Pressure-sensitive recording sheet

PATENT OFFICE PATENT SPECIFICATION No. 284880 class: 15 b 17/02 lnt. El.: B 41 m 5110 expenditure day 12 October 1970 THE NATIONAL CASH REGISTER COMPANY IN DAYTON (U.S.A.) DruckempfindIiches recording sheet announced on 31 October 1968 (A 10610/68); stressed priority “Pateutansprflche 1 - 5 and 9 from 2 November 1967 (680251), PatentamprUche 6, 7, 8 and from 2 July 1968 (770878) (registrations in the United States of America). Beginning of the patent continuous “15. Feber 1970. The invention concerns a pressure-sensitive “autogenous” recording sheet, which contains all necessary components, in order to produce when influencing pressure the Druekmuster appropriate colored indication. Bekalmte autogenous ckuckempfindliche Aufzeielmungsblätter consist of a carrier sheet, which exhibits a coating of bio caps, which a colorless Farhreagens solved in an oily solvent to contain and in their direct proximity see fine TeiIehen of the mineral Attapulgit to find, which causes as a sour adsorbtereudes reagent the transformation colorless color reagent into its colored condition. This Aufzeicbnungsblätter is very susceptibly more gegentlber during the handling the same unintentionally caused pressure. Since Attapulgit is a mineral insoluble in the oily solvent, a further disadvantage arises as a result of that the reagent is on the surface of the Attapulgitteilchen. In order to switch off the latter disadvantage, one suggested, replacing the Attapulgit by a sourly reacting öUösliches phenol. The phenol is loosened in dern solvents oily from the broken open caps released and forms a colored oily liquid, not by RST an adsorbent surface reaction, but by a acid base Reaküon, with the colorless reagent extremely easy flowing is permitted and thus a complete reaction with the Gcsamtmasse of the color reaction means, what there the case is not, where in oil a Ilichtlösliches material is used. It turned out however that such sheets do not respond correctly to pressure. The invention decreases the disadvantages mentioned, by planning a autogenous Aufzeiehnurtgsblatt with a double coating of the carrier sheet. The first, lower layer consists of a multiplicity Miktokapseln, which contains one or more normally colorless chromogene connections solved in solution in a solvent, from very short cellulose fibers and from a sourly reacting clay/tone, and the second, upper layer, which see in direct proximity to the first layer rules, contains at least a phenolic resin, kaolin and alternatively a salt of an element of the group of 95 9.B, an element of the group of 2A or a transition element, depending on, soft color or hue of the indication is wished. Everyone of the two neighbouring layers can contain a bonding agent, and zw. up to 20% of the entire solid quantity. It was shown that by this structure the sheet can be together-rolled and/or rolled up, without thereby a unerwtlnschte color reaction arises due to the relative motion between two of its winding situations, if rolling up seh closely effected and it nevertheless maintains its AmprechempfindLichkeit for during the writing and marking ausgeflbten pressure, so that it is suitable for example for the production of sets of forms. Such recording material, which exhibits on the one hand no “Versehmiereffekt”, on the other hand however a sufficient sensitivity possesses, is of special importance, where a such sheet material is handled by Papierbearboitungsmaschinen and Dmckmaschinen, DO t, where its treatment stands except control or where it unbe - is correct is, how many sheets for the production of a Mehrfachformularsatzes use finding see. Accordingly the invention a durckempfndliehes consisting of a carrier sheet plans recording material, which carries a multiplicity of by dirt aufbreehbaren lvlikrokapseln, of which everyone a solution from at least a normally colorless basic chmmogenen connection contains, which drink reagent, which is added to the bio caps, with Berflbxung with one become colored. The according to invention on eiclmungsmaterial is characterized by it that the citizen sheet two layers finding with one another in unmitthlbarem contact exhibits itself, of which the first, lower i0 layer from a mixture from Mikzokapseln, very short cellulose fibers and much purifies particles of sourly reacting kaolin exists and of a mixture of very fine particles of a sourly reacting ö1iösllchen phenolic polymers and sourly reacting kaolin consists the second, upper layer. In the following tables the best suitable components, like them in the compositions of the first, are untern layer as well as the second, upper layer available are mentioned, as well as of them zulässi s and most favorable KonTent2ationen. First layer: Permissible KonzenGünstigster concentration range stepping ion range of components in thread - % in thread - % a basic chromogene solution containing Mil okapseln very small cellulose fibers much purifies kaolin particle talc strength to 1 to I to 0 to 8 to 3 to I 0 to 3 to 7 (if available) to I 0 second layer: Components from individual particles existing 01lösliches sour phenolic condensate very fine kaolin particles very fine particles of calciniertem kaolin calcium carbonate permissible concentration range in thread m/o2 to 0 to 0 to most favorable concentration range in thread. I0 to 16 to 8 to 18 (if available) 4 to (if available components of strength Latex, e.g. StyroI Butatien Gummioder Butylgummi Latex Gummiarabikum Zinkchlorid polyvinyl alcohol permissible concentration range in thread 2/0 0 to 0 to 12 0, 8 to 0 to 0 to Gtlnstigster concentration range in thread -070 to 13 (if available) 2 to 8 (if available) 1 to 3 3 to 17 (if available) i to 6 (if available) a number basic cbxomogener materials can be solved in easily volatile or non volatile, from one or more components existing hydrocarbons, whereby those hydrocarbon aromatic (or other one alkylated) organic solvents, e.g. toluol, xylene, paraffins and Cycloparaffine, e.g. Cs - until c1 s - paraffins and Naphthene, halogenierte Kohlenwasserstofle, Biphenyl and tetrachlorethylene e.g. chlorinated, to be can. The solved chromogenen materials become in totally enclosed the Verwöndung according to invention. Generally at least 1 thread in that solvent should grant - % preferably of the chromogenen material existing in a surplus of L o and an appropriate quantity of a phenolic poI ymeren material to be soluble, thereby! 0 an effective reaction comes off. In the preferential Ausfllhrungsbeispiel the solvent should be however in the situation solving a surplus of the polymere material in order to use the existing chromogene material as completely as possible and to thus guarantee the maximum colour in a reaction place. In the following examples are mentioned fflr suitable oil-soluble basic photo chrome connections, but are not the invention not on the use of these connections limit Arylphthalide, like 8, 3 - to - (p-Dimethylaminophenyl) -6 - dimethylaminophthalid (Kristallviolett Lakton); 8, 8 - to (p-DL - methylaminophenyl) - phthalid (Malachitgrün Lakto); 9-Diäthylami o-spiro (12-H-benzo xanthen -12, l' phthalid); 3, 3-bis (1 - Äthyl-2-methylindol-3-yI) - phthalid; Leucauramine, how from N-Halopheny! -, in particular n (2,5-Dichlorophenyl) - leucauramin; Ecyl aura mine, like N-Benzoylauramin and N-Acetylauramin; Aura mine, like N-Phenylauramin; insatiated a-0 - Arylketone, like DianisyIidenaceton, Dibenzylidenaceton and Anisylidenaceton; basic Monoazofarbstoffe, like p-Dimethylaminoazobenzol-o-carbonic acid (methyl red), 4-Aminoazobenzol (oil yellow AAl]), and 4-Phenylazo -1-naphthylamin; Rhodamin B lactams, like n (p-Nitro-phenyl) - Rhodamin B lactam; Polyarylcarbincle, as to (p-Dimethylaminophenyl) - methanoI (Michler HydroD, KristalIviolettcarbinol and Malachitgrtlncarbinol; 8 ' - Methoxybenzoindolinospiropyrane, like 8 ' - Methoxybenzoindolinospiropyran, 4, 7, 8 ' - - Trimethoxy benzolndolinospiropyran, 6 ' - Chloro-8' methoxy benzoindolinospiropyran; Aminostyrylchinoline, like p-Dimethylaminostyrylchinolin; Fluorane, like 2-Chloro-6-diäthylamino-3-methyl - fluoran. Although a g can find oße number more oil-solubly, i.e. in organic Lösungsmifieln of soluble phenolic resins in this invention use, the sour phenolic reagent consists mainly of a permanently fusible, linear, oil-soluble condensate of an aldehyde, e.g. an aliphatic aldehyde, like formaldehyde, or an aromatic aldehyde, like Benzaldehyd, and one or more parasubstituierten Phenolen, whereby the condensate mentioned normally contains in the Dv.rchschnitt three to eight repetitive phenolic units. If the condensate is applied as aqueous dispersion on the paper, it should exhibit a softening point of at least 60oc, preferably of %oc. One receives the softening point for a given condensate as follows: Resin particles become on a gradue! l staff warmed up from 50 to 110oC aufgestäubt. After 1 min by means of an air flow those particles, which do not stick to the bar, are blown away. The temperature of that point at the staff, to which the resin particles begin to stick first, is the softening point mentioned. The Parasubstituenten knows c1 to c1 z, normal, ISO, tertiary or Cyclo alkyl, aryl, Aralkyl and alkene aryl as well as e.g. p-substitutes phenol with different p-Substiülenten to be, from those. Mixtures with the same aldehyde to be condensed can. If p-Alky! - to be used, the p-alkyl-Subsfituent normally contains substituted Phe - nole in such condensates 4 to 9 carbon atoms. AI suitable p-substituterte phenol, which can be condensed with formaldehyde and used in this invention, is mentioned in the following some examples " p-Methylpheno1; P-Äthylphenel; P-n-Propylphenol; P-n-Isobutylphenol; P-t-Butylphenol; pn amyl phenol; P-n-Hexylphenol; P-Cyclohexylphenol; P-n-Heptylphenol; P-n-Octylphenol; p-ISO-octylpheno! ; polarize, 1.3, 3-Tetramethyl-butylphenol; P-n-Nonylphenol p-Decylphenol; P-Undecylphenol; P-Phenylphenol; P-Benzylphenol; P-Tolylpheno!: Isomers the phenol mentioned and mixtures, which contain 7 in each case, wei or several the above phenol or their isomers. The preferential softening point mentioned of 73°G and over it is selected, in order to avoid a softening of the resin during drying the upper layer in usual Beschichtungsvorrichümgen. A such softening or causes difficulties behn for meals and with further processing steps, there the resin e.g. at warm Meta! loberfächen would cling. In addition the danger exists when that the resin particles flow together and in such a way form resin agglomerates, which are not as well effective regarding the Farberzeugnng as the individual particles. the one which can be planned, consisting of individual particles, in the paper-manufacturing industry kaolin is general under the designation China Clay " well-known and is unequalled as in the coating, in oil and water insoluble oil-adsorbing material. White kaolin is used, which represents an ideal a material due to its white color, its blättchenförmigen particles, which lend unequalled coating characteristics in an aqueous mash to it, its frequent occurrence, to its general use in Papierherstellungsund Papie working on industry and its low costs. Naturally there are many other materials of mineral condition, which in place of kaolin use will can and also einemVergieich with this regarding its favourable characteristics withstand. Other kinds out of the individual particles existing and essentially colorless, in water and ÖI unsolvable sourly reacting minerals, which exhibit the necessary adsorbent characteristics and of those some Bentonite are, are considered than equivalents of kaolin, although they are regarded from the theological point of view not as good as kaolin. In eister line from Kao! in and pheno! ischem resin existing upper layer in accordance with this invention can be sensitized with metal salts, for example with Zinkchlorid. The Hinzufolgen of these salts increases the Farbaktiviemngsn igung the mixtures from kaolin and phenolic resin and increases also the Widerstanddähigkeit opposite color chwund the colored form of the normally colorless chromogenen connections. As metal salts such are suitable, dis a Werttgkeit of 2 exhibit. After their meaning there is salts of the 2B-Metalle, i.e. from zinc, cadmium and mercury, the 2A-Metalle, i.e. from calcium, magnesium and strontium, and the transition metals, i.e. from manganese, cobalt and nods!. The effective metallic connections, which are helpful for the production of the layer composition in accordance with the invention as well as for the production of kaolin and phenolic resin containing Papterbeschichtungen, are the halides, nitrates, sulfates and acetates of metals from that zinc, cadmium, mercury, calcium, magnesium, strontium, Barinm, manganese, cobalt and nickel comprehensive group. in a11gemeinen through derL additive of salts of the metals of the groups of 2B, 2A and the transition metals results into the coating mass a larger Inte consisting of kaolin and organic resins ität the printing and a increased ruggedness of the printing in relation to light and warmth. Of that selection managing specified of materials a number of different Zusammensetaungen can be made on dry phloem, from which an aqueous mash is then prepared. With this mash a finished paper sheet or one can still hates paper web during their production to be coated. Further this mash can do also as a Dispersionsbeschichtuug on sequential 88 filma a tige course from synthetic organic polymers, from which recording sheets, - volumes or - touches be manufactured can, or also on arbitrary other carriers in the most favorable in each case and/or desired thickness to be laid on. The aqueous dispersion out of the individual Tei! - chen existing material can for example of 30 to 80 thread - % water and 70 to 20% firm reaction means consist. Still another adhesive is added to the coating mass, in order to achieve the necessary adhesion of the particles at the carrier. However no such Klehernittel is to be used, which is inclined to cover the particles. Also should be admitted no more adhesives, than for achievement the desired adhesion necessarily, since otherwise the color reaction activity was decreased unnecessarily. In connection with liquid Austauschund additives also silica-gel must be mentioned, since it is capable of the presently/immediately strong colouring of oil solutions from normally colorless chromogenen materials and represents a good oil receptor for oil coloring materials. Always then, if the particles of kaolin and sourer polymere material exhibit a leiohte delay of the color reaction due to their situation in the carrier sheet, the additive of silica-gel is in a quantity up to that drinks polymere material due to its Eigenschai%en specified above appropriately, but is not necessary its use for the invention in its simplest form. The expression “acid” used in the description includes completely generally also Lewis acids and is bescbxänkt in no way on a special definition. The autogenous recording material according to invention provided on a side with two layers can be on its back provided with a dmckempflndlichen transmission layer, over e.g. to produce a copy of the printing on an underlying sheet. Suitable fibrous substrate can be made easily of a liquid, generally aqueous mash or a wet mass of arbitrary paper-forming fibers, which form an even fibrous course, whereby the most common fibers are cellulose fibers from rags and wood, which are usually used for the production of paper. Other intermittent, arbitrarily oriented fibers as well as mica panels and panels from synthetic mica or other fiber screen end of solids (e.g. Fibers from Polyacrylnitrüen, polyesters and PP, which can be processed in a paper trade machine from a mash to an even document from fibrous material) to be able to be used likewise. Example 1 " a preferential example of a autogenous recording sheet, which results in a black pressure in the case of breaking the caps open according to the influencing Drackmuster, consisting of two layers, is described in the following: Composition of the first layer: Thread - % in the Bestandtelle dry layer a solution from Kristallviolett Lakton and 6 ' - Chloro-8' methoxy indolino benzopyry! ospiran containing micro caps cellulose fiber of very small length, in the Hande! as “Solka Floc” available and by the manufacturer, the company Brown CO, Berlin, New Hampshire, the USA as BW-200 designation very fine particles of calcinierten kaolin (e.g. of the Fkma Englehard of mineral and Chemica! Corporation, Men! o park, N.I., the USA, under the designation “X-1624” refugee) talc strength 58, 8 14, 7 14, 7,5.9,5.9 - 6 Nr.g84880 composition of the second layer: Components very small particles of a phenolic resin mixture from 80 thread like polymerisiertern Para alkyl phenol and 20 thread - % polymeEisiertem Pataphenylpheuel thread % particles of kaolin Zinkchlorid polyvinyl alcohol, very fine in the dry layer 14, 0 calcium carbonate, rubber atabicum 12, 60, 8, 0 3, 0 2, 0 in this was used a new, a black dirt resulting in color. 1, 3, 3-Trimethyl-6' chloro - 8 ' - methoxy - [2tH - I1 - benzopyran-2, 2 ' - indolin] 3-bis (p-Dimethylaminophenyl) became -6 - dimethylaminophthalid, also under the designation the Kdstallvio with 3! Ett Lakton admits is mixed, and a solution of this mixture in a L5sungsmittelmischung from 2 Gew. - Parts chlodertem Bipheny! and I Gew. - Part of a hydrocarbon mixture with low steam pressure ('Magnaflux-Ö1 ") became in totally enclosed. “Magnaflux oil” contains 50 VOL. - And a Kauri Butano points % Naphthene, 49% paraffins and 1% aromatic connections! - Number of 29, 2 up. Of ftlr the two layers necessary components an aqueous Dispersten was made in each case. The first, lower layer was manufactured by Dispergterung of all materials with water up to a total solid content of 24%. The second layer composition became by Mah! EN of the phenolic resin on a Teflchengröße of 2 m in a 16% igen solution out rubber arabicum and water manufactured. A dispersion of all components of the second layer was diluted up to a Gesamtf ststoffgehalt of 30% and applied with a Meyer staff No. 7 over the first layer. The two layers possess in each case a dry weight of 5, 5 to 7 g/m2. The relationship of the solid content of the sour mineral more gegentlber po! ymeren material can strongly vary. The Beisptele is valid in particular fflr for paper coatings. In the case of the production of paper with the two layers from reaction materials only such Mengenwerte should be used, be guaranteed the one reaction and resulted in a closed paper web. Example 2: Composition of the first layer " Bestandtefle micro caps with 1 1/2 thread a Poigen solution from Kristallviolett Lakton and 3, 3-bis-kp-Dimethylaminophenyl) -6 - dimethylaminophthalid in the same solvent mixture as in example 1 cellulose fibers of very small length (“Solka Flox”) described very fine particles approx.! cinierten kaolin CX: 624”) talc strength thread - % in layer 58, 8 14, 7 14, 7,5.9,5.9 - q tmckenert - Nr.284880 composition of the second layer: Components see small particles of a phenolic resin mixture from 80 thread - %0 polymerized Para alkyl phenol and 20 thread - to % polymerized Paraphenylphenol “thread - a/o in the dry layer 14, 0 very fine particles of kaolin strength Latex rubber arabicum very fine particles calcinierten kaolin Cx-1624 '') 59, 8 8, 0 4, 0 2, 0 12.7 B e i s p i e 1 8: This example corresponds to example 2, on it that instead of the mixture out polymeri - siertem Para alkyl phenol and polymerized Paraphenylphenol in the second layer 14% of a resin from polymerized Paraphenylphenol is contained. As a result of breaking the caps open a blue pressure arises. B ice p IC 1 4: With this example in place of the Para alkyl phenol in example 2 for the second layer 14% of a condensate are used to the formaldehyde and p-n-Nonylphenol. The first coating corresponds from example 2. when breaking the caps open arises a blue pressure. B e i s p i e 1 5: With this example the second layer in place contained the resin to polymerized Para alkyl phenol in example 2 14 o of a condensate from formaldehyde and para tertiary Butylphenol. Otherwise the same materials were used as in example 2. In the case of breaking the caps open a blue pressure results. Example 6: Another composition for the second layer in place in the examples of the 1 and 2 described was manufactured as follows. “160 g of a condensate of formaldehyde with a commercial p-Octylphenol, which polarizes mainly to, 1, 3, 3-Tetramethylbutylphenol, 40 g Paraphenylphenolhatz (driven out in the trade under the designation " Vareum 523” by the company Reichhold Chemieals Inc., White Alains, New York, Vth pc. A.,) consists, 20 g rubber arabicum and 220 g water into a meal device was given and min long treated there. to 140 g see resulting in dispersion became with 315 g kaolin, 60 g Calcinmcarbonat, 200 g of a solution from 20 Gew. - % Zinkchlorid in water and 150 g of a solution out! 0 Gew. - % polyvinyl alcohol in water mixed. The arising dispersion became! min long with a Dispersator through-mixed, with 165 g water on a solid content of 50% dilutes and with a Meyer staff No. 7 so on the paper applied that a coating with a dry weight of approximately 5, 5 g/m2 ergiht itself. 2 the endgtlltige composition of the coating as follows " white Papierboschichtungskaolins (like it in the USA in Georgia and Süd-C0xolina, in Great Britain in Cornwall, in the Czechoslovakia, which Soviet Union and Germany are promoted) was very fine particles consisting components very fine particles of 12, 7 o of a p-Octy! - phenolformaldehydhoxzkondeusats and 1, g°] o rubber - arabicum calcium carbonate Zinkchlorid polyvinyl alcohol of solids in thread - % 63! 4! 2 8 3 B e i s p i e 1 7: A further composition for the second layer, those together with after the examples the 1 or 2 gesture of! lten first layer to be used can, " components of solids contain the following components in thread - o very fine particles refuses paper coating kaolin (like it in the USA in Georgia and Stld Carolina, in Great Britain in Cornwall, in the Czechoslovakia, which Soviet Union and Germany promote become) very fine particles of a phenolic resin mixture (including I, 2q% rubber arabicum) calcium carbonate Zinkchlorid Ätherisierte strength 58 14 12 8 8 B e i s p i e I 8: A further composition for the second layer, those together with after the examples! or 2 gesture of! 1ten first layer to be used can, contains the following components: Components see fine particles weifen of paper coating kaolin Sebx fine particles of a PhenolformaIdehydharzes (including 1, 9.7o/o rubber arabieum) to Caleiumcarbonat Zinkchlorid polyvinyl alcohol of solids in thread - qo 61 14 12 8 B e i s p i e 1 9: A further composition itlr the second layer, which znsammen with the first layer manufactured after the examples 1 or 2 be used can. contains the following components: Components of solids in thread - o very fine particles of white paper coating kaolin much purifies particles of a phenol formaldehyde resin (including 1, 2T] o rubber arabicum) calcium carbonate Zinkchlorid polyvinyl alcohol 63 14 12 8 3 example 10: A further composition for the second layer, which can be used together with the first layer manufactured after the examples 1 or 2, contains the following ßestandtefle: Components of solids in thread - to °7o see fine particles white Papterbeschichtnngskaolins very fine particles of a Phenolformaldehydhatzes (including 1.27% 63, 0 rubber arabicum) Paraphenylphenolharz calcium carbonate Zinkch! orid Polyvinylalkoho! 11,2 2.8 12, 0,8.0,3.0 Beispie! 11: A further composition for the second layer, which can be used together with the first layer manufactured after the examples I or 2, contains the following Best of portions: Components of solids in thread - % very fine particles of Papierheschichtungskaolin very fine particles of a phenolic resin mixture (including 1, 27% rubber arabicum) calcium carbonate Zinkchlorid polyvinyl alcohol 66 14 12 3 i0 Nr.284880 example 12: A further composition for the second layer, which can be used together with the first layer manufactured after the examples 1 or 2, contains the following components: Components very fine particles of kaolin very fine particles of a phenolic resin mixture (including i, 2 ° o rubber arabicum). Calcium carbonate Zinkchlorid polyvinyl alcohol of solids in thread. 14 12 II 8 example le: A further composition fflr the second layer, which can be used together with the first layer manufactured after the examples 1 or 2, contains the following components: Components of solids in thread - a/o 56 very fine particles of kaolin very fine particles of a Phenolhatzmischung (including i, 27% rubber arabicum) Caleiumnarbonat Zinkchlorid polyvinyl alcohol 14 12 3 example 14: A far a composition for the second layer, those together with first layer manufactured after the examples 1 or 2 to be used kaml, contains the following components of the I0: Components very fine particles of paper coating kaolin very fine particles of a phenolic resin mixture (including 1, 27°/o rubber arabicum) calcium carbonate Zinkchlorid polyvinyl alcohol of solids in thread m/o 14 0 8 3 example 15: A further composition for the second layer, which can be used together with the first layer manufactured after the examples 1 or 2, contains the following components: Ii - NR of 284880 components very fine particles of Papierbesehichtungskaolin very fine particles of a phenolic resin mixture (including 1, 27% rubber arabicum) calcium carbonate Zinkchlorid polyvinyl alcohol determines % 69 14 6 8 S fuel element i play 1 6 in thread -: A further composition ftlr the second layer, which can be used together with the first layer manufactured after the examples I or 2, enthä! t the following components: Components of solids in thread - o very fine particles of white paper coating kaolin much purifies particles of a phenolic resin mixture (including 1, 27% rubber arabicum) calcium carbonate Zinkchlorid polyvinyl alcohol 57 14 18 8 3 B e i s p i e 1 17: A autogenous Aufzeiehnungsblatt, which results in the Druckmuster corresponding a black pressure in the case of breaking the caps open, provided with two layers, is prepared in agreement with the procedure in accordance with example 1, however hiebei those become following aufge - compositions for the first and second layer led used. Composition of the first layer: Thread - % in the components dry layer micro caps with a solution from Kristallviolett Lakton and 6 ' - Chloro -3 ' - methoxy indolino benzopyrylospiran cellulose fibers of very small length (“Solka Floc”) very fine calciniertes kaolin (“X-1624”) talc strength 54, 8,8.8 25,0 3.7,7.7 composition of the second layer: Components of thread - much particle of a mixture from thread - % of a condensate from formaldehyde purifies % in the dry layer and polarize! , 3, S-Tetramethylbutylphenol and 20 thread - % of a condensate from formaldehyde and p-Phenylphenol 14, Caleiumcarbonat very fine particles of kaolin Zinkehlorid polyvinyl alcohol rubber arabicum Butylgummilatex o! o, o 59, o 8, o 0 2 0 0 B e i s p i e 1 18: An exhibiting antogenes recording sheet, which results in the Druckmuster corresponding a blue pressure in the case of breaking the caps open, in agreement with the procedure in accordance with example 1 one prepares for two layers, however those are used below specified Zusammensetznngen fflr the first and second layer. Composition of the first layer: Components of micro caps with a solution from 1, o Kristallviolett Lakton in the same solvent as in example 1 cellulose fibers of very small length (“Solka Floc”) very fine ealciniertes kaolin (“X-1624”) talc strength thread - % in the dry layer 84, 8,8.8 25° 0,3.7,7.7 - 13 - No. 9,84880 composition of the second layer: Much particle of a mixture from thread 4o of a condensate from formaldehyde purifies and polarizes components, i, 3, 3-Tetramethylbutylpheuol and 20 thread - % of a condensate from formaldehyde and p-Phenylphenol calcium carbonate very small particles of kaolin thread - ffo in the dry layer 14, 0 i0,0 59.0 Zinkchlorid polyvinyl alcohol rubber arabicum Butylgummilatex 8.0,4.0 2, 0 S, 0 B e i s p i e 1 1 9: A autogenous recording sheet, which results in the Druekmuster corresponding a blue pressure in the case of breaking open the caps, consisting of two layers, manufactured in the procedure of example I, with however the composition the first layer of those Beispie! and the composition of the second layer corresponds to 18 as follows is: Composition of the second layer of components very small particles of a condensate from FormaIdehyd and p-Phenylpheno! Very fine kaolin strength styrene butadiene Latex rubber arabicum very fine calciniertes kaolin CX-Z624 ") thread - % EN of the dry layer 14, 1 58.0 3.0,6.0,1.9 12.0 B e i s pi e l 2 0: A autogenous Aufzeiehnungsblatt, which results in the Dmckmuster corresponding a blue pressure in the case of breaking the caps open, consisting of two layers, becomes in accordance with the procedure of Beispie! 1 gesture of! lt, possesses however for the first layer the composition in accordance with example 18 and for the second layer the composition in accordance with example 19, only with the difference that with the latter in place of the condensate from formaldehyde and p-Phenylpheno! a condensate from Fotmaldehyd and polarizes, 1.8, 8-Tetramethylbutylphenol is used. Example 9.1 “a autogenous recording sheet, which results in the Druckmuster corresponding a blue pressure in the case of breaking open the caps, consisting of two layers, is prepared in accordance with the procedure by t3eispiel 1, possesses however does the first layer a composition in accordance with example 18 and for the second layer a composition in accordance with example 19, with the exception that with the latter in place of the condensate from formaldehyde and p-Phenylpheno! very fine particles of a mixture from 85 Gew. - °/o a condensate from formaldehyde and p-1,1,8, 3-Tetramethylbutylphenol and thread - % of a condensate from formaldehyde and p-terliärem Butylphenol to be used. Example 22: A autogenous Aufzeiehnungsblatt, which results in the Druckmuster corresponding a black pressure in the case of breaking open the caps, provided with two layers, is prepared in accordance with the procedure by example 1, possesses however for the first and second layer in example 17 the compositions specified, with the difference that during the composition for the second layer in place of the used Kondensatgemisehes a condensate from formaldehyde and p-1,1, 3, 8 - - Tetramethylbutylpheno! one uses. Example 23: A autogenous recording sheet, which results in the Druekmuster corresponding a black pressure in the case of breaking the caps open, provided with two layers, becomes in accordance with the procedure of Beispie! 1 prepared, possesses however for the first and second layer in example 17 the compositions specified, with the difference that during the composition for the second layer in place of the used Kondensatgemisehes a condensate from formaldehyde and p-n-Nony! - phenol is used. Fuel element play 24: A autogenous sheet, which results in the Druckmuster corresponding a blue pressure in the case of breaking the caps open, provided with two layers, is manufactured in accordance with the procedure by example I, whereby however the composition for the first and second layer is selected as follows " composition of the first layer: Thread 4o in the components dry layer micro caps with a solution of 1, 5°/o2, 5-Dichloro-phenyl-leucaummin in the same solvent mixture as in Beispie! i Ce! lulosefasern very small length 84, 8 (“Solka Floc”) very fine calciniertes kaolin (“X-1624”) talc strength 8.8 25,0 9.7,7.7 composition of the second layer: Thread m/o in the components dry layer much purifies particles of a condensate from tertiary Butylpheno! and formaldehyde Kao! [n Zinkehlorid Butylgummilatex polyvinyl alcohol 2.0 8! , 0! 0, 0,3.0 4, 0 B e i s p i e 1 26: Two layers an exhibiting aufogenes sheet, that when breaking the I&lt open; apseln the Druckmuster appropriate tin-upper-red and/or orange pressure, in accordance with the procedure by example 1 is prepared, wohei the composition of the first and second layer results in as follows [is selected: Composition of the first layer components of micro caps with a solution of i, 6°] o tin-upperred (2-Chloro-6-diäthylamino-8' methylfluoran) in the same solvents as in example i cellulose fibers of very small length (“Solka Floc”) very fine calciniertes kaolin (“X-1624”) talc strength thread o in the dry layer 54, 8,8.8 25, 0 3, 7,7.7 composition of the second layer: Much particle of a condensate from tertiary Butylphenol and FormGew purifies components. o in the dry layer aldehyde kaolin Zinkchlorid Butylgummilatex polyvinyl alcohol 2.0 81, 0 10.0 3.0 4, 0 example 26: An exhibiting autogenous recording sheet, which results in the Druckmuster corresponding a rosafarbenen pressure in the case of Auforechen of the caps, in accordance with dern procedures after example 1 is prepared for two layers, whereby the composition of the first and second layer is selected as follows: Composition of the first layer: Components of Mikmkapseln with a solution of 1, 57: /o pink one [9 (D [äthylamino spito (12-H-benzo xanthen-12,1-phthalid)] in the same solvents as in example 1 cellulose fibers much gerindet length thread - % in the dry layer 54, 8 (“Solka Floc ") 8, 3 very fine calciniertes kaolin (” X-1624 ") 25, 0 talc 3.7 strength 7, 7 composition of the second layer: Components see fine particles of a condensate from tertiary ButylphenoI and formaldehyde Kaoltn Zinkchl ID Butylgummilatex P olyvinylalkohol to thread - % in the dry layer 2.0 81, 0 I0,0 3.0,4,0