DE1447785A1 - Process for eliminating the harmful effects of contaminating oils and fats on aqueous solutions that can be applied to layers - Google Patents

Description

PATENT LAWYERS DR.-1NG. BY KREISLER DR.-1NG. SCHONWALD DR.-1NG. TH. MEYER _{COLOGNE1 # DE1} CHMANNHAUS Dipl.-Phys. GRAYE

Cologne, November 30th Mr / Breu 1964

Applicant J. Company Β · Ι. du lont de Nenrnurs & Company

Wilmington 98, Delaware United States τοη America

Procedure for eliminating harmful influences contaminating oils and fats on aqueous solutions that can be applied to substrates

The invention relates to the purification of aqueous solutions or Dispersions that contain water-permeable, macromolecular, organic colloids, in particular it relates to new photographic materials

In various aqueous systems, the presence requires ▼ • non-cleaning oils and fats processing and quality · - problems that occur especially with such coating gates occur in which the surface tension of these contaminating substances differs from that of the material to be applied. Small areas then remain under these conditions of the end product after the coating process is at least partially unsupported. ”They are identified in the photograph as "repellent spots" ·

The invention becomes in the context of a method for removing repellant ("repetition") causing contaminants oils and fats · from photographic emulsions before coating explained, SI "IUBt" loh but without or with no minor

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Modifications carried over to other aqueous systems which have the same cleaning problems. One puts photographic Silver halide emulsions are made by making silver halide precipitates in an aqueous colloidal medium and uses gelatine as a forming colloid due to its character as a natural substance, the diversity and impurity of the raw material used in its manufacture and the manufacturing process used, gelatine contains natural animal oils and fats. These natural ones Oils and fats leave behind by exposure photochemicals caused by the emulsion with actinic light No reaction, but they cause rejection, when the gelatin emulsion is drawn onto a support · During the manufacture of photographic gelatin or photographic In addition, emulsions are occasionally unintentionally neglected by various mineral oils, which were used to lubricate the equipment used and also cause rejection *

It is known in photographic technology to add wetting agents or surface-active agents of various types to an emulsion before coating in order to support a uniform spreading of the emulsion during coating and to counteract the formation of blisters and repellent blemishes . rofeltam uniform adhesion between eineai water repellent "rägerfilm and overcome n a hydrophilic emulsion%, ^ edoeh assets these substances <i ± e AbstoSuag causing Yerschmutsumgen not off * Si © wear awar help"! the ünters © Hiese in Ofearflncheuspaanungen within the Imulßion to veraindera and accordingly öi® training repelling stains to some extent herabzudrückea These emulsions in oil or]? 0ttv®rußreiaiguiigeK. bring a different kind of Abstoßimg _e Suaätzlicli to

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the adhesion of an emulsion to an erroneously counteracting one Force these harmful substances can also repel between two daulsion layers as well as between an abrasion-preventing layer and an emulsion layer cause · the repulsion The point of defect produced generally presents itself as a spot of approximately circular outline. The spots have different sizes, there are those with a diameter of about 1.2 ca and those that only represent a small point The Terfahrer! the invention oient to the harmful Exposure to polluting oils and fats in aqueous Coating solutions that contain a water-soluble, macromolecular, contain organic binders. According to the invention, the solution with microcrystalline is used for this purpose Cellulose particles brought into contact.

You can add the microcrystalline cellulose in finely divided Introduce the mold, stir the mixture and then the rope containing the impurities filter off. According to an embodiment of the invention set «* cellulose of such a particle size that the Jinselteilohen do not have to be removed, i.e. remain in the system without causing undesirable effects. In the end a filter coated with microcrystalline cellulose can also be produced and then the contaminated one Pass aqueous solution through this pilter.

Microcrystalline cellulose is available in the trade, process for their production are known. The following procedural steps are particularly important

Any kind of purified cellulose, as'äi. ·. it is natural or regenerated cellulose, undergoes a controlled acid hydrolysis by · The acid destroys or removes amorphous parts of the

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original cellulose chains. the remaining ones, nods Adhering parts are then in non-fibrous or crystalline form, a result of the tearing of the Continuity between the crystalline and amorphous areas of the fine (! «Fuge · The crystalline aggregates are then washed with water and subjected to mechanical disruption or disruption. Their mechanical disintegration can be different Because of »for example by milling in one Mill, operated by cutting machines at high speed or by the action of high pressures in the order of magnitude 350 to 7) 0 kg / cm · The crushing is carried out preferably in the presence of an aqueous medium and then dries the aggregates until they appear as crumbling, free-flowing, granular * dry, finely divided mass is present.

The microcrystalline gelulose particles have spores interspersed with that strong. Show affinity to natural oils and petroleum · Every particle can have its own weight adsorb excess oil. The weight ratio adsorbed oil s microcrystalline cellulose is in the range of a certain particle size of, for example 5 to ISO microns at around 1.1 / 1.2 t 1. When the Cellulose aggregates in aqueous dispersions or solutions do not trigger any chemical processes because the particles are inert and insoluble; after the addition they preferentially and selectively adsorb all the insoluble ones present oils ocier fats

According to those who are in the middle without technical interest The cellulose particles are an embodiment of the invention added to a qelatin silver halide emulsion and with this mixed «The resulting dispersion is then ■ weeks removal of the particles through standard filter paper

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suitable bore size filtered · The particles have that oil present in the bump ion adsorbs »accordingly the oil is removed during the filtration

According to a further embodiment of the invention, in aggregates with a particle size of 5 to 65 microns diameter gate are incorporated, after which the resulting, ans Iellttloeeteilchen ur, a gelatine-halide emulsion existing dispersion not filtered, but to the desired one Base is poured on · Because of the small particle size of the cellulose particles used, the photographic Properties not affected, on the other hand all oily impurities rendered harmless

Another embodiment of the invention covers it a suitable pad, such as filter paper, with the cellulose particles and then use such a filter for filtration the silver halide emulsion to gate the coating's remove oily impurities from the emulsion

The method of the invention basically applies to everyone

aqueous systems containing oil drains are in question, Preferably, however, for light-sensitive gelatin-silver halide emulsions -

The following examples are the same as aqueous gelatin solutions relate, in particular to aqueous selatine silver halide emulsions, the invention is not limited to gelatine as a water-permeable organic colloid. Aqueous solutions other macromolecular colloids synthetic or natural Rerbeesern can be found in the same catfish.Aqueous solutions such as casein, albumin, 3up * r polyamides, agar-agar, polyvinyl alcohol, olyacrylamides and polyrlnylaoetals. The method of the invention can also be used

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eur treatment of certain other polymers or blends Use clay polymers, for example to treat ▼ on PolyTinyl-N-vinyllactams, butadiene / acrylonitrile copolymers « Vinyl acetate / vinyl stearate copolymers, styrene / butadiene copolymers, alkyl and acrylic & acid resins in combination with gelatin. Aqueous gelatin silver halide emulsions » which «contain polymeric substances» such as dextrin to improve the layer properties Dextran, and olyvinylpyrrolidone, can be used in the same way freed from contaminating oils and fats according to the invention will"

The invention can be carried out with all aqueous gelatin solutions that are used to form clay gelatin-containing sub-layers, intermediate layers, filter layers, dyes and pigments that absorb selected light wavelengths, as well as clay layers that protect against abrasion. The invention can also be used transferred to aqueous diversions of water-permeable, organic colloids »They contain special substances such as silver halide grains» magnetizable «substances or phosphors in suitable aqueous media, such as water, aqueous ethanol, etc. they are obtainable from aqueous dispersions of 698,235 'ier generically described copolymers of Tinylidenchlorid / methacrylate / itaconic acid in the US Patent 2 · blank All Gelatir.e silver halide emulsions see, "Improvement rfindungsgemäß n, for example those based on clay silver iodobromide, silver bromochloride or silver bromide. Great results can be achieved not only with black-and-white photography and X-ray image emulsions, but also with emulsions for AbArelffilm and for

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printing processes and photographic emulsions for dl «color photography. Further fields of application are the dyes containing emulsions! According ien US Patents 2,380,032, 2,380,033 and 2,927,024, also known optical "sensitizing dyes containing · emulsions as well as those" in which non-optical sensitizers such as unstable sulfur Schwefelsensibilatoren containing Torliegen · Examples of the latter allyl isothiocyanate, allyl diethyl thiourea, phenyl isothiocyanate and sodium thiosulfate, also include the polyoxyalkylene ethers according to ÜSA patent 2,400,532 and the polyglycols described in US patent 2,432,549. The method of the invention has also proven itself in cleaning clay suI-sions » the other» non-optical sensitizers, such as amide ·

corresponding to US Pat. No. 1 925 508, and metal salts corresponding to US Pat. No. 2,540,085. Conventional antifoggants, see B. Bensotriaxol and Triaeain-ene, gate beds, also common Hardening agents, for example chrome alum, Pormaldehyd new as well as other auxiliaries, such as matting agents, plasticizers » tinting substances in the whitening agent

The new method of the invention shows Tiele Teraüg primarily the fact that it is effectively pointing · removes «impurities from aqueous systems without influencing the effectiveness of the corresponding dispersions or emulsions itself ·· It releases the material drain Different coating methods lead down greatly in which these impurities cause particular difficulties, as rües especially in ΰ; r photographic technique of the pail let. Another advantage is that it is old microcrystalline Cllulose particles impregnated Piltermas, as described above, Tielen can throw filter operations in an adapted manner.

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The following examples illustrate the invention. Unless otherwise stated, all quantities are «as To view weight information.

example 1

A dye was added to an aqueous gelatin solution maintained at 38 ° and containing 5 % inert gelatin made from bovine bones, which served to facilitate the display of repellent stains. A portion of this solution was, as described in US Pat. Nos. 2,627,088 and 2,779, poured onto a non-colored support made of polyethylene terephthalate and dried. The coated gelatin layer was chilled to 10 ° and at 30 ⁰ C and J55% relative humidity dried. During their examination, small repellent spots were found occasionally.

Ordinary petroleum-based lubricating oil was added to the remaining portion of the solution with stirring in amounts of 1 Ji, based on the gelatin present. A portion of this solution was then in the manner described on an uncolored Base film made of polyethylene terephthalate and cast dried «When testing the cover, many were able to larger repellent fleeke can be found.

Microcrystalline degraded cellulose (level-off DP cellulose) was added to the remaining portion of the gelatin solution contaminated with lubricating oil and stirred for 5 minutes · Particle size of the microcrystalline cellulose 10 to 65 microns; 2.5 %, based on the gelatin present, were added. The solution was then filtered through conventional filter paper and then applied to an unstained film support as described above. When the coating was tested, no repellent stains could be found any more.

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Similar results were obtained if instead of Bone gelatin made from pig skin gelatin was applied * while the lubricating oil was made by cod liver oil (animal oil) or olive oil or cooking oil as vegetable Oil replaces *

Example 2

A highly sensitive, aqueous motion picture emulsion was prepared from gelatin and silver iodobromide containing 7.3 % iodine, 92.7 % Bro "and 6 % gelatin! the emulsion was color sensitized. Part of this emulsion was poured onto an uncolored support made of polyethylene terephthalate and dried. After pouring the emulsion was quenched to 10 ° and dried at 30 ° and 35 % relative humidity. During the inspection, isolated small repellent stains could be found.

SSta remaining portion of the snulsion was silicone oil, i. a Dow-Coming 35-B silicone emulsion, put into which Ethyl alcohol had been incorporated for the purpose of separating out the oil. 1 Jf was added based on the weight of the gelatin present. A part of this emulsion was then as already described for the initial emulsion, on one Dyed polyester carrier filament applied and

dries. The XHLe test showed that there were many repellent stains, “with partly smaller, partly larger diameter ···· *.

Section! remaining, old siliconBl contaminated portion of the ■■ ulslea was elkrokrlatalline cellulose in quantities of 2.5 Jl, based on the gelatine present, and stirred for a few minutes. The emulsion was then duvened tlbllohe »filter paper filtered and then whole Analogous to the work catfish already described, applied to an undyed SohiahtvrSger made of polyester and dried. The test showed an upper pull that was completely was free ven repellent the stains.

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The original emulsion as well as the contaminated and subsequently microcrystalline cellulose treated emulsions are simultaneously in a sensor (type IB) exposed and 6 1/2 minutes at 20 ° with a developer with the following composition

Water 750 cm ⁵ G IMfethyl-p-amino-
phenol hydrosulfate 0.8 B. Sodium sulfite
(dehydrated) 90.0 B. Hydroquinone 1.0 G borax 3.0 G Potassium bromide 0.1 m? Rest? Water su 1000 c

The sensitoss * trisohes obtained with the construction lon are made Data i

iSameness Gaisaa Sehleiesv

education

. 1 * 003 0 * 7 ^ 0 * 22

Baulsion 1.225 0.79 0, X3

Dies® Zalslen. prove that the process of the invention is uneJä ^ tXgi. S, iriwiricung to <»ina een» ibilized fotagv & ftamlm Snulslon

Example ^

Siner wSsarigen at 38 ° ge & altenen öelatiiielösung * 5% inert "au" child # rknoehsn produced Gelatin · containing a dye was added to "A portion of this LS-suzig was coated on a colorless SohiöfettrSger polyester" Uifgebraehfr and dried * where mar * place the coating at 10 ° at the atmospheric pressure and at ^ 0 ° and ^ 5 % relative humidity

tredsnefee. The examination of the oil eye showed isolated® repellent stains on

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Normal lubricating oil became the remaining portion of the solution In amounts of 1% by weight, based on the gelatin present, given. Part of this solution was on an uncolored Polyester optical carrier applied and analogous to the treatment of the 1 × approach dried. In the subsequent examination, many repellent stains were found to be different Size can be determined. The retained part of the with Gelatin solution contaminated with lubricating oil was filtered through conventional filter paper, the surface of which was previously coated with a Layer as microcrystalline cellulose (layer thickness: 0.25 mn) was coated. The solution then became how applied to the other parts and dried, after which a coating completely free of repellent stains Template.

To cover the filter paper, a solution containing 25% microcrystalline cellulose in distilled water was eaten on filter paper carried by a fabric. For various samples, the layer thickness was adjusted to 0.20, 0.25 and 0.30 mm. All of the coated papers were found to be effective when used in the Sieleher manner.

An aqueous gelatin solution containing 5% gelatin, kept at 58 °, was added, based on gelatin, with 1 % brewing oil. The solution was divided into several portions and microcrystalline cellulose was added in the following amounts:

. % microcrystalline cellulose, sample Sr. based on gelatin present

4 16

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The samples were applied to an uncolored polyester-based support without filtration. With the exception of sample no. * 1, all samples proved that the repellent Effect of the lubricating oil had been turned off.

In addition, the addition of solid particles gave off microcrystalline cellulose gives the coatings a dull, dull character «as if they could be written on with pencils Mr. 2 emerges. Orad of matting:

Sample Ij 0 Sample 2 « little Sample 3 « moderate Sample 4: strong Sample 5 « very strong

So it follows that microcrystalline cellulose too this can be used »if desired, to give certain products a matt surface *

Example 5

With an aqueous sublayer solution of a mixed polymer of vinylidene chloride / methacrylate / itaconic acid according to CSA patent specification 2,698,235, the procedure was of Example 1 is repeated. The sublayer solution was treated in the same way as the gelatin solution, the results corresponded to the data given in Example 1.

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Claims (1)

Pat entail »ρrüch e 1 ») Process but elimination of harmful fluids, contaminating oils and fats on aqueous ·» ^ Substrate can be applied «solutions or emulsions, dl« a v.asserlöalichee, macromolecular, colloidal »* organic es Am. contain products, characterized that the solutions are brought into contact with microcrystalline cellulose particles. 2) Method according to claim 1, characterized in that » that in the solutions of degraded D.P.- »cellulose consisting of “brush parts dispersed. 3 ·) Process according to claims 1 and 2, characterized in that the cellulose particles have one particle size Tone 5 bit XSO micron available 4 ·) Method according to claim 1 to 3 »characterized in that the cellulose particles τση the aqueous Filtered off excess solutions 5 *) Process according to claims 1 to 4 * characterized in that "light-sensitive silver halide grains are kept dispersed in the solution by the binder" 6.) Process according to claims 1 to f »characterized in that oleatins are used as colloidal binder applies. 7 ·) »photographic material · consisting of a 8 chi ch ttrilger and at least one applied «β im waaser «iurofel & Bsige» colloidal binder, rorsugsweiss Layer containing oilatins, characterized by the fact that the layer contains microcrietalline oil components * For example, it has a partial height of 5 to 65 microns. 809902 / Ö72Ö 8 ·). ¥ ·. graphic material according to claim 7 » && ureh characterized, d & B the layer of white Halogsna lifter gelatine *« emulsion is · 9.) photographic material according to claim 7 and 3, thereby i? eksnnz? rlehnet that? Ie layer microcrystalline Cellulose parts in such an amount that one matted layer surface was formed « 809 902/0720