the layer is. 20. Photosensitive, photographic silver halide element according to claim 19> characterized in that the compound in an amount of 0.1 to 5 g per 1 kg of the photographic wetness is included. 21. Silver halide photographic photosensitive element according to claim 1 to 20 ·, characterized in that the compound is in a hydrophilic colloid layer is present, this layer initially being drawn onto the support. 22. Silver halide photographic photosensitive element according to claim 1 to 20, characterized in that the compound in a hydrophilic colloid layer is included with a hydrophilic colloid layer is covered. 2J). Light; e: ap cortical, photographic. Silberhalo- gewi uelciiviii nah ; · ¹ ! iVun Claim 1 am 22, thereby gckerin ^ oichno t, if; / i! t; s BATH that it contains a hydrophobic colloid. 24. Photosensitive, photographic silver halide element according to claim 1 "to 2J, characterized in that it is gelatin, albumin, as the hydrophilic colloid
Contains polysaccharide, a cellulose derivative, polyvinyl alcohol, a polyacrylamide or mixtures thereof. 25 ♦ A method of making a silver halide photographic photosensitive element, wherein
at least one hydrophilic colloid layer is applied to a carrier, characterized in that at least
a hydrophilic colloid layer in contact with a compound represented by the following general formula RCCETII (CH ₂ ) _n - ⁺ H - E ₂ CH - (CH) - CÜO i ^x is drawn up, wherein E is a saturated or unsaturated hydrocarbon group having 7 to 21 carbon atoms, 1?
and Ep alkyl radicals, hydroxyalkyl radicals or polyalkylene oxide chains each with 1 to 18 carbon atoms, E ₇ , and Ii ₁
a hydrogen atom or alkyl radicals with 1 to 4 carbon atoms, η an integer of 2 or more and χ the numbers 0 or 1 mean. 26. The method according to claim 25, dadui'ch characterized in that the compound in at least one hydrophilic
Colloid layer is drawn up. 27. The method according to claim 25, characterized in that that we put on at least one layer that the Compound and a hydrophilic colloid contains. 28. Ancestors according to claim 27, characterized in that ccke ^ mssiclv- 0 9 8 16/1165 ^BÄD net that the coated layer continues «in silver halide and the layer of a photographic, photosensitive silver halide emulsion layer consists. " 29 · The method according to claim 25 to 2S _1, characterized in that a hydrophilic colloid »containing gelatin is drawn up. 30. The method according to claim 26, characterized in that the hydrophilic layer from the initially the layer applied to the carrier - 31. The method according to claim 26, characterized in that that the hydrophilic colloid layer with a hydrophilic Colloid layer is coated. 32. The method according to claim 27 »characterized in that that the layer is applied as an antistatic layer. 309816/1 165