DE1571819A1 - Thermographic process for the production of heat-resistant copies - Google Patents

Description

PATENT LAWYERS

dr. MC "'FP-: ent

DIPL. I. / ν ¹ ·. \ '· Α. " NJITZ ύ;' - ι ■..; - u [i: .ι

TtLl.! W.1 2UwItO

June 22, 1968

G 1568 - De / My

Agfa-Gevaert AQ ₉ Leverkusen> Federal Republic of Germany

"Thermograph! This method of manufacture heat-resistant copies "

Priority: Great Britain from June 22nd, 1965

26 468/65

The invention relates to a method for recording and reproduction of information and records of any kind by means of heat _o In particular, the invention relates to a thermographic method for producing heat-resistant copies ·

It is known, graphic originals by means of a heat-sensitive To reproduce material that contains chemical reagents that, when heated, produce a colored product

BATH - ¹ - 00981 A / 0899

form duct. The copies made with such materials however, they have the disadvantage that they are not heat-resistant are.

In the method according to the invention for recording sound information, a recording material is used which contains a reactive compound or composition that is destroyed, blocked or reduced in reactivity or removed from the material by the action of the imagewise or template-wise applied or induced heat. In the unheated areas, this compound or composition remains available for the reaction with a compound applied to it or can be transferred to a recording medium, for example by diffusion, tearing out or evaporation. or chemical "nature" is produced, for example a change in light absorption, or a change in color or color density. " A change in color can be produced by a color _{coupling reaction 9} and a change in color density by a leaching reaction.

The way in which heat is applied or formed or is supplied as a template is not important. For various forms of embodiment of the image or submission wise

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Heating, which can also be used in the present invention, is based on the Belgian patent specification 656 713 referenced. According to the embodiment especially described there, a source for infrared radiation is used The recording of information supplied in the form of visible light was used to supply the required thermal energy. od ^ r records is not, however excluded, since this light can be converted into heat, for example in the recording material itself. For

such an application of visible «Lieht in the Wärmedeutsche patent application A 52 4-94

the drawing is especially on the / <pritic. Patent applications 20 818/65 and 21 985/65).

The heat to be supplied during the recording stage can be obtained by conduction of thermal movement, for example of infrared absorbing image markings on a Üri. ;;: eel, to which heat-sensitive material is fed, is, ccoch preferably in the heat-sensitive material even by converting electromagnetic radiation into heat in substances that are in the heat-sensitive material are distributed and are in thermally conductive contact with the compound or composition that has been destroyed in reactivity or blocked from the thermosensitive material to be removed by warming, are generated.

siscn at which such substances ·.:; .. ·, be v.'ändt «is particularly to the Belgian

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Patent 657 502 and German patent application A 52 4-94- (British patent applications 20 818/65 and 21 985/65).

A direct or reflective exposure technique can be used to obtain positive, legible copies. However, a reflective exposure technique is preferably used and a recording material is used which is contained in the recording element (e.g., the layer), or in an element or coating which is or which is in a thermally conductive relationship therewith contains a substance or substances which absorb or absorb the copying light and convert or convert it into heat. The transparency of the recording material used for reflection exposure is preferably such that at least 20 % and at most 80 % of the copying light are transmitted. For such an exposure procedure, reference is made to German patent application A 52 4 ° A (British patent applications 20 818/65 and 21 985/65). Pie reflective exposure is possible in the practice of the present invention not only when the information to be recorded is supplied or is a visible light pattern, but also when it is supplied as a pattern of infrared radiation when an element is used (whether or not it is part of the Recording material or not) which transmits a certain amount of infrared radiation, but with regard to

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the radiation reflected from the original is heated selectively or differentially (cf. Belgian patent specification 664 329) Regardless of which mode of operation is chosen, it should be noted that substances which absorb copying light (or infrared radiation) and convert it into heat, if desired in and / or on a layer other than the heat-sensitive layer of the heat-sensitive material, provided that there is sufficient thermal contact to conduct the heat generated here into the heat-sensitive substances. Such another layer may be another layer of the thermosensitive material or "a layer (e.g.," a self-supporting layer or a supported layer or coating) that constitutes a material or part of a material separate from the thermosensitive material; in other words, a thermal pattern can first be created in a separate element and passed therefrom to the thermosensitive material. I ^{1 For} the two last-mentioned embodiments, especially with regard to the use of a radiation source and copier that emits primarily infrared radiation, reference is made to Belgian patent 664 329

In its preferred form, the recording method according to the present invention comprises the following features:

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a) The provision of a recording risk or element ₉ that is a reactive compound, ζ Bo a coupler; contains, which is generated by the action of thermal movement, which bilcV or template-wise by image or template-wise reflected electromagnetic radiation in a substance or substances ₉ which is or are homogeneously distributed in the heat-sensitive element bawo material and this radiation absorbs or respectively absorb and transfer into heat or = transfer, destroyed, blocked in reactivity or from de ja. Element can be removed, and

b) contact of the exposed recording element or material with a recording material or element, which contains a reaction component for the still available compound or composition, with it the conversion of this compound or composition by diffusion into dissolved, vaporized or molten Condition on this receiving element, possibly together with softened binder (if a there is such a thing), which tears out during the subsequent separation of the elements, can take place »

When using the reflex exposure method, the intensity the exposure and the sensitivity of the recording element containing the radiation absorbing substances contains, which convert the applied radiation into heat, chosen so that after absorption of light or

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other rays directed at the original and the light-sensitive layer evenly (not differentially) hit the resulting heating practically no or only a slight inactivation or no or only slight loss of reactive compound or composition caused you additional image or template-wise V / arm, which results from the image-like or original-white reflected radiation, provides the practically usable image or radiation in the recording material Elimination of this compound or composition on a submission basis.

It should be noted that when using a reflectographic. Eipositionarbeltsweiee the original to be reproduced must be an original, the image or template area or an image or template background which reflect or where the copying radiation bsw reflects ZoBo light, or a slide, which has image or original areas that absorb the copying light, and that during the exposure bit its back in contact with a material or in close proximity to a material which copying light is reflected, held «,

After these general remarks about the conception the invention is followed by a detailed description of the composition and structure of various heat

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can be sensitive materials of types of radiation sources and Exponierungs-, Entwioklungs- and transfer procedures, v / elk in the present invention is applied ₀

To make a thermosensitive material suitable for use in accordance with the present invention, becomes a color reactive or color bleaching compound or Composition that is destroyed by heating, blocked in reactivity or removed from the element can., with or without a binder, applied to a suitable carrier o The carrier can be permeable, so that the Compound or composition can be incorporated therein by impregnation. Trap used a binder this binder can be selected so that it can be transferred to a recording material in a softened state.Suitable binders are e.g. gelatin, carboxymethyl cellulose, tragacanth, alginic acid and the salts or esters thereof, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, ethylhydroxyäthyloelluloee, xthyloellnlose, Polyvinyl butyral, cellulose triacetate, cellulose aoetobutyrate, ethyl cellulose p-sulfonic acid benzoate, sucrose benzoate, Polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, copoly- (vinyl chloride-alkyl acrylate), copoly- (nitrostyrene-maleic acid-monoethyl aaleinate), Copoly (styrene monoethyl maleate), copoly (vinyl methyl ether)

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maleic anhydride), copoly- (maleic acid / nitroetyrene) ₉ öopoly- (vinyl chloride / methyl acrylate / ethyl acrylate), partially nitrated copoly (methyl acrylate / styrene) or natural resins and Waohse, e.g. carnaubawaohs, beeswax and rosin.

Obviously, also a combination of two or more of the enumerated binders, z "B _e is a mixture of gelatin and carboxymethylcellulose, gelatin, and polyethylene in an emulsified state, and carnauba a Äthyloellulose

The binder and the heat-sensitive compound or composition are preferably used in one common. Solvent dissolved. Water-insoluble binders can be dissolved in a suitable organic solvent, but they can also be used as an aqueous emulsion (latex) _o Solvents that can be used to produce the heat-sensitive layer include water, methanol, ethanol, ethylene glycol monomethyl ether, methylene chloride, acetone, Cyclohexanone, diethylene glycol, amyl acetate, dioxane, diethylene glycol monoethyl ether, trichlorethylene, toluene or a mixture of at least two of the above solvents o

The flexibility of the heat-sensitive layer can be increased by using plasticizers such as glycerin, sorbitol, poly-

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glycols, polyethylene glycols * stearic acid and the esters of which, esters of adipic acid and sebacic acid, polyethylene sebacate, PolyäthylenaJlpat, Mmethylglykolphthalat, Alkylarylsulfonaten, chlorinated bipheayl compounds, castor » oil, pino oil, triphenyl phosphate, tricreayl phosphate and dibutyl phthalate guaranteed.

The following table shows suitable combinations of Color reaction components »which are suitable for use in the recording material suitable (column A) and iferbreaktionsverbindungen that are suitable for use in the recording material suitable (column B) compiled

1. Connections? Eliminate sulfur, such as dithiooxamide, ihioacetamide and p-plienylenedithiourea

Inorganic and organic salts or soaps from Elsen., Copper, silver, mercury, lead, nickel, cobalt and cadmium, such as copper stearate, silver! - kicked, silver stearate, Sj.1-berbehehat, Silver palmitate, mercury stearate, Lead acetate, lead stearate, Lead aryristate, nickel acetate,

009814/0899

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BATH

• t Nickel stearate, cobalt «= 5ο oxidizing agents, such as stearate, cadmium stearate Benzoyl peroxide and tetra- and lead benzyl mercaptide. 2. Acids, such as oxalic acid ohlorchinoh. Connections «against lind malonic acid Changes in pH are sensitive, e.g. 4. Coupler for the diazo Leuco malachite green, leuco type, like 2,3-IIliydroxy- raethyl green, leukofuchein
• naplithalin, rhloroslucinine and leukolia amine green. ulic resorcinol. All connections that when oxidized, the color ▼ change, e.g. p-Cblor- anilln, Hethyl-p-amino- phenol sulfate, H, H'-Di me thy1-p-phenylenedi amine, Antipyrine, pyrogallol, Catechol and 4-meth- oxy-1-naphthol. Aronic diazo compounds dungen, ZöB- das 4- (N _f N- Piäthylainino) -benzoldi- aaoniura double salt with

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00 9 8 U / 08 99 bad GFJS.'m

Ii,

5. i-phenyl-3-pyrazolidinone and derivatives such as 1-phenyl-4-methy1-3-pyrazolidinone and 1- (p-tolyl) -5-p! ienyl-3 ~

pyrazolidinone.

Z carbon chloride, p-nitrobenzenediazonium fluoroborate, and p-diethylaminobenzene diazonium tetrafluoroborate.

Silver salts "as silver nitrate and silver behenate, <? Oldsalze _y as gold chloride and Goldstearat, Triazoliumrerbindungen such as 2, 3-Diphenylnaphtho ^ T, 27triazoliumohlorid and 2-rPhenyl-3- (o-carboxyphenyl) naphtho ^ l" _f g7triazoliumchlorid, Tetrazoliumverbind Ungen , such as 2,5-diphenyl-3- (o-arboxyphenyl) -2 «1,3,4-tetrazolium chloride and 2,5-diphenyl-3- (pmethoxyphenyl) -2,1,3,4-tetrazoliufl chloride, leukophthalocyanines, such as phthalogen blue IB (Farbenfabriken Bayer AG, Leverkusen) O

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6. 8-Hydroxy-1,2 _t 3t4-tetrahydroquinoline and derivatives.

7 «Phenols and naphthols, a.BοPyrocatechol * tert-butylpyrocatechol, pyrogallol j, tert-butylpyrogallol, 4-amino-1-» naphthol, 4-methoxy-1-naphthol _s resorcinol, 2,3-dihydroxynaphthalene and 1, 4-dihydroxynaphthalene. Inorganic and organic salts or soaps of bison, copper, silver, gold, cobalt and cadmium, bis (III) chloride, iron (III) tearate, iron (II) chloride, iron (II) sulfate ₉ iron (II ) stearate, copper (II) chloride, copper (II) stearate _f Silt emit rat, silver behenate and cobalt (II) chloride *

Oxidizing agents such as xalium dichromate and ammonium molybdate.

Inorganic and organic salts or soaps of iron, copper, silver, gold, mercury, Nikkei, cobalt, cadmium, cerium and tin, ZoB. Iron (II) stearate, iron (II) chloride, iron (II) chloride, bis (II) sulfate, iron (II) stearate, copper (II) sulfate, copper (II) chloride, copper (II) -stearate, silver! stepped _f silver stearate, silver behenate,

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Gold (III) chloride, gold stearate, • Mereurostearate, nickel stearate, cerium (IV) stearate and tin dichloride ·

Oxidizing agent, vde potassium dichromate, Ammonium molybdate, ammonium vanadate and quinone derivatives, like tetrachloroquinone.

Nitroso compounds, p-vie Hii ^ eodimethylanilln and N-llttroBodiphenylamin ·

8. Compounds that contain an active methylene group, such as N, N-dimethylbenzamide and N-methylacetamido

9ο amines, such as p-phenylenediamine, m-phenylenediamine and diethanol-5- »bromo-2-aiainothiazole, ζ .Β _β 2-ethylamino-4-phenyl-5-bromothiazole and 2-diphenylamino-4-phenyl-5-bromothiazole .

Aromatic aldehydes and ketones, ζ, Bo-tetrachloroquinone, 1,4-naphthoquinone, 2-chloronaphthoquinone, 5-chlorovanillin, p-di-

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ORIGINAL

10 · Nitroaoderivate, ζ. B. N-nitrosodiphenylamine, p-nitroeodimethylaniline and 1-Mi troeo-2-naphthol.

11. Iriaaen blindnesses, such as 1,3-diphenyl triasent

, -KH-M = N-.

12. Aromatic amines and aromatic Aminohydroxyverbi ndungen, ZcB, 1-Amino-2-narhthol, 3-Hydroxychinolln, p-Phen.vl ¹ * -

methylaminobenzaldehyde and 2,4-dinitrobenzaldehyde.

Aromatic hydroxy compounds, e.g. pyrogallol, gallic acid, methyl p-aminophenol sulfate and 4-methoxy-1-naphthol.

HetallaaXze, a.B. Eiaen (II) sulfate and cobalt acetate.

Amines, for example 2 _t 5-diaainotoluene and beneylaniline.

Coupling agents for the diazotype, e.g. 3-hydroxy-2-naphthanilide and ^ hydroxy-H ^ -naphthyl- 2-naphthamide.

Compounds containing sulfur, e.g. celiac sulfide, sodium trithionate-thioacetamide and thiourea.

SilbersalE8r e.g. _e silver nitrate,

BAD ORISlHAL

diamine and m-phenylenedi arain. Silver behenate silver stearate » Gold salts, e.g. gold (III) chloride and gold stearate.

Mercury salts, e.g. mercury behenate.

Cadmium salts, e.g. cadmium chloride.

Oxidizing compounds «z. B. Eisendll) -βtearate, copper (II) chloride, copper (II) atearate, cerium (IV) sulphate, ammonium vanadate »sodium bromate, potassium dichromate, ammonium molybdate and Tetrachlorquinone.

NitroaoTerblndurigen, e.g. o-KitroBobenzoic acid sodium as » p-IIi trosodimethylaniline, N-nitrosodimethylamine and N-nitro- sodiphenylamine.

Aromatic diazonium compounds, e.g. p-diethylaminobenzene

13 «Hitro compounds, z _o Bo2-Hitro ~ 4-chloroaniline, 1-chloro-2-nitro-4-diethylsulfamoylbenaol and dinitroresorcinol.

14o compounds which release alkali when heated, ζ "Bo the bescliriebo- NEN compounds in British Patent Specification 933 363" and alkaline compounds ρ ζ .33.Diäthanolainin, l'etramethylguanidin, p-Phenylendiaraln and triethylamine »

diazonium trichlorozincate and 2-hydroxy-4-sulfonaphthalenediazonium salt.

Metal salts, eg _o iron (lII) chloride, iron (II) sulfate, and cobalt acetate.

Oxidizable compounds such as 4-aminodiphenylamine-2-sulfonic acid.

Compounds that change color when the pH changes, e.g. the leuco form of p-nitrophenol, Phenolphthalein, bromothymol blue, chlorophenol red, bromocresol purple, Oxonol carbatoffees and 1,2, 3,4-tetrahydro-4- ^ 5- (3-methy1-2-benzothiazolinylidene) -äthyliden7-xanthylium-tetrachlorferrat * (III).

Mixtures of a diazonium salt and a coupler, e.g.

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Combination of p-diethylaminobenzene diazonium tetrafluoroborate and phloroglucine.

As a radiation-absorbing substances in heat conductive relationship with the heat-sensitive, reactive compounds or -. ³ ^ r composition or present in the recording element, is present, are, for example, be "infrarotabaorbierende and / or eichtbares light absorbing pigments, Zo) 3 ₃ dispersible dyes are used. The following pigments are mentioned in particular: CuQ, graphite, oxides or sulphides of heavy metals with an atomic weight between 45 and 210, such as manganese, nickel and lead sulphide or these heavy metals themselves in finely divided state, such as silver, bismuth, lead, iron, Cobalt and nickel.

According to a particular embodiment, the heat-sensitive recording layer is during the exposure to visible light in thermally conductive relationship with uniformly colored substances before, the light of a certain! Peile absorb the visible spectrum and convert it to heat _o A heat-sensitive recording

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βohioht, which is optically sensitive to this Veiee, can be used to record patterns colored lights · More details about substances? the absorb visible light and convert it into heat,

German patent application A 52 494, can be found in the British patent application 21 985/65) «

It should be noted that mixtures of these colored substances can also be used, so that light of the entire visible spectrum is absorbed. In addition, these substances do not only need to be used in the area of absorbable spectrum) they can absorb in infrared Bertloh, although the latter absorption is used to record red-colored image or template labels preferably * o lower as is balanced

The colored substances or mixtures of these substances absorb when used for optical sensitization the waroe-sensitive layer preferably light, since at least one of the primary colors (red, green, blue) or subtractian colors (cyan, purple, yellow).

Substances which absorb visible light or a part of the visible spectrum and in which absorbed light energy is converted into heat are, for example, "dyes which »U the classes of azo dyes, the triarylmethane dyes

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substances, the xanthene dyes, the acridine dyes, the Methine dyes, the azine dyes, the phthalocyanine dyes, the anthraquinone dyes, and related dyes.

In order to achieve a locally high enough heating effect for image differentiation according to the present invention, these dyes are preferably used in a finely dispersed state. The grain size of the dyes is preferably less than 0.1 μ .

The recording material preferably has an optical one Density from 0.03 to 1.30; in the case of reflective exposure, it preferably has an optical density for the light to be absorbed from 0.20 to 0.60.

The reaction compounds in the heat-sensitive sole

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are preferably used in an amount of 10 ~ ⁷ to 10 * hol / m.

The support, if any, for the heat-sensitive element is selected according to the exposure technique used; for example, whether a "contact copy" is used in which the radiation passes through the original the heat-sensitive layer is transmitted, or a "reflex copy", the radiation being transmitted through the heat-sensitive

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lent layer is let through to the original o In the latter case The carrier should absorb as little copying light as possible ο If the heat-sensitive element is a self-supporting If a layer is, the recording material does not, of course, need to contain a support for such a layer

. Several variations are possible in the direct contact copying method that such a heat conduction is generated only in a smaller extent (ZOB by _t is no pressure applied). The thermosensitive layer contains a substance which absorbs the copying light and converts it into heat Layer brought ₉ which in this case is sufficiently transparent for the copying light · «,

The normal method of reflex copying uses the original ZoBo a scribble copy, with the image-bearing surface in thermal contact with the heat-sensitive layer

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brings, and the exposure takes place through the latter "

According to a special reflex copying method, which is described in more detail in the examples and illustrated in the accompanying drawing and also in the Belgian one Patent 664,329 is described, the heat-sensitive layer is during the reflectographic Exposure not in actual thermal contact with the original chosen to be the copying Light reflected image-white »or contains a background, that reflects this light. Located in this pail eioh the heat-sensitive layer in uniform thermal contact with a subβtans or with substances that absorbs or absorbs the copying light and it converts or converts into heat, and that or those on and / or in either an element of the heat-sensitive material or a separate element, e.g. Copier forms, exists or exists · For more details about such an apparatus and a separate one Element is referred to the Belgian patent specification 664 329 »

The heat-sensitive compound or composition which remains unchanged d, _{0 o} h after imagewise exposure by heat still present, or can be developed on the recording material itself transferred onto a recording material ₉ which a reaction component for this

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Compound or composition contains the transfer can be carried out by means of a liquid or by non-differential (uniform) supply of a harmless (non-destructive) amount of heat in order to reduce the heat sensitive imaging compound or composition to vaporize or melt so that they are in this state can diffuse into the recording material.

The harmless heat preferably causes the heat-sensitive element an increase in temperature between 50

and 25O ⁰ O.

The effectiveness of the recording with electromagnetic radiation, which supplies the energy required for heating the recording elements8, depends essentially on the intensity of the radiation energy. For example, a recording layer _f which does not provide sufficient differentiation in the concentration of heat sensitive reactive compound or composition with a particular source of electromagnetic radiant energy can be fully effective if the energy level is increased substantially.

Radiation energy of short duration and high intensity is preferably used.

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Laiüpenconatrulctionsen and systems j which can deliver radiation of high 3n ~ veneit & fc in very short periods of time ₉ are all known alone

Light sources with a high radiation intensity and a relatively short exposure time are the so-called flashlight lamps, especially the discharge lamps, which use an inert gas included *

In the present invention, good results are obtained with a Wenon gas discharge lamp which can deliver an energy of 300 to 3000 W * see in a period of 10 "* to 10 seconds. More details about a copier which contains such a discharge lamp are found in Belgian Patent 664,868. "They intensity of the emitted light is in the infrared range high and especially high in the areas dee visible spectrum. Ee can easily temperatures bie BU 400 ⁰ C are obtained in the radiation-absorbing substances by a Blltzliohtbeliohtung high intensity is applied «,

It is possible to use a number of flash tubes working simultaneously or to use a suitable one To obtain image diffraction, flash a single tube at appropriate intervals. Reflectors and

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Bovine optical components can be included »in order to achieve maximum uniformity of irradiation.

'lie d UOH eS'.iaa the naohf oil constricting examples show IRFC e, i uuoh möglioh _(according to the invention, in particular geiijlß cm · h ;.:. l r ^ igegebenan Übertragungaarbeitawaise, Mehrfuchkcpien of only one die.? or Mater to obtain "d: ö d.irch image-wise heater, a recording material, which is defined here, was formed",

Bi? WUR-.Ι-ϊ "Irar the Aifzeiclinung patterns elektromagnetisuhar Stishlung b3ijont _s dooh should be noted that the ILrfin · ag, as well as record Wäriaemustem includes 9 whose ifärme in wärmeempfindlicl'.en element or warnervipfindl. A layer is abeoi'bierl "and that it is possible to form a heat-absorbing image in the recording material itself" e.g. if this material is provided with a light-sensitive silver halide layer or a layer in which an image containing silver is provided by diffusion transfer can be formed »as for example in the patent application de: · same applicant dated }, June 19'J6 inAt the internal file number G .1566 and the title" Aiuzeiohnunjja- und Wärmeaul'aelchnungsmaterial "(British guide taiiiuöldung 23 79! 5/65 ) is described to

fertilize nmr ganannten different PtJente and patent applica "aollten in conjunction with you? herein are taken into account * and biJ.den part of the disclosure.

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The following examples illustrate the invention without aie to restrict · »

At a D 1 e 1 1

A cellulose triacetate carrier becomes heat sensitive Coating applied, which is produced as follows:

10 g of powdered Oelluloseeaeetobutyrat (3 »G.:Aoetat» 2.04, Butyrat «O ₈ 71) for 1 hour in a ball mill with 0.5 g of HuS mixed composition are added 300 com acetone) and then is another half hour _o milled to the resulting suspension a solution of 1 g of thioacetamide in 99 cc acetone added, the whole composition is coated so that the coating according to Iroeknen has an optical density, measured by permeability, of 0.44 ₀

As shown schematically in the attached Fig. 1, the heat-sensitive material 39 is with its heat-sensitive layer 41 on a graphic, opaque Original 42, the light-absorbing image or original markings and has a light reflective background ο There is l: an intense pressure applied so that no actual heat contact of the light-absorbing image markings with the heat-sensitive pull. " The cellulose tetra acetate transparent support 40 is one

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Flashlight lamp 43 applied, which contains Xenongaa · The electronic flashlight generates a light intensity of 1600 W * eeo.

After the flash exposure, the heat-sensitive material is brought into contact with a recording paper and placed between a pair of lumps »as in Fig. Inclined 2, · performed The exposed "heat-sensitive material 39 and dae receiving material 36 are compressed between the rollers 37 and 38, wherein the former roll is heated to a temperature of 13O ⁰ · O.

H oh separation of the two elements is obtained a legible _(pink positive copy of the original on the recording material _β latter material is as follows zubereitett

On a paper carrier with a weight of 90 g / m 2 the following composition applied in a ratio of 12.5 m / kg:

Ethyl © € lluloB8 «with a SuI) S ti tu 30 g

tlonagrad of 2.45 in ethyl groups

Miekeletearate 10 g Amyl acetate 970 com <

When the coating is dry, the recording paper is ready to use.

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Example 2

Example 1 is repeated, but the amount of thioaoetamide in the heat-sensitive section the same amount of oxalic acid is replaced

A sheet of paper is used for all recording material soaked with the following solution and then dried *

Sodium sulfite 20 g

Fuchsin 50 g

Water 580 com

A legible, positive, pink copy of the original is obtained on the recording paper

Example 3

Example 1 is repeated, but the amount of thioaoetamide in the heat-sensitive layer by the the same amount of 2,3-dihydroxynaphthalene is replaced.

A sheet of paper with a weight of 90 g / m, which was soaked in a 5% aqueous solution of 2,5-diethoxy-4-benzoylajninobenzoldlazoniumchlorzincat.

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Han receives a legible, positive, pink copy of the original _{0 on the recording paper}

Example 4

Example 1 is repeated, but with the heat-sensitive one Layer the henge of thioacetamide through the the same amount of p-phenylenediamine is replaced »

^{A paper carrier of 90 g / m 2 is} used as the recording material, on which the following suspension was coated in a ratio of 12.5 Yes 2 Ag

Ethyloellulose with a degree of substitution of 2.45 in ethyl groups 20 g

Silver stearate 10 g

Acetone 970 ecm

Han receives a legible, positive, brown copy of the original on the recording material.

Example 5

The following is applied to a polyethylene terephthalate support heat-sensitive layer applied »

Cellulose peacefcobutyrate (sub- 10 g

degree of institutionalization acetate »2.1,

Butyrate * 0.75) ^BAD ORIGINAL

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Carbon black O ₉ 5 g

N-nitrosodiphenylamine 1 g Acetone. 489 com

This thermosensitive coating has an optical density, measured by transmittance, of 0.61 _β

The recording material is produced ₉ using a paper

ρ ο

of 90 g / m in a ratio of 13.5 m / kg with the following Composition is coated.

Ethyloellulose with a 20 g degree of substitution of 2 "45
of ethyl groups

Gallic acid 10 g

Acetone 970 ecm

If one proceeds as described in Example 1, is receive a legible, positive, brown-gray copy of the original on the recording material »

Example 6

Example 5 is repeated, but with the amount of N = nitrosodiphenylamine due to the same amount of tert-butylpyrogallol and the amount of gallic acid in the absorbing material due to the same amount of ferrous stearate is set

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A legible, positive, purple-gray color is obtained Copy of the originals.

Example 7

Example 5 is repeated, the amount of N-nitro-diphenylamine being the same as the amount of Phlorogluoln and the amount of gallic acid in the receiving material by replacing the same amount of p-diethylaminobenzene diaeonium tetrafluoroborate.

You get a legible ₍ positive * * brown-gray copy of the original «

Example 8

Example 5 is repeated, except that the amount of N-Iltrosodiphenylamine duroh the same amount of 8-hydroxy-1,2t3t4-tetrahydroohinoline and the amount of gallic acid The same amount of egg (III) stearate is produced in the recording material.

A legible, positive, purple-gray copy of the original _{c is obtained}

Example 9

Example 5 is repeated, except that the amount of N-NitrosodlphenylaBln duroh the same amount of 4-methoxy-

• J I -

BATH 0098U / 0899

1 «naphthol replaces and all suture material the all such material described in example 4 is used «

A legible, positive, green copy of the original β is obtained

If the carbon black is omitted from the recording material, no image differentiation is obtained on the recording material The receiving material is colored uniformly green 1 of the above ethanolic solution of erythrosine, a known optical sensitizing dye, is replaced, image differentiation cannot be obtained either, even if the added amount of seneitivation solution is increased to 5 com

Example 10

Example 5 is repeated, except that the amount of N-HitroBodiphenylamine is replaced by the same amount of ρ-phenylenedithiourate and paper as described in Example 4 is used as the recording material « After drying, the recording material has an optical density, measured by means of the transmittance, of 0.29.

This gives a legible, positive _f brown copy dee original "

" ³² ~ 0098U / 08

Example H

Example 5 is repeated except that the amount of N » Nitrosodiphenylamine by the same amount of 1,, 3-biphenyltriazene and the amount of gallic acid in the receiving paper by the same amount of 3-hydroxy-N-2-naphthyl-2-naphthamide is replaced «,

A legible, positive, orange-red copy of the original is obtained

Example 12

A paper of the parchment type with a weight of 60 g / m is coated with a heat-sensitive layer composed of the following composition!

Cellulose acetobutyrate 10 g (degree of substitution acetate =
2.1, butyrate «O ₉ 75)

Carbon black 0.5 g

Tetrachlorohinone 1 β

Aoeton 489 ecm

After drying, the material has an optical density värmeempfindliche ₉ measured by permeability, of 0 ₉ 48 o

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H / Q839

A paper of 90 g / m 2 is used as the recording material, on which a coating of the following composition is applied in a ratio of 13 »5 m / kg »

Ethyl cellulose with a substitution of 20 g of 2.45

Ethyl groups

4 ~ methoxy-1-naphthol 10 g

Aoeton 970 com

A legible, positive, blue copy of the original is obtained if one proceeds as described in Example 1 ₀

Example 13

A polyethylene terephthalate support becomes heat sensitive Coating applied from the following composition!

Cellulose acetobutyrate (degree of substitution: acetate «2.04,
Butyrate ~ 0.71)

Carbon black 0 ₉ 5 g

Dithiooxamide O ₉ 5 g

Acetone - 439 com

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Q098U / ^

Haoh drying be ait et da · värae-sensitive indigenous material optical view ρ measured by means of the i) urohlä88lgkelt, from 0.54.

A paper τοη 90 g / m is used as recording material, on which lets the following suspension layered

Xthyloellulose with a substi- 20 g tution degree of 2.45 in ethyl groups

Silver berries 10 g An \ y: uoetat 970 com It is suspension layered in such a way that an amount _t

jn syllable]

is present.

Silver behenate, which _{corresponds to 0 f} 15 in silver, per m ²

If you follow the procedure described in Example 1 proceeds, you get a legible, positive, brown copy of the original.

Example U

Example 13 is repeated, except that the amount of carbon black in the heat-sensitive material by the same amount of feinertelltea nickel sulfide is replaced o

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0098U / 0899

A legible, positive _P brown copy of the original e is obtained

Example 15

Example 13 is repeated, but with the amount of Soot in the heat-sensitive material is replaced by the same amount of indigo blue (0.1.73 000).

A legible, positive brown copy of the original is obtained on the recording material. "

Example 16

Example 13 is repeated, except that the amount of sithioozamine in the heat-sensitive material is reduced by the the same amount of tert-buty catechol is replaced.

A legible, positive, brown copy of the original is obtained on the recording material

Example 17

Example 13 is repeated except that the amount of dithiooxamide in the heat-sensitive material is the same Amount of 1-phenyl-3-pyrazolidinone is replaced. By repeating the transfer stage five times, each time with another image acquisition sheet, five can be sharp Copies of the original are received,

0098U / 08 & 9

Bets ρ ie 1 18

A cellulose triacetate backing with an undercoat as a hydrophilic ftolloidsohioht varaelisn is, with a heat-sensitive layer composed of the following composition covered:

Polyvinyl alcohol 30 g

Pear methylolurea 20 g

p-toluenesulfonic acid 5 g

aqueous dispersion »the 130 ecm per 100 ecm 0.5 g of silver.

black and 3.4 g gelatin

contains

5% ethanolic solution 20 ecm by terto-Buty! catechin

11? 5 aqueous solution of 30 com Saponin

Water ad 1000 ecm

Haoh Irooknen has a heat-sensitive material optical Mohte, measured by means of the transmittance, of

An image receiving material is prepared by immersing a porous paper of 90 g / m 2 in an aqueous solution of ferric chloride, followed by drying the paper

BAD OR ¹ GWAl. .. ₃₇ "009614/0899

After reflux exposure to flash, such as Described in Example 1, the heat sensitive material is moistened with water and then 20 seconds pressed against the recording paper described above Pulling both materials apart creates a legible, positive, blue-gray copy of the original on the recording paper received

Example 19

Example 1 is Aderholt _t but the wärmeempfindliohe layer is exposed through a Silberbilddiapoaitiv means of transmission x

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009814/0899

Claims (1)

PATEHT CLAIMSi 1. Procedure for recording baw. Reproduction of information and records of any kind by the imagewise or present-wise action of heat on a heat-sensitive8 recording material which consists of or contains a heat-sensitive element ₈ which has a reactive compound or composition »characterized in that a reactive compound or composition which can be removed, destroyed, or converted to a non-reactive or less reactive form by heat, the heat being applied imagewise or in a manner sufficient to effect the removal, destruction or transformation of the compound or composition to such extent cause that the decrease in the concentration or reactivity of the compound or composition can be ascertained in the image or in the original » 2. The method according to claim 1, characterized in that the decrease in concentration is displayed by means of a * a color change generating reaction. 3 · Method according to one of claims 1 or 2, characterized in that the heat-sensitive element according to imagewise exposed to heat is brought into contact with a receiving element, which is a reactive component for contains the still available compound or composition that affects the latter element by diffusion ₅₉ 0098 U / 0899 " _{BAti 0R} , q _INAL sion in a dissolved, vaporized or molten state, ' if necessary, transferred together with old softened binder, which is torn out when the two elements are separated will. 4 · Method according to one of claims t to 3 »thereby characterized in that the heat-sensitive element is blld- or template-wise heated by heat originating from electromagnetic radiation that is absorbed in substances that are in a thermally conductive relationship with the element. 5β method according to claim 4, characterized in that that the substances are evenly distributed or dlsperglert in the heat-sensitive material. 6. The method according to any one of claims 1 to 5 »aadureh, characterized in that the heat-sensitive element is exposed reflectographically imagewise or template-wise to electromagnetic radiation which is absorbed by substances and converted into heat which is in thermal contact with the heat-sensitive compound or composition are at the time of exposure 7. The method according to any one of claims 1 to 6 _9, characterized in that the heat-sensitive material is an op- - «Ο - ⁸ ^ Ofi! _{G) N} 00 981 ^ / 08 99 ^c having tables density, measured as permeability, between O _1, 05 and 1.50. 8 «Method according to one of claims 4 to?, Characterized in that the heat-sensitive material dispersed Contains infrared absorbing and / or visible light absorbing substances which convert light into heat convert· 9 ° method according to claim Θ, characterized in that that the heat-sensitive material contains finely divided carbon black. 1Oo method according to claim 8 or 9 »characterized in that that the thermosensitive material transmits at least 20 and at most 80 $ of the copying light. 11 »Method according to one of claims 1 to 10, characterized characterized in that the image or template-wise heating of the heat-sensitive recording material used Energy is generated by a high intensity radiation source that incorporates infrared light and visible light emitted in a very short time interval » 12e method according to one of claims 4 to 11, characterized in that the heat-sensitive element is exposed imagewise or template-wise visible light and the egg 8AD 0RJ3IN4! - 41 - 0098U / 0899 ment in dispersed form a substance or a mixture Clay contains substances that make up a particular rope of the visible spectrum absorbed 13 · Yar ferries according to claim 12, characterized in that » that the heat-sensitive element in finely divided form contains a color substance or a mixture of substances, which absorbs visible light that corresponds to at least one of the primary * or subtraction colors Method according to one of the preceding claims, characterized in that the heat-sensitive element as the reactive compound 1-0? henyl «-3-pyrazolidinone, 1,3-di ~ phenyltrlazine, 'ietrachlorquinone or 4-methoxy-1-naphthol , contains. ι 15ο method according to claim 14? characterized, that the heat-sensitive element after the image or before » layered exposure to heat brought into contact with a transfer material and 1 ~ henyl-3 ~ pyrazolidinone, which has remained intact, is transferred to it by thermal or liquid diffusion, where it reacts with a reducible silver salt. 16o heat sensitive material, characterized by at least one heat-sensitive recording layer that contains a reactive compound or composition which 0098U / Ö899 can be removed, destroyed or converted into a non-reactive fora by heat and is in a heat-conducting relationship with substances that absorb electromagnetic radiation? how does this radiation flow into Convert heat. 17 · Heat-sensitive material according to claim 16, characterized in that the heat-sensitive · material an · optical · density «between $ 0.0 and 1.90 has · 18 Heat sensitive material according to one of claims 16 or 17ff characterized in that the sub * ataiuian infrared absorb. 19 · Heat-sensitive material according to one of claims 16 or 17, characterized in that the substances make up a beatimote part of the visible light Absorb spectrum. 20 · Heat-sensitive ·· material according to one of the claims · 16 to 19 · characterized in that the reactive · compound or composition in a binder is brought in 21 · Wfindlich ·· Material according to claim 20, in that the bond or combination is incorporated into the hydrophobic binder. - 43 - 0098 U / 08 22o heat-sensitive material according to any one of claims 16 to 21 »characterized in that the compound or composition is in a carrier which is transparent to infrared and / or which is transparent to visible light C ^ p ρ is introduced in a ratio of 10 "* ³ to 10""mol / m. ORIGINAL 0098U / 0899