DE1448785A1 - Process for marking time-changing electrical processes in a recording instrument and material for carrying out the process - Google Patents

Description

PATENT AGENCIES ■ 17/19/56/25/22 7 STUTTGAR-T Λ £ 2 - April -1963 DRYING. WOLFF and BARTELS long street si

TELEPHONE: 296310 υ. "72"

^{TELEX: 07223} ^ ₁ 448785

f Dr, Expl .

-Nr ₀ 118 861

Eastman Kodak. Company, 343 State Street, Rochester, Uew York State, United States of America

Method for recording time-varying electrical processes in a recording instrument and material for implementation of the procedure ο

The invention relates to a method of recording time 'changes in electrical operations in registering instruments and in particular to a novel light-sensitive "multi-layer color paper for performing the method C

The invention is based on the object of a for the recording of time-varying electrical

'trischen.Processes specific photo-

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to develop graphic material that doesn't like many of those already proposed or known for this purpose photographic recording materials, especially high-intensity ultraviolet light sources required for exposure, but with ordinary tungsten lamp light can be used. The invention specifically aims to provide a "color photographic material." be provided, the recording. supplies in three different colors, whereby

. a high degree of "overlap ' ¹ without being informative
loss allows IM ** and a considerably increased

Storage capacity »provided per unit area 'should be »- ■. -

It has now been found that a photographic material is particularly suitable for this purpose which is able to produce two color images or dye images in two emulsion layers which, in order to be able to move between the two dye images and between each individual dye image and the neutral image, "'which, .by combination of the two dye images is formed, i is a maximum visually © selectivity _to-i, ^{e.rhalten>,:> -} v5orzugs: weis.e ⁱ z with ^be; ug on each other" köm- < : pili: emeutärfa ^ b.ig: i: s; feÄ / 'jrtfe ^ Bi *

der .die iEairlKadfer ^ M ^

'ö' Ma * eriältf

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The material in question is exposed in 'an, for example', recording instrument - with light - of different colors, on the one hand with direct white light, on the other hand with light from two different and optically separable areas of the visible spectrum - as is the case for the rest can be cut out of the tungsten light used by appropriate color filters while it is moved in a plane sen “right to the plane of light bundles, which are reflected, for example, by corresponding galvanometer mirrors in the instrument in question -forming layers a latent light, while a second light consisting of light from a first part of the visible spectrum ^: in one of the image-forming layers and a third light bundle consisting of light from a second part of the visible spectrum in the other image-forming light a latent Image generated. The how The exposed or exposed material described is then color-developed, fixed and bleached as usual, using a developer compound v & m,! S $ .p. -p ^ b / eaylendiatein: The obtained ^ arbjjicte ^ ial'Weist .danach, a neutral.-Xjixa .des · wed ^ ejavi-Loioiifb ^ iidels ^. as well as a -. ■ - ■■

BAD 809806/0873,, _w

colored image of the second light beam in a colored one image-forming layer and a second colored image of the third light beam in the other colored image-forming layer on ..

The term "improperly sensitized" means that the sensitized material is not intended for the manufacture of ! Color photographs can be used.

According to the invention, a method for recording time-varying electrical processes in a registering instrument is accordingly provided, in which the electrical processes are converted into light beams, one of which consists essentially of white light and a second beam of light from a first section of the visible spectrum and a third bundle of rays consist of a second section of the visible spectrum and the strength of which is proportional to the electrical processes taking place and the bundles of light rays being recorded by a photographic recording element which is moved perpendicular to the plane of the rays of light. The method is characterized in that the light beam is on. a photographic element composed of a support and two-color images forming silver halo. . genMemulsionsschiehten-b. stands _for the against light. ■ different and optically tri-saabar regions of the spectrum - ^; are sensitive and that subsequently the latent images generated in the silver ■■ ■ halide coating

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BAD ORiGiNAL

Treatment of the photographic element with a p-phenylenediamine type developer and a fixing agent to be developed *

To carry out the 'method according to the invention material "consists in its simplest form of a support coated with a light-sensitive silver halide emulsion layer which is sensitized to light of a part of the visible spectrum and contains a color-forming coupler, is coated, on which a further photosensitive silver halide emulsion layer is applied which is opposed to light of another part of the spectrum is sensitized and the. also contains a color-forming coupler, the. forms a dye whose color is that of the The dye formed in the first photosensitive layer is complementary to the image. G-em according to a modified one Embodiment of the invention, this layer can contain a combination of two couplers that are used in the Color development

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Form dyes which together absorb love of color, which is preferably the complement of the light absorbed by the dyes formed by the first layer. The two emulsions must be sufficiently different with regard to their sensitivity _f or sensitization, so that what is visible for

used Xicht

the exposure can be bewastefeeii / filtered out,

the

to popularize / one emulsion but not the other, and vice versa ι

These two photosensitive layers are preferably by a hydrophilic colloidal mixture such as gelatin or a "selatin substitute for each other" separated, with expedient-in this intermediate layer a non-diffusing reducing agent such as for

Example of a hydroquinone derivative with ü * © te * «?» It * bulkier

/ Side chain is incorporated. ;

In a particular embodiment of the material used according to the invention, this has on the support a) a blue-sensitive coupler, a coupler forming a G-dye and a coupler forming a magenta dye ehtbalten.de silver halide emulsion; h) a grelatine sandwich

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layer and c) a green-sensitive silver halide emulsion, one of which is a cyan dye forming coupler contains.

In other embodiments of the invention, the color photographic material contains a blue sensitive one Layer with a cyan dye forming coupler and a green sensitive layer with two a yellow dye or a magenta dye-forming coupler; or it contains a blue sensitive layer with a cyan dye forming layer Coupler and a yellow dye-forming coupler and a green-sensitive layer a magenta dye forming coupler; or it contains a blue-sensitive layer with a coupler for forming cyan and a coupler for forming magenta, as well as one green-sensitive layer with a coupler for the formation of yellow, or it contains a blue-green-sensitive layer Layer with a coupler for the formation of magenta as well as a green-sensitive layer with a coupler for the formation of a blue-green color

co -

I _n . Substance and a coupler for the formation of a gel-

ο ben dye. Alternatively, in each of the ten-called *** photographic 3? Arbmaterialien the grünempfindliehe layer disposed on the support and be

ο can

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blue sensitive layer / furthest from that Carrier removed and located over the relevant intermediate layer.

- 8 -,, ■■■; ..

In. Another embodiment of the photographic material used according to the invention consists of a transparent support and. which is one of .lichtempfindlichen layers on one side of the carrier and the second photosensitive layer on the other side dee ^l. Rigers provided, d ,. H. the carrier also serves as an intermediate layer *

In another embodiment, a bleachable filter layer is arranged between the two light-sensitive layers of the photographic material, called one. Contains dye which lies in the spectral range, whereas the lower light is sensitive _: it is sensitive, lets through is, or the bleachable dye is directly in the. Carrier incorporated _r if this is between the sensitive sons,

Sehließjich the individual light-sensitive layers may also contain several citrata ^ such as, for example, in the first layer ;, two 'New York Convention in accordance with the invention used photographisehen materials. ', although from a highly sensitive and a low- "' -

SADORIQINAt

sensitive emulsion consisting of strata that are both 'sensitized to the same part of the spectrum and produce the same dye image. Similarly, the second layer can also have an or contain multiple strata.

In addition, instead of the one of the light-

and sensitive layers used / coupler combination specified above individual couplers can also be used. For example, a red dye forming coupler - or a coupler for red - instead of the combination of a coupler for yellow and one Couplers for purple can be used; "further .a 'coupler for green instead of the combination of a coupler for yellow and a coupler for cyan, etc. The specially used combination of light sensitivity the emulsion and color-forming coupler is not critical as long as the color images produced can be easily distinguished from one another. Preferably, however, couplers are used which are in the two light-sensitive layers produce dyes, whose color is approximately complementary with respect to each other.

It is advantageous to cover the outermost layer with a hydrophilic colloid layer made of, for example, gelatin

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or a gelatin substitute to coat the sir this splint will provide the necessary protection.

in, the intended for the use according to the invention Color photographic materials can use the emulsions as photosensitive silver salts various common silver salts, including silver bromide, silver iodide, silver chloride, Silver chloride bromide, dilber bromide iodide, etc. contain.

The emulsions can chemically according to any of the for this purpose Usual processes can be senaibllized.-They can be matured with naturally active ftelatine or by adding sulfur compounds or reducing agents such as stannous salts or amine compounds be sensitized,

In the preparation of the silver halide dispersions for the silver halide emulsions used here can be used as a carrier for the halide during its BiI-. dung G-elatine or any other colloidal Material like colloidal albumin, a cellulose derivative or a synthetic resin such as a polyvinyl compound can be used.

Any of the "useful dye sensitizers" can also be used like any of the suitable color-forming compounds (or couplers) in the photographic material be used.

These materials are not limited to the use of any particular coupler because all that is required is that in the two photosensitive Layers formed dyes are distinguishable from each other and preferably consist of complementary colors, such that they together one Form image with a neutral density.

The coupler compounds can be used in suitable solvents dissolved and dispersed in a hydrophilic colloid, if desired, place a filter in Incorporating the material will be in the hydrophilic colloidal intermediate layer advantageously uses all those bleachable filter dyes which have a suitable optical "transmittance. These dyes are then bleached by the solutions that can be used in development.

For the intermediate layer and the outer layers of the invention The material used is known to each of the hydrophilic materials such as Q-elatine or liquid substitutes for

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Gelatin can be used as they are. also for the

selbsi;

position of the silver halide emulsions / are used,

• Non-diffusing reducing agents advantageously used in the intermediate layer are of course allowed the light-sensitive layers do not

it

• Damage and / should otherwise damage aeren oxidized poriii preferably not react with the color-forming couplers. Reducing agents that are particularly beneficial used weroeii can, 'are the öurch higher Aliiv 1-gruppai substituted = hydroquinone compounds.

For the production of the one used according to the invention photographic materials are a large number usable by a variety of carriers including typical photographic carriers from the usual Paper carriers or those that: iiit one against water ■ resilient öcnichtvie zua example with ϊοΐν -ethylene, polymeric hydrosols, gelulose nitrate filßi, Celluloceacetate film, poljvinylacetal film, polystyrene- · film ', polyethylene terephthalate film ubsr. are coated.

The photographic material was produced by the company. Training is carried out with Yorteil in various recording instruments, "return devices", Möhrkanaloszillographen or - "any other apparatus

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used who are able to enter from a electrical signal to generate a light signal. An ordinary tungsten light source is used as the light source - used for a recording (blasting) -

i.e.

Bundle unfiltered e # »3? is used without a filter V. while another (second) bunch with a turkey, which lets light through - only the first of the two light-sensitive layers is sensitive to it is, and a third bundle - with another filter that lets laughs through, for that only second of the two light-sensitive layers sensitive is to be filtered.

The exposed color photographic material is in a developer containing a phenylenediamine developing agent contains, developed, then in an ordinary Sodium thiosulfate fixer fixed · and either contained in a common sodium ferricyanide * - the bleach bath or with serrichloride as a bleaching agent bleached. '.

The following examples explain the invention in detail:

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1440785

-H-

• Example. 1

A gelatin layer coated with a barium sulfate, i.e. a so-called barite layer Gel sized strip of a photographic ^ Paper backing was coated with an ordinary, washed gelatin-silver chlorobromide emulsion, which was sensitized to blue light and in which two different gelatin dispersions were intimately mixed in, of which one of a dispersion of a coupling agent dissolved in a solvent and forming a purple-red dye lers, while the other one, a yellow one Dye-forming couplers also included dissolved in a solvent and in the form of its. Solution in which gelatin was dispersed. There were approximately: equal amounts of the couplers in question in the

Emulsion used. *. Another wt ^ Öhniiche Selatiiie ^ SÜbei "-chloriäferomideittuisioii was then applied to the first Emül3ionsschich.t - _t was sensitized to * green light and intimately a solvent solution Elatine ö-one a" cyan dye-forming coupler in with-a dispersion Finally, a gelatin coating layer or top layer was applied to this layer.

■ au

8 0 9 8 Q.6 / 0-8 7 3

- .15 -

Example 2

The photographic material prepared in Example 1 In a multichannel oscilloscope, three separate mirrors were reflected by three galvanometer mirrors LientbänderIn exposed, with a bundle of light consisted of olfram light through a blue sir. 'A rat filter had passed through while another light bundle consisted of V. tungsten light that passed through

catch _ww «g» 8 was,

and a third (and final) light beam consisted of unfiltered voltaic light.

The exposed or exposed as indicated Material was further treated as follows:

1.3 minutes of development at 38 ° C in a solution of the following composition i

Benzyl alcohol 12.60 ml

Sodium hexametaphosphate 2.00 g

sodium sulfite, dehydrated 2.10.g

sodium carbonate, monohydrate 26.80 g

Sodium bicarbonate 2.90 g

Potassium bromide "0.48 g

Sodium chloride 0.70 g

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Hydroxylamine sulfate 2.10 g

4-Ämino.-il-äth3 / l-i \ [- [beta-methan-

sulfonamidoathyl l-m-toluiain-

sesquisuifst, iLonohj / drat ₌ . - 4> 20 g

■■■■ ■ Filled up to the liter with water

Fix for 1 minute at 38 C with a dilution in the ratio of 14 parts, barrels to 1 part solution produced .fixing bath, whereby üie "solution" was added as follows:

Sodium sulphate. i60.0 g

Ammonium chloride 50.0 g

iJatriumsulfit, dehydrated. 15.0 g

Acetic acid, 28> 48, ^; gml

Boric Acid, Crystallized 7.5 g

Potassium alum 15 * 0 g topped up with passer to the liter

3. 1 1/2 packs of bleaching at 38 ^Ρ C in a bath. the following composition; . . ,. . . '. "

Potassium ferriefanide ■ "■. '60.0 g

Disodium OBphat. - 13.0 g

Monosodium phosphate. 5.0 g

Matrium Droicid. 15, Cg Lit c.asser topped up to the liter

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- 17 - ■.

4. Wash in water at 38 ° G for 3 minutes

5 ·! 'Rock

A good 3-channel record was thus obtained. The recording made with the! »Tepid bundle of light v.ar red, the one made with the green light beam blue-green and the record made with the unfiltered light beam was neutral Density. Each individual record was clearly distinguishable from the other two.

The terms used in the example üntwicklerverbindung, namely 4-amino-is-äthy 1-1- (beta-inethansul-f onamidoäthyl) -m-toluidine sesquisulfate monohydrate can "ground by other conventional p-phenylenediamine Entwicklerverbindun _s en replaced, for Example by 4-amino-U-ethyl-N-beta-oxy-ethy1-ί-methylahialinsulfat} 1ί-ethyl-bβta-methanesulfonafflidäthyl-3- [methyl-4-aminoaniline sulfate, H-ethyl-beta-methanesulfonamidoethyl-4-aminoaniline 2 -Amino-b-diethyltoluidine hydrochloride} 4 ~ ii-ethyl-Si-beta-oxyethylaminoaniline etc.

All named developer connections are thereby characterized as having a primary amino group. ·

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example 3

Other photographic materials were produced in a similar manner>. the other combinations of Sensitivities and couplers than that. in example 1 "used. The layer arrangement of several of such materials is indicated below, the photosensitive layers in each case sensitizing optiacE Silver halide "= contained.

a) top layer

Blue sensitive layer - cyan coupler Intermediate layer

Green sensitive layer - auto and purple coupler

Sap'ler carrier

fo) top layer

Srüniampfindlieiie Seittcht - Purpurrötkttppier 2wiachinachtc & t

Biauempf Indian Sehicilt - BlaugyÜa- mM Gelbkuppiör Päpierträger

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c) Top layer ......

Blue sensitive layer - magenta coupler intermediate layer

G-green sensitive indigenous layer - Jilaugriin and G-elb couplers Paper carrier

ά)! Top layer "

Blue sensitive layer - yellow coupler Intermediate layer

Grünerapfindliche Jchicht - ⁱ Bl .ugr n and I / ^{urpurrotkuppler!}

Papierträoer

e) top layer '■. .. Green-sensitive ochicht - yellow coupler Intermediate layer

Blue-sensitive ochicht-ulaugr ^ n- and i'urpurr-red couplers .

Papierträoer .. · ^; ■ -

Similarly, any die & er materials can be created by changing the spatial position of the light-sensitive Layers are changed, so Kunii / ά j * as i'follows be changed;

f) top layer

Gr ^: sensitive layer - jslir.gr'in- and ruriurrut- '* S09B06 / 0873

- 2o - ~ ■ -. - ■■: ■■; : ■

Interlayer ■ "-. · -

Blue-sensitive layer-field couplers

Paper carrier ■

The photographic used according to the invention " Material provides three different colored records, 'resulting in a high degree of overlap with no loss of information allowed, and where in it at the same time a considerably increased inf ormatic storage capacity per unit area compared to the known ~

-Materials
"ten." Black and \ Y * eiß / provided, is pronounced differently- * ■ -

dräcfctj / You can use this to create one or more recordings in a colored picture and further records in to a colored picture. which is the approximate The complement of the first colored image is, as well as, finally, still: a third approximately neutral, colored record. The - at least, in the preferred ones - Materials formed by both parabolic figures are in terms of their hue, as already several times emphasized, complementary and therefore contrasting. ■ -. both "with each other and with a neutral density image, as you can see at the sntnickein aer. Cursing., The.:. exposed to white light forms as much as (at all) possible. Last but not least Advantage of the material used according to the invention "is"

"" "· - ■■ SAO ORfGiNAL

809806/0873 . ': _? v ,: * ', <; * .; .;>;:

see again the usability of ordinary tungsten light sources to be mentioned for the stated purpose.

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Claims (1)

Patent claims 1. Method of recording time-varying electrical processes in a recording instrument, in which the electrical processes in the light beam nbeams are converted, one of which is a beam of rays essentially of white light, a second beam of light from a first section of the visible spectrum and a third bundle of rays consist of a second section of the visible spectrum and whose strength is proportional to the expiring electrical processes and wherein the light beam from a photographic recording element recorded which is perpendicular to the plane of the Light rays is moved, characterized in that the light beam "is on a photographic Element are composed of a support and two colored images forming silver halide emulsion layers consists of different and op- önzi <■ Table trl-aebarer regions of the spectrum can, and in that subsequently in the silver halide latent images .erzeugten by treating the element with a developer photographiscben 'ii-phenylenediamine and a fixing developed · ⁵ wetdöiu /. ' 2 “Photographic material for carrying out the method according to claim 1 _f daduiroh characterized daee ~ 23 - it consists of a support and two colored pictures Silver halide emulsion layers that oppose φϊΐη via light from different and optically adjustable regions of the spectrum are sensitive., 3. Photographic material according to claim 2, characterized in that the emulsion layers by a hydrophilic, preferably gelatin-containing colloid layer are separated. 4 · Photographic material according to claims 2 or 3 » characterized in that the emulsion layers are sensitized to the light of the visible spectrum 5 »Photographic material according to claims 2 to 4, characterized in that the two emulsion layers contain color couplers which are produced by "color development Form color images that are complementary to each other, 6. Photographic material according to claim 3, characterized in that the. Colloid layer · a bleachable one Contains dye that is permeable to light to which only one of the emulsion layers is sensitive * is. 7 · Photographic material according to claim «" ^ .thereby characterized in that the colloid layer has a through 809806/0873 Hydroquinone compound -containing a higher alkyl radical = '■. - ' δ »Photographic material according to claims 2 to 7, • characterized in that one of the emulsion layers is green-sensitive and forms a ßlaugreen dye _; Contains coupler, and that the other emulsion layer is sensitive to blue and contains a "yellow dye-forming" and a magenta-red dye-forming coupler » 9. Photographic material according to claims 2 "to 7", characterized in that one of the emulsion layers is sensitive to green and has a G-elbe dye ■ "'forming and a purple-red dye forming _; Kupple'r contains, and that the other emulsion only happens is blue sensitive and contains a cyan dye forming coupler. ΙΟ »Photographic material according to claims 2 to 7, characterized in that one emulsion layer is green-sensitive and one is a magenta dye forming coupler, and that the other emulsion layer is only blue-sensitive and a jslagreen dye forming coupler and an oil dye forming coupler Contains couplers. 809806/0873 - 25 - 11 «Photographic material according to claims 2 to 7, characterized in that the one emulsion layer • Is sensitive to green and has a coupler which forms a cyan dye and a yellow dye forming coupler, and "that the other emulsion layer is only blue sensitive and contains a magenta dye forming coupler 12ο "Photographic material according to claims 2 to 7, characterized in that one emulsion layer is green-sensitive and one is a cyan dye forming coupler and a magenta dye forming coupler, and that the other emulsion layer is only blue sensitive and contains a yellow dye forming coupler. 809806/0873