DE2939243A1 - PHOTOGRAPHIC MATERIAL AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

The present invention relates to an improvement in the preparation process for silver halide photographic materials containing an antihalation layer derived from the surface of the support other than that on which the photosensitive emulsion layers are formed can be easily removed and materials containing can be obtained according to this method.

Photographic materials must be protected from the halation that occurs again on the light due to the backing of a photographic material sensitive layers of reflected light takes place »

This halation can be prevented by a light-absorbing layer, generally called an "anti-halation layer" which is coated on the surface of the support other than that on which the photosensitive emulsion layers are formed. These antihalation substances are generally composed of an in a natural or synthetic binding resin dis pergated dye or pigment.

There are two alternatives in the formulation of these antihalation layers: 1) the "decolorizable type" in which the dyes or pigments contained in the antihalation layer are decolorized during development; and 2) the "removable type" in which the binding resin is soluble during development.

In the removable type of antihalation layer, binding resins become soluble in aqueous alkaline solutions must be, and soot or colloidal carbon that is in

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dispersed in these resins.

Some of these resins are described, for example, in U.S. Patents 2,271,234, 2,327,338, 3,392,782, and im BE patent 613,472 indicated.

In some of the latest development systems for black and white and color photography, the film is converted into a swelling (not removing) pre-bath which contains an alkali solution is high in salinity. According to the method, this solution can serve other functions (e.g. as a pre-hardener or developer solution) or its sole role can be to dissolve the anti-halation layer (e.g. a pre-hardener). bath or a solution removing the substrate); then the film leaves the alkali solution and is washed with water to to remove said antihalation layer. It may also be desirable to have a magnetic track on the side of the base that has been freed from the aforementioned antihalation layer to apply.

Usually the swelling bath may have the antihalation layer do not dissolve, but only convert the acidic groups of the binding resin into salts in order to make them water-soluble.

In order to prevent contamination of the swelling bath, the resin of the antihalation layer must remain solid and in the Do not dissolve the swelling bath if it is also neutralized in the swelling bath mentioned. An insignificant removal of the anti-halo layer in the swelling bath is necessary. especially to avoid any scratches on the film. During a subsequent washing stage with water and before As the material enters the first development bath, the antihalation layer must be easily and completely removed. Sometimes this stage of washing with water becomes complete Removal of the antihalation layer under water jets Pressure used.

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However, it is very difficult to formulate an antihalation layer to have a complete removal by water jets alone permitted. When you get into the aqueous alkali solutions Easily soluble binders used for complete removal by means of simple water jets to allow, the strength of the anti-halation layer becomes too low to withstand the swelling bath and the layer shows a tendency to swell. to contaminate the end of the bathroom. On the other hand, if you have a Binder with a low solubility in the alkali solution used to provide strength to the layer in the swelling bath so get that? it does not contaminate the bath, so is complete removal of the Anti-halation layer by means of simple water jets is not safe and remains behind on the substrate a thin film of the antihalation layer as a haze. Therefore, it is common in the relevant photographic treatment, after or during the washing step with water jets, the phctographic material immersed in the flowing Kasser with perforated rollers, the

are covered with a soft material, or with Bring brushes in contact to remove the remaining antihalation layer. One not quite perfect 25th

working mechanical action of the rotating rollers or Brushes from wear and tear or from defects of the same often causes incomplete removal of the antihalation layer.

A material with a resistance in the swelling bath

and, in a subsequent washing step, easily removable antihalation layer, is described in US Pat. No. 4,039,333; this layer contains a resin mixture which consists essentially of a terpolymer containing 10 to 25% alkyl acrylate units, 52 to 65 % alkyl methacrylate units and 18 to 30 % acrylic or methacrylic acid and

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consists of a resin that is soluble in aqueous alkali solutions

However, this layer is not completely removable by means of water jets and without the mechanical work of the contact rotating rollers or brushes brought with it.

the main object of the present invention is therefore to use anti-halation shields for black-and-white and color photographic materia » to obtain lien, which are essentially not removed in the usual swelling alkali baths which, however, in the usual washing stage by means of simple water jets (i.e. without the mechanical Work of cleaning rotary rollers) can be completely removed.

These alkaline swelling baths and washing steps are in the art of color positive films commonly known as, for example, from Charleton C. Bard and James E. Dumm in "Journal of the SMPTIi", 80 (Jul 1971), 56 * 1-569. A special reference can to the ECP conditions described therein. More precisely, it is the task of the present Invention to provide a material and a method for its manufacture that can be used in the usual ECP processes

has the following characteristics:

Pre-bath (a sodium sulfate,: A) m.Qz. lower than sodium hydroxide and borax 10 seconds, containing alkali solution) _{fi) Insignificantc Hnt}

at 27 ⁰ C

from 10-20 seconds.

distance in times

Washing bath with Wasserstrah: C) Full Entler at 27 ⁰ C or 20 ⁰ C in a fernung (oh / .i: Reinigungsdrchwalzen) time of 2 seconds

(with a usual _e a water consumption

of II, ¹ * liter / min at

a pressure of 0.5 atü including water treatment).

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The m.Qz. Is the minimum swelling time for a standard solution given in Example 8 of the specification, i.e. the minimum time the material must remain in the prebath for the antihalation layer to be completely removed in the following washing stage, under normal conditions and including the mechanical action of rotating cleaning rollers which are provided with mohair as a cleaning material, as described in the Journal of the SMPTE cited above. A substantial removal of the antihalation layer corresponds to a removal of at least 80 % of the layer, as measured.

Insignificant clearance (ie, a removal that is acceptable in the ECP process noted above) has been estimated to be no more than about 50 % _t, and in most cases less than about 10 to 20 % of the layer.

As observed, the process is critical in that it provides mean values of the aperture in the layers were not found. They were either high (unacceptable), or low (acceptable). Complete removal of the layer means 100% of it Distance.

Other alkali swelling and washing steps are those that are commonly known in the art of color reversal films, with an alkaline swelling step (called rem-jet remover) and a washing or rinsing step of | pre-hardening and neutralization

follow stage. I can draw particular attention to the conditions of the EM-25 process. Line another more specific object of the present invention is to provide a material and a method for its manufacture that in the EM-25 process the following Features has:

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Rem-jet remover faus: A) m.Qz. lower than 2 the first development second tank overflowing solution) at 52 ° C

Rinsing with water jet: B) Complete removal (without cleaning rotation in a time of

rolling) at 52 ° C for 3 seconds (under the

conditions described above).

M.Qz., substantial removal and complete removal have the meanings already mentioned above.

Another object of the present invention is to provide a material having a removable antihalation layer so that at the end of the process it is possible to carry out some auxiliary work steps on the layer support, such as applying a magnetic track.

These and other objects of the present invention are accomplished by using an antihalation device applies the one in a binding material that in aqueous alkali solutions is soluble, contains dispersed antihalation agent, which consists essentially of a mixture of two copolymers (lower alkyl methacrylate-acrylic or methacrylic acid), the acrylic or methacrylic acid mengcn in the two copolymers and the mixture ratio of the two copolymers are such that one in the above-mentioned swelling bath is swellable and solid. -uJ by means of simple washing treatments layer removable therefrom is obtained. Before-

Sometimes this antihalation substance is soot, this one Alkyl methacrylate is methyl methacrylate and this acrylic or methacrylic acid is methacrylic acid. Of the preferred percentages of acrylic or methacrylic acid in the first copolymer is 40 to 50, preferably 42 to 4G and the most preferred

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The range is 45, while in the second copolymer it is 20 to 30 .. preferably 22 to 26 and the most preferred range is 25, the percentage of the first copolymer preferably being 30 to 501 of the blend with the second copolymer. A resin which is soluble in an aqueous alkali solution is preferably added to the above-mentioned mixture of the two copolymers as a substance which regulates the viscosity of the antihalation composition. Preferably ¹ ^ this resin is a carboxyl group-containing synthetic copolymer or cellulose derivative, more preferred resin is tin Hydroxypropylmcthylzelluloöephthalat.

Accordingly, the present invention relates to an improvement in preparation of a photographic material comprising a

Layer support, at least one silver halide exposure layer applied to one surface of the support and an anti-halation layer applied to the other surface of the support, which is useful in a process that includes a swelling alkali bath and a subsequent water-washing bath, wherein said anti-halation layer must be swollen without being removed are or is removed in the abovementioned washing bath, with the improvement! consists in the fact that the said antihalation layer essentially consists of an »antihalation substance ( e.g. dye, pigment or soot)

and d?.: n Mixture of two copolymers of a low 30

Alkylirethacrylate and acrylic or methacrylic acid. The first copolymer is richer in acrylic or methacrylic acid (so one in the swelling stage at least partially removable antihalation layer is obtained when using said first copolymer applies alone), and the second copolymer is less rich in acrylic or methacrylic acid (^ o that

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29392A3 cine in the swelling and unsquillable in the desired time and therefore an unremovable antihalation layer is obtained in the subsequent water washing step, when using said second copolymer alone), the amounts of acrylic or methacrylic acid in both Copolymers and their mixing ratio are such that one swellable and non-removable in the abovementioned swelling bath and removable in the abovementioned washing bath Antihalation layer is obtained. 10

The present invention also relates to a photographic material consisting of a support, at least a silver halide emulsion layer coated on one surface of the support and one the antihalation layer applied to the other surface of said substrate, said Antihalation layer consisting essentially of an antihalation substance and a copolymer mixture of a lower alkyl methacrylate and acrylic or methacrylic acid as determined above b.

More specifically, the present invention consists of an antihalation layer photographic material as described above, said layer consisting essentially of an antihalation agent and a copolymer blend of alkyl methacrylate wherein said alkyl of Has 1 to 4 carbon atoms, and acrylic or methacrylic acid, and preferably consists of a copolymer mixture of methyl methacrylate-methacrylic acid.

The present invention also consists in a antihalation layer of a photographic material, as described above, wherein the anti-halation layer consisting essentially of a said Antilichthofstoff and a mixture of

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Copolymers of lower alkyl (preferably methyl) methacrylate and acrylic or methacrylic (preferably methacrylic) acid wherein the first copolymer is 40 to 50 weight percent Acrylic or methacrylic acid and the second copolymer 20 to 30 percent by weight acrylic or methacrylic acid, preferably the first copolymer 42 to 48 percent by weight acrylic or methacrylic acid and the second copolymer 22 to 28 percent by weight Contains acrylic or methacrylic acid and the most preferred amount of methacrylic acid in the first copolymer 45 Weight percent and in the second copolymer is 25 percent by weight. According to the present invention, the mixture contains of the two copolymers 30 to 50 percent by weight of the copolymer richer in acrylic or methacrylic acid. The present The invention also consists in a photographic material as described above, in which the antihalation layer in addition to the antihalation agent and the copolymer mixture, preferably one soluble in an aqueous alkali solution polymeric resin as the antihalation layer viscosity regulator, the preferred resin a synthetic copolymer or cellulose derivative containing carboxyl groups, and more specifically hydroxy propylene methyl cellulose phthalate is. Other types of these alkaline aqueous solution resistant resins are in the art

known.
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The antihalation layer of the present invention preferably contains 30 to 42 percent by weight of the lower alkyl (preferably methyl) methacrylate-acrylic or methacrylic acid copolymer richer in acrylic or methacrylic acid, 53 to 60 percent by weight of the lower alkyl (preferably Methyl) methacrylate-acrylic or methacrylic acid copolymer and 0 to 15 percent by weight of the above in an aqueous

Alkali solution of soluble resin.
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We found the two that

Lower alkyl methacrylate-acrylic or methacrylic acid copolymers forming anti-halation agents of the present invention have a different Must contain percentage of acrylic or methacrylic acid.

Namely, we have found that the antihalation layers of photographic materials the two individually used co include polymers of the present invention, when immersed in an aqueous alkali bath containing sodium sulfate, borax and sodium hydroxide Color positive film are immersed for a time of 2 minutes, in the case of the copolymer richer in acrylic or methacrylic acid, so soft that a mechanical contact scratches away the antihalation layer completely and, in the case of the copolymer less rich in acrylic or methacrylic acid, the above Layer remains firm, even if a mechanical one

Contact is present

We have found that antihalation layers in photographic materials that Bination of the two copolymers of the present invention have as a binding resin when they are in a Alkali bath, as written above, to be immersed for a period of 2 minutes, remain firm and keep their original shape, even if they are in Above mentioned pre-bath are exposed to mechanical contacts, and can be easily and completely removed in the subsequent water washing stage. From The anti-loft layers existing in the individual components either soften too much in the prebath or not enough.

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The removability of the antihalation layer in the on the The swelling level in the pre-bath following the washing level depends partially on the swelling time and pre-bath temperature and, of course, also on their nature and storage conditions away. An indicative parameter useful in characterizing the behavior of an antihalation layer is the minimum swelling time in the pre-bath at a certain temperature. As said above, the m.Qz. the minimum time which the material must remain in the pre-bath in order to remove the antihalation layer in the next To achieve the washing stage with water under normal conditions, the mechanical work of a cleaning rotary roller including. With a swelling time in the pre-bath that is lower than the m.Qz. is, is this Layer not completely removable from the base of the photographic material in the washing stage, also know this contains the mechanical action of the rollers or brushes; against it becomes the antihalation layer completely removed in dcT Kasch level if the swelling time is the same or greater as the m.Qz .. and the Kasch level is also the mechanical one Includes action of rollers or brushes.

We have found that the copolymers less rich in acrylic or methacrylic acid (lower alkyl methacrylate-acrylic or methacrylic acid), when used alone, have antihalation layers with a m.Qz. at 20 ⁰ C from 50 to 120 seconds, the ge

3Q is certainly higher than the swelling time usual in the prebath of the photographic treatments; when the anti-halation layers for a time of 24 to 48 hours at 105 ⁰ C and 25% RH are mounted to advanced aging conditions to simulate the material, we have found that the same layers tend to infinite m.Qz. to have, that is, that they are no longer

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can be swelled. On the contrary, the acrylic or methacrylic acid richer copolymers (lower alkyl methacrylate-acrylic or methacrylic acid) when used alone are used, anti-algae layers with a m.Qz. from 7 to 8 seconds, which is certainly less than the swelling time customary in the prebath for photographic processing; furthermore, when the layer is stored as described above, it tends to double its m.Qz. value.

On the contrary, we have found according to the present invention that the combination of the two copolymers of present invention as binding resin-containing antihalation layers have an m.Qz. value of 8 to 9 seconds have and also that the m.Qz. for the same as above described, stored layer remains the same or increases slightly.

A means of determining the full removability of the antihalation layer after the previous The existing alkali bath has left and is then exposed to the washing bath, which consists only of jets of water under pressure exists, is the determination of the optical absorption density in the visible spectrum of the remaining veil, which receded from the thin film of the antihalation layer and has not been completely removed.

In the experiment we noticed that the antihalation layers of photographic materials, which or methacrylic acid less rich copolymers of low rigem alkyl methacrylate and acrylic or methacrylic acid as contain binding resin, after a / m.Qz. that layer at that temperature corresponding swelling time in the prebath, if it is a water bath with simple water jets under a pressure of 0.5 atü, as in the usual treatment lungs, or even 0.1 atmospheres, none Veil or any of the optical density of the layer that

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If the photographic processing is not exposed, the same fog (i.e. the antihalation layer is not removed) for the same at 105 ° C and 25% RH. for 24 and i »Leave layers stored for 8 hours. 5

We have also noticed that anti-justice layers of photographic materials employing the acrylic or methacrylic acid-rich copolymers of lower alkyl methacrylate and acrylic or methacrylic acid as the binding resin included, after a swelling time in the pre-bath, which the m.Qz. corresponds to this layer at the respective temperature, leave a heavy haze when subjected to the same washing stage, both if they have been stored and if they have not been stored

On the contrary, we found that

Antihalation layers of photographic materials, the di? Copolymer combination of the present invention contained as a binding resin, after a the m.Qz. The swelling time corresponding to that layer does not leave a haze in the prebath if the washing stage with simple water jets under pressure and without further mechanical work be exposed, regardless of the type of storage state of the anti-halation layer

The two copolymers differ from one another in their percentage of acrylic or methacrylic acid: One is richer and can be 40 to 50 percent by weight Acrylic or methacrylic acid, and the other is less rich and can contain 20 to 30 percent by weight acrylic or methacrylic acid. Both copolymers have an intrinsic viscosity (in ethanol at 25 ° C) from 0.1 to 0.5, preferably from 0.15 to 0.3, with higher or low values are known to be chosen to be a to obtain higher or lower binding capacity.

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In accordance with the present invention, the first copolymer preferably contains 42 to 48 weight percent acrylic or acrylic Methacrylic acid and the second copolymer 22 to 28 weight

Percent acrylic or methacrylic acid. 5

According to the present invention, the particularly preferred content of methacrylic acid is 45 percent by weight first copolymer (methyl methacrylate-methacrylic acid) and 25 percent by weight in the second copolymer (methyl methacrylate-methacrylic acid). Both copolymers are insoluble in water at room temperature and easily soluble in an aqueous alkali solution at room temperature.

The mixture ratio between the at

Acrylic or methacrylic acid richer copolymer and the acrylic or methacrylic acid copolymer is less rich in the antihalation-Zwsamnensetzung the present invention may change under certain limits, whereby an excess of these limits .. ² ^ richer of acrylic or a copolymer Mcthacryl In the prebath there is less firm antihalation layer, while an excess over these limits of the copolymer, which is less rich in acrylic or methacrylic acid, is a

There is an antihalation layer, which is then

can be more difficult to remove at the lower Kasch level.

We have found that in the mixture of the two copolymers the content of the copolymer richer in acrylic or methacrylic acid compared to the total content of the two resins is from 30 to 5% by weight

can change, with the remaining part consisting of the acrylic or methacrylic acid less rich copolymer.

We have found that has under customary conditions of photographic processing an overall ^ ₅ mixed, good jFestigkeitseigenschaften in pre-bath and good Entfembarkeitseigenschaften in the subsequent washing step with simple water jets

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preferably from 53 percent by weight of the copolymer containing 25% methacrylic acid (methyl methacrylate-methacrylic acid) and from 47 percent by weight of the copolymer containing 45% methacrylic acid (methyl methacrylate-methacrylic acid). stands.

We have also found that the binding material in which the antihalation agent of the present invention is dispersed, besides the mixture of the copolymers described above, usefully solubilizes others in aqueous alkali Liche, natural or synthetic resins, such as those known in the art, such as cellulose acetophthalate, hydroxypropyl methyl cellulose acetyl phthalate, hydroxypropyl methyl cellulose phthalate, maleic anhydride mixed polymers and vinyl comono- ricre, acrylic and methacrylic acid-containing copolymers, etc. Because we found that some amount of these resins are useful in the blend of copolymers of the present invention is for the application of the antihalation layer to the support of the photographic material suitable composition viscosity Z.u obtained.

Kir have found that HydToxypropy) methyl cellulose phthalate is appropriately the preferred one Is resin and that its amount can vary from 0 to 15% by weight of the total amount of the resins of the anti-halation composition according to the invention; too high amounts change the properties of the antihalation layer fr..B. in the presence of hydroxypropyl methylcellulose phthalate, they cause the layer to have a low strength in the pre-bath).

The antihalation composition of the present invention is obtained by adding the antihalation agent dispersed in a solution of the copolymer mixture in an organic solvent as described above.

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The preferred antihalation agent is Russ, u.z. finely ground carbon that consists of Particles with a diameter of 1 to 100 are rough. Many finely ground types of carbon are available known, but the best are those that are produced by a simple ball mill with the copolymers of the present invention, such as Vulcan XC-72 (manufactured by Cabot Corp.), which is also very conductive. Dispersed colloidal carbons or antihalation dyes can also be used.

Many types of dispersing tools can also be used to disperse carbon black and to obtain permanent dispersions; the dispersants well known in the art are those Polynaphthalene sulfonates.

Many useful solvent combinations have been found to address the above To obtain copolymer solution according to the present invention. As is known, these solution combinations according to the special substrate on which. the antihalation composition of the present Invention to be applied should be selected. Appropriate solvents are e.g. methanol, acetone, Methyl cellosolve, ethylene glycol, etc.

The antihalation composition of the present invention can be applied to the hydrophobic layer-J ₀ carrier of the photographic material by various techniques, namely by the injection molding, roll, Gegenrakel-, air knife order lancing Niken applied, v / ground.

The substrate is generally cellulosetria ^ etat, but other layers, such as

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Polyethylene terephthalate can also be used, and good adhesive strength is also obtained the antihalation layer, even without using the underlayers known in the art. 5

On the other surface of the support there is at least one silver halide emulsion layer applied, such as silver bromide, silver chloride or silver iodide emulsions or Emulsions containing mixtures of silver halide, such as silver bromoiodide or silver chlorobromide emulsions. Any type of emulsion known in the art that is bath treated or treated is useful in the present invention.

The present invention will now be explained in more detail with reference to the following examples.

The production of useful in the mixture of binding resins of the inventive composition copoly * - \ mers will now be given in the following examples.

Example A.

4,800 ecm of ethanol, 2 ¹ JO g (2.8 mol) of methacrylic acid, 720 g (7.2 mol) of methyl methacrylate and 4.8 g of azo-bis-isobutyronitrile were placed in a three-necked flask in the order given. The mixture was then refluxed on a water bath for 24 hours.

and the resulting solution was cooled to room temperature. The cooled solution was poured into a large volume of water with vigorous stirring so that the polymer precipitated. The product was then filtered, washed with water and dried at 60 ° C. under air for 24 hours. The yield was 845 g (88 %) . The weight content of the methacrylic acid was 25 %.

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The viscosity in ethanol at 25 ⁰ C was 0 _f l8 ml / g.

Example B.

4,650 ecm of ethanol, 430 g (5 mol) methacrylic acid, 500 g (5 mol) methyl methacrylate and 91,3 g azo-bis-isobutyronitrile in the order given introduced * The resulting mixture was then treated

delt as given in example A. The yield was 28 Jf, the content of methacrylic acid was 45 % and the intrinsic viscosity in ethanol at 25 ° C. was 0.23 ml g.

The present invention will now be illustrated in the following examples in comparison with some prior art examples

the technology explained.
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Example 1 (state of the art)

One surface of a 140μ thick cellulose triacetate film was coated with a dispersion of the following composition at a speed of 30 ccm / m:

Copolymer (methyl methacrylate-methacryl

acid) of Example A 36 g

Vulcan XC-72. (manufactured by Cabot Corp.) 9

Lissatan AC (codensate of naphthalene sulfone

acid and formaldehyde, manufactured by ICI) ---- 0.9 g

Acetone - "- 2Ö0 ecm

Methanol 630 ecm

Methyl cellosolve - 100 ecm

Water - - - ^? 0 ecm

The coating was then at 105 ⁰ C ^; Dried for 15 minutes and obtained an antihalation layer that has an optical density in the visible spectrum of about

1 had.
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Example 2 (prior art)

An antihalation layer was made as in Example 1
but using the copolymer
(Methyl methacrylate methacrylic acid) of Example B

in an amount of 36 g, instead of the resin of Example A,

Example 3 (invention)

An antihalation layer was prepared as in Example 1, but using a Genisch
of 19 g of the resin of Example A and 17 g of the
Haerzes of Example B, instead of the resin of
Example A.

Example 4 (invention)

An antihalation layer was prepared as in Example 1, but using a mixture
of 19 g of the resin of Example A, 15 g of the resin of Example B and 2 g of Hydroxypropylmethylzel-

lulosephthalate, instead of the resin of Example A.

Example 5 (prior art)

A surface of a 140 μ thick cellulose triacetate film was blown at a rate of 30 cem / m ²
with a dispersion of the following composition
coated:

271 ethyl acrylate, 231 acrylic acid and SOl
Terpolymer containing methyl methacrylate
(as indicated in U.S. Patent 4,039,333) ZO g

Hydroxypropyl methyl cellulose phthalate 10 g

Vulcan XC-72 10 g

Lissatan AC 1 g

Acetone 460 ecm

Methanol 420 ecm

Methyl cellosolve 50 ecm

Water --- 70 ecm

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The coating was then dried at 105 ° C. for 15 minutes and an antihalation layer was obtained which had an optical density of about 1 in the visible spectrum.

Example 6 (prior art)

An antihalation layer was prepared as in Example 1, but using cellulose acetohexahydrophthalate in an amount of 36 g instead of the resin from example A.

Example 7 (prior art)

An antihalation layer was prepared as in Example 1, but using cellulose acetophthalate in an amount of 36 g instead of the resin of Example A.

Example 8 (comparison of the invention with the prior art Technology)

The other surface of the support than that on which the antihalation layers of Examples 1 to 5 was applied in the order given with an undercoat, a blue-sensitive one Layer, a red-sensitive layer and a green-sensitive layer, with intermediate layers and one 25th

Protective layer coated around a photographic

Color positive film. All of these materials were then immersed in a standard pre-bath of the ECPg process, which had the following composition:

Sodium sulfate 100 g

Borax 20 g

Sodium hydroxide 1 g Water up to 1,000 ccn.

The pH of this bath was 9.25 and the immersion time of the five materials was 120 seconds at 20 ° G.

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Under these conditions, the antihalation layer of Example 2 in the prebath mentioned in the essential removed. The same removal took place with an immersion time of 15 seconds, the the usual time in the photographic ECP process, As described above, _f This behavior caused sludge formation and contamination in the pre-bath. In contrast, the antihalation layers of Examples 1, 3, 4 and 5 were essentially not removed under the same immersion conditions.

Example 9 (comparison of the invention with the state of the technique)

The antihalation layers of Examples 1 to were in the prebath of Example 8 at 20 ° C or 27 ° C and the minimum swelling time (m.Qz.) required for the complete removal of the anti-halation layer in the usual washing stage with water and Cleaning rotary rollers was necessary, was measured (the ο

Washing stage was with water at 20 C and below one

Pressure of 0.5 atü with 11.4 liters / min water consumption and mohair as cleaning material). The same procedure was repeated with other samples of the same antihalation layers stored for 24 and 48 hours at 105 ° C and 25 % rP. In the following table the m.Qz. values are reported at 20 ° C of the various antihalation layers under fresh and stored conditions (values at 27 ⁰ C are shown in parentheses):

Antihalation layer

of the example 1 2 3 4 5

Fresh 120 "(SS") 7 "(3") 9 "(4") 8 "(4") lCr (4 ")

24 hours

Storage - 13 "(16") 9 "(4 ^M ) 9 ^Μ (5")

48 hours

Storage · 14 "(7") 12 "(6") 12 "(6")

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Example 10 (comparison of the invention with the prior art Technology)

The antihalation layers of Examples 1 to 5 were placed in the pre-bath described in Example 8 for a time corresponding to their m.Qz. values and then washed with water and without cleaning spinning rollers.

The same procedure was repeated with another 2 ¹ * and hours at 105 ⁰ C and 25% rP, stored samples

the same antihalation layers applied. In the following table, the remaining, as optical Absorption density of the haze of the antihalation layer measured in the visible spectrum.

Anti-lighthcf layer

of the example 12 3 4 5

Fresh 0, CJO 0.36 0.00 0.00 0.09

24 hours

Storage. = 1.00 0.38 0.00 0.00 «1.00 48 hours

Storage * 1.00 0.40 0.00 0.00 = 01.00

Example 11 (comparison of the invention with the state of the art) - "*

The other surface of the substrate than the-. those on what the antihalation layers of the examples 4, 6 and 7 were applied, in the order given, with one undercoat, two red-sensitive layers and two green-sensitive layers

Layers, one yellow filter layer and one blue

sensitive layer,. -nit intermediate layer, and coated with a protective layer, one. Xinaxar Reversal Film. All three materials were then treated in the usual EM-2S treatment stages, e.g.

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Solution / level temperature ( ⁰ C) ', time (sec.)

VoThärter 51.7 ± 0.1 37

Neutralization 51.7 ± 2.8 32.5 Rem-jet remover 51.7 ± 2.8 2

Irrigation 5i, 7 ± 2.8 3

The rinsing was carried out simply with water jets without cleaning rollers, as in the usual rinsing. Under these conditions the antihalation layer of Example 4 remained solid and without any removal in the usual neutralizing bath; in the usual rem-jet remover it had an m.Qz. value of 1 second and in the rinsing stage it was completely removed with simple water jets without a film

to leave the antihalation layer. The anti-light Courtyard layer of Example 6 behaved like that of the above example in the usual neutralizing bath had an ra.Qz. value of 1 second in the usual Rem-jet remover, but in the rinsing stage with simple water jets a residual film was left behind. Eventually the antihalation layer became of Example 7 is essentially removed in the usual neutralizing bath and therefore the emulsion side of the film is stained and consequently the treatment solution is contaminated.

The term "weight percent" means the weight percent of an individual component over the total weight of the copolymer components.

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ORIGINAL INSPECTED /

Claims (1)

VOSSlUS- VOSSIUS- HILTL -TAUCH N ER · HEUNEMANN -RAUH PATENT LAWYERS SIEBERTSTRASSE A ■ 8OOO MÖNCHEN 86. PHONE: (O89) 47 * 075 CABLE: BENZOLPATENT MDNCHEN · TELEX S.J9453VOPAT D u.z .: P 333 (Ra / ko) 2 7 SEP 1979 Case: F 3M / 31O MINNESOTA MINING AND MANUFACTURING COMPANY Saint Paul, Minnesota, V.St.A.
10 ^w Photographic material and process for its production " Priority: September 27, 1978, Italy, No. 51275 A / 78 Claims 1. Photographic material consisting of a support, at least one deposited on a surface of the support. carried silver halide emulsion layers and one on the antihalation layer applied to another surface of the substrate for use in photographic processing, which includes an alkaline swelling bath followed by a water wash bath wherein said antihalation layer swollen in said swelling bath and im said Wash bath is removed in predetermined times, thereby characterized in that said antihalation layer consists essentially of an antihalation fabric and a Mixture of two copolymers of a lower alkyl meth acrylate and acrylic or methacrylic acid, in which he ste copolymer is richer in acrylic or methacrylic acid and 030015/0851 ORIGINAL fNSPECTED Γ I the second copolymer is less rich in acrylic or methacrylic acid and wherein the amounts of acrylic or methacrylic acid in both copolymers and the mixture ratio are such that one swellable in said swelling bath and one swellable in said Wash bath removable antihalation layer is obtained. 2. Photographic material according to claim 1, characterized in that the first copolymer is a copolymer of alkyl methacrylate, wherein said alkyl is 1 to 4 carbon has atoms, and acrylic or methacrylic acid containing 40 to weight percent acrylic or methacrylic acid, and that second copolymer a copolymer of alkyl methacrylate, wherein said alkyl has 1 to 4 carbon atoms, and acrylic or methacrylic acid, which contains 20 to 30 percent by weight of acrylic or methacrylic acid. 3. Photographic material according to claim 2, characterized in that the first copolymer is a methyl methacrylate-methacrylic acid copolymer which is 42 to 48 percent by weight Contains methacrylic acid, and the second copolymer is a methyl methacrylate-methacrylic acid copolymer containing 22 to 28 weight percent methacrylic acid. 4. Photographic material after arrival Claim 2, characterized in that the first copolymer is a methyl methacrylate-methacrylic acid copolymer, which contains 4S wt .- * methacrylic acid, and the second copolymer is a methylraethacrylate-methacrylic acid copolymer, the 25 wt .-% methacrylic acid contains. 5. Photographic material according to claim 2, characterized in that it is richer in acrylic or methacrylic acid Copolymer represents from 30 to 50 percent by weight of the total copolymer content. 030015/0851 6. Photographic material according to claim 1, characterized in that the anti-halation layer, in addition to the anti-halation substance and the mixture of the two copolymers, is a resin-like viscosity-regulating layer in an aqueous alkali solution soluble substance. 7. A photographic material according to claim 6, characterized in that said resin is a synthetic resin containing carboxyl groups Is a copolymer or a cellulose derivative .. 8. Photographic material according to claim 6, characterized in that said resin is hydroxylpropylnethylellulose phthalate. is. 9. Photographic material according to claim 8, characterized in that the antihalation layer is 30 to 2 percent by weight of the lower alkyl methacrylate-acrylic or methacrylic acid copolymer richer in acrylic or methacrylic acid, 53 to 60 percent by weight of acrylic or methacrylic acid is less rich in lower alkyl methacrylate Acrylic or methacrylic acid copolymer and from 0 to 15 percent by weight of the resin soluble in the aqueous alkali solution. 10. Photographic material according to claim 2, characterized in that said antihalation substance is carbon black. 11 · Process for the production of a photographic material according to claim 1, characterized in that one on applying an antihalation layer to the substrate, consisting essentially of an antihalation substance and a mixture of two copolymers from a lower alkyl methacrylate and acrylic or methacrylic acid, in which the first copolymer is richer in acrylic or methacrylic acid and that 030015/0861 second copolymer of acrylic or methacrylic acid is less rich and wherein the amounts of the acrylic or methacrylic acid in two copolymers, and the mixture ratio are such daft a swelling in said bath swellable and removable washing bath in said antihalation layer is obtained. 10 15 20 25 30 35 03001 B / 0851