DE1197102B - Heat sensitive copy sheet - Google Patents

Description

GERMAN

PATENT OFFICE

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<ί'ί ", ΓΟ I * ' Ό> ι

rna iij

1960

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The invention concerns the themographical reproduction of graphic rOdginafettiinnariins ^ besöndiere - verweiidljaMfe ■ - :. .newer; -heat-i sensitive copy sheets ^. - ij, vA - :, 'j: s vr ^ nV. <ύλπ

A; rbeJianiites thermographisGhe &;^important:; .Res produktionsyerfahren ·, which, extensive, application at the Repraduktiori / Vön-Schriftvsfechsoln, a; Bj typewriter letters, -finds,. Consists therein; ; that a wäOTeempfindlcfees'Kopierblatt £ a / warming conductive contact with a: graphic, Oraginat m compresses, .-. the -short -.Zeit;, i "is teQsiy .bfestmöt, Zr example, with an on infrarötenKAiiteilen !; rich radiation / which on: the CMginaiicantstartdeneWarmfe will show., on. the .. copy sheet. transmitted ^ with a corresponding sicfetbarei change ^ iherf ^f 5 is called. In doing so, a reproduction of the original is achieved. ■: ■ ... ·: -.:-.-, ν, · πο .: r _f! . _: t ■■■;] _,> ■ ^ ■ The heat-sensitive-copy-sheet-must-be for the. of - ■ ReprodnMiönsverfahreiis voi * ruling TempemtUEjnasiGh ^ ^ and can sichtbariieägiei reindeer, which, this -TefflpefatiHt, usually imported range: from ungefäör -9Θ; t "is 150 ^Q C, as indicated by indireJcte · measuring methods fermitteit wir4i · - The. Copy sheet 'must; simultaneously suitable soaps ^r "'^ f üöt more normal Mandhabiingsr andi VerwendungsbedM- ^ 5 öihne conditions without appreciable Verfaiferaigimd ¥ e * - {ust represents sensitivity Jängerer:... For example, time kept throw .: - .:"-.' : ■ - · ''^-:; ~ <;■>': .- -.- "- z: i ^ ^r <\ . According to experience, new types of thermal acceleration are proposed for the copy sheets, -the'. 'Theh-ge * raanateo requirements are sufficient ~ -. L ; /' I i water-free organic triazenes, - which are obtained by the keodeösatioii of diazo compounds with primary or secondary organic amines, no matter what substitutes are used, are now a well-known group of ink intermediate products, the widespread use of cellulose in ink printing The latter process normally involves the acid hydrolysis of the triazene and the subsequent coupling of the released diazo compound with a coupling component to form a water-insoluble dye. The required acidity and moisture are generated by the tissue that was previously with a paste of the triaceae and the coupling component, which is subjected to the action of water and acetic acid, a modified process ¹ requires dea ^: addition of a base containing nitrogen which can be distilled with water vapor to? the Diifck- · 5a paste; by removing the base by treatment with steam, the alfcality Minnesota Mining ^ ändfMätkifäefeFirig "■ '" - "Company, St. PaM, MMni = <V. St. A.)

Representative: q

, Dr.-Ing. H. Ruschke, patent attorney,

itfi & l ·, St: Paul, Mimt --'- ■ - '· ν

(832,178)

derftMi £ chuiigrfeeiiabgesetizt - trnd: "the hydrolysis and coupling etfraagKoht-fJo-f. ·, .-: · =; -.: /.-: .- v; -:; -...: ·::: ■ ' .. ".- .:

rDäie-fählicBe'Bdharidlung is in: Printing of the G "weföeii · z ^ eclstaäßig 'and-completely satisfactory, but can be used as a product of writing * stföckenijußdfätefefeeav graphical originals are transferred by theimendagräfeeav> gr '- a lighter -fiüehiigen stiekstoffbaltigfcn -Bäse'Wäre may dfe Notwend% fceit' ^ "eiriet 5 Wasserdampfaestillatiött to * uingehen 3 ;: but JvetdüiSten ί such 'substances already h & L ^{RäumtempetaiHtf:} aM thin layers und.sind ißeistens-giftigiriAiBsifieseii ^ and Other reasons are the use of: mixtures of triazene and coupling components in the production of heat sensitivity! iKoptörbIätter, - which are suitable for thermographic reproduction of graphic originals, very inexpedient; consequently, such an application has not yet been attempted ^ ·.; - "-: ■ ';' ■ -. ...- ;; /: -:: ~ r ::. ■■. :.: .. .1 ^':::

Surprisingly, it has now been found that warm-sensitive Soprian leaves are resistant to treatment under normal storage conditions and that the reproduction of graphic originals by means of t & erniograpbiee & fc procedures in the absence of water ^. or 'Acid vapor errtiöglidien ^' with triazene and coupling components as the only reaction * partially obtained: Can. ::.
: Although the substances capable of action are otherwise: “treated! or. a solid, dry-mounted binding agent

3 4

can be used, they are preferred together are 3-hydroxy-2-naphthanilide (Naphthol AS) and

»With a suitable film-forming binder as 3-hydroxy-N-2-naphthyl-2-naphthamide (naphthol

thin surface coating on a carrier fleece, e.g. B. AS-SW).

made of paper, or a transparent film, although a dye-forming reaction was involved . Further layers can e.g. B. as a top 5 of a triazene compound and an azo coupling Sächenschutzüberzüge or to improve the component in the presence of water and acid contrast or the opaqueness is always present vapor, it has been found that many of the be. A preferred structure consists of thin possible very specific combinations in the semitransparent paper, which do not undergo any visible reaction with a thin form of sheets and under the conditions of triazene, coupling component and binder used in thermographic heat-sensitive sheets of a mass of copying processes. However, it was coated, whereupon a thin, opaque layer was found that the ingredients applied when mixed in the pigment-binder layer making a mixture of glacial acetic acid and ethanol in the room, so that old color changes in the warm temperature or moderately elevated temperature immediately sensitive layer through the paper 15 react in a visible way, also in the form of and against the opaque background - copy sheets are fully reactive and can be seen. excellent for the production of normally resistant

The triazene constituent of the thermosensitive thermosensitive thermographic co-

Layer can be suitable by the formula piercing sheets.

A _x JsJ = N ν R ²⁰ The test is expediently carried out by

I just a few crystals (about 10 mg)

R 'of each reactant in 5 ecm one

Solution of 10 parts by volume of glacial acetic acid and 90 parts by volume are reproduced, in which Ar is given an aromatic part 95% ethanol and before remainder, R an organic residue and R 'an organically 25 is shaken. Substances that represent an ocular residue or hydrogen . According blickliche and show distinct color change if their composition and their preferred they are tested in this manner are, for the production process can manufacture such compounds useful heat-sensitive co useful as pierblätter suitable by primary or secondary amines. If, in the experiment, stabilized aromatic diazonium compounds are not shown, temperatures in the range from about 25 to 37 ° C are not observed. The color change that occurs for these copy sheets is noticeable if the substances used are triazenes are not strongly colored, and theirs are also ineffective in the copy sheet.
preferred representatives are even practically colorless. The then appropriately chosen reactions Se are resistant to actinic irradiation, tion participants are preferably separated in a z. B. ultraviolet light, and not hygroscopic. 35 Binder solution as extremely fine particles They are solid at normal room temperature and dispersed, the dispersions then mixed and at moderately elevated temperatures. They can optionally be applied over a thin paper or a film that runs through at room temperature within the prudent film. Water-resistant polymeric settlement range from about 90 to 150 ⁰ C melt, binders such as polystyrene, polyvinyl butyral and are in any case practically not in the case of ethyl cellulose are preferred, and the suitable temperatures are volatile. Examples of inert liquid solvents for the respective compounds of the specified composition and polymer can easily be determined. The over- properties, which is for the production of the inventions coated nonwoven dried at moderate temperatures overall to the invention the heat-sensitive copy sheets to any premature dye-forming as proven suitable are 1,3-Diphenyltriazen to avoid 45 reaction.

l, 3-dipfaenyl-3-methyitriazen, l- (2-carbomethoxy- The nature of thermographic reproduction

phenyl) - 3 - phenyitriazene, 1 - (2,5 - dichlorophenyl) - process makes direct measurement of the during

3-phenykriazen, l- (pN-methylacetaminophenyl) - the process in the heat-sensitive copier

3-phenyltriazien, l- (p-diethylaminophenyl) -3- (p-acetal sheet) at the prevailing temperature.

aminophenyl) - triazene, 3,3 '- dimethoxy - 4,4' - this is an indirect process of temperature

phenylenbis - [3 - methyl - 3 - (sodium methylene carbide determination applied, in which a piece of a

oxylate) - 1 - triazene] and 3,3 '- dimethoxy - 4,4' - di- copy sheet for a moment against a

phenyienbis-P-methyl-3- (sodium-jS-ethylene sulfonate) - heated metal test block at a known temperature

i-triazene]. temperature and every visible effect on the

A large variety of coupling components, 55 sheets is observed. Copy sheets in this which are capable of coupling with diazo compounds to dyes to sample of colorless or pale colored leaves, is known, and such comparison in those with clearly visible and ratio linkages are reversible in general according to the invention comparable moderately intense color at temperatures between. So many aromatic hydroxy can be converted to about 90 to 150 ⁰ C, provide off the thermo-active Methytenverbindungen, the graphic as Azokupplungs- reproduction of typewritten components are compounds, aromatic amino compounds and 60 drawn results in terms of known pieces also according to the invention or similar graphic Originals with to be used as clutch components. The thermographic copying machines.
very reactive aromatic hydroxycup- The preparation components according to one of the following examples are preferred, of these 65 copier sheets provided were found to be suitable within the temperature range specified are the arytamides of 3-hydroxy-2-naphthoic acid and those in the art as »naphthol AS «- (anilidic acid) - provide satisfactorily clear and distinct thermo series are known, particularly suitable. Examples of graphic copies of graphic originals. the

Leaves are usually faintly colored when they are made, but suffer when they are made prolonged storage or normal treatment in normal offices no noticeable change in their Coloring and remain fully sensitive to heat. Copies are made immediately by exposure to the thermal image and obtained without the use of solutions, vapors, or any other additional treatment. The copy sheets can produce images in virtually any color you want including the ordinary preferred blue-black.

In some cases, the triazene and the coupling component can slowly interfere with each other Forming colored reaction products react when mixed together in the binder solution will; and the copy sheets made with such substances are also discolored during storage and lose their sensitivity. The resistance of such mixtures can can be improved by e.g. B. the proportion of binder is increased or by binder and Solvent components are chosen in which the triazene and the coupling component are less are soluble, or by being coherent but practically separate coatings from mixtures of Triazene and binder or coupling component and binder are produced. Inert additives, z. B. Pigments and fillers can optionally be added for certain purposes; so improved z. B. Titanium dioxide the resistance of the sheet, increases the copying speed of the sheet in thermographic »front printing ^ reproduction processes and provides a whiter background for the colored warmed images. (If the copy sheet lies between the original and the radiation source, the working method is called "front print" or "front print".) Further changes that fall within the scope of the invention are possible and are based in part on the following illustrative but not limiting examples

example 1

A binder solution was prepared by dissolving 144 parts by weight of polystyrene resin in a mixture of 288 parts of acetone and 168 parts of commercially available heptane. 1 part of a triazene compound, a solid, water-soluble, stabilized with amine tetrazotized o-Dianisidinverbindung was that decomposes at about 255 ⁰ C, was dispersed in a ball mill in 4 parts of the binder solution. Separately, 1 part of 3-hydroxy-2-naphthoic anilide was also dispersed as a coupling component in 4 parts of binder solution. The two dispersions were mixed with one another and applied to card tracing paper by means of a spreading knife set to an opening of 0.05 mm. The sheet was dried at room temperature. It was light yellow in color and remained externally unchanged after standing for a long time at room temperature. Pieces, which were heated by short touch with a metal block at about 15O ⁰ C, were given a deep blue color; the same took place in the heated image areas when the sheet was used in a thermographic reproduction process.

The triazene component was made by reacting sodium methylaminoacetate and tetrazotized o-dianisidine obtained in aqueous solution. The substance precipitated in the form of light yellow crystals, when the solution was brought to pH 8.5 with sodium hydroxide, it was filtered off and dried.

The product decomposed at about 235-255 ° C. Due to the manufacturing process, analytical tests and other reasons the substance was named 3,3-dimethoxy-4,4'-diphenylenebis - [3 - methyl - 3 - (sodium methylene carboxylate) -1-triazene] identified.

The triazene and the coupling component were also tested in glacial acetic acid-ethanol solution. The reaction started immediately and the solution became intensely blue in color.

B e i s ρ i e 1 2

Dispersions of reactants were prepared as in Example 1 except that the amount by weight of the reactant was half the amount of the binder in each case, acetone and heptane were used in equal amounts by weight, and the total volume was sufficient to produce a mixture suitable for coating. The mixture was applied to card tracing paper in a thickness of 0.07 mm and dried, and a further coating of a mixture was then applied over this layer, which consisted of the following uniformly ground components: 27.2 kg of zinc oxide pigment, 0.9 kg of one under the name "Santocel C" (trademark of Monsanto Chemical Comp., St. Louis, Missouri, USA.) commercial extender and 75 g of phthalic anhydride in a solution of 2.7 kg of a resinous copolymer of equal parts styrene and isobutylene in 60 kg Heptane and the sheet was dried again. "Santocel C" is a silica airgel that has an average particle size of 3 to 5 microns, a refractive index of 1.45 to 1.46, a dry bulk density of 0.08 g / cm ³ and a surface area of about 130 m ² / g owns. The analysis shows a content of S1O2 of about 90 to 91.5%, of volatile components from 4 to 5% and of sodium sulfate from 2 to 3%.

The copier paper obtained was white and opaque. By heating to about 150 ^° C., a blue coloration was produced in the reactive middle layer, which was clearly visible through the practically transparent carrier paper and against the opaque white background of the outer coating.

Example 3.

5 g of 3,3'-dimethoxy-4,4'-diphenylenebis (3-methyl-3-phenyl-1-triazene) were dissolved in a solution of 15 g of polyvinyl butyral in 80 g of ethyl alcohol. 8 g Naphthol AS Supra-Hydroxynaphthanilid as Coupling components were separately in a solution of 12 g of polyvinyl butyral in 80 g Ethyl alcohol suspended. Same parts of both sus-

(10 pensions were mixed, applied to clear polyester film and made into a permanent heat-sensitive copy sheet with a pale yellowish tint that dried when heated was colored blue.

When the two reactants are mixed in small amounts in the glacial acetic acid-ethanol test solution they reacted immediately to form an intense blue color.

Claims (1)

imrn The triazene component of this example is in the lOibrili üribiö Jim i ^ gpp fäiülos ;! urid djjteear; i) iuridieiiTäDiu% (ioesi-igiiinlgBsetitteii iili I -fiiffaihdta & d Ifttei! in b de « q tMbfigfenri-an] -bothii Ingredients are not decisive;. "Provided :. Colours. gg uuid vhnaini sb-iu ' anti! dOPfoigemiÄsung. vtol ^ finlyvinylbotyrälharz. in äthanoHgelölstu OjS 5eifc (ü <Biy6iBriSihl n ^ gelödtji €} feiefe iGewichi * gimigi ^ dl * lbGi (ieIifL <isιmgen ^ w ^ ιotoivefΠliseht) unÖ ^^ düK ^^ diidbpapieEria fen runs) i the ^ ofaccr ■ " became i & ft- gg gteIäe £ Bari the.·; tgegeibleinBBBJ iMBtaHbttiäcriTViHi gISQfiC would ^ iituid-'Jioan ^ Bl ftön .ßeprfj ^ faapccdii / gedfddkfe} Qtri & fnaJfc najHiijdeOTififtermbgrarAis ^ eanVeretfehErtfen '^' ekHErtfen? i enata ι Se. <mik> bofara räcneigies rb &slrafaMKiiwt'dei SV bnu ^ l
- \ iDts ^ Tariazqd Md that no D ^ oo ^- t3oa Mßrmfoo sni'j? «B .bsoioA part 40 kHlargowkdfl rliiDQO'ifinifAcefony gdBät / Separated 4OjTtUSj tuner iWy / oigepqijosiiife jTQ &riRDlvyiäylbXifJfralharxin'Acetoafgsameebdn unds tJamjti jvist - 'i ^ riKHppktegekcaliponenteodietesuBeispids sfeosde Dütttaacichniingspapier fwerdcn ^ unfäehst imiJi! eticr düimeripgleiciönäßigenjfSchkifiiider ArstenrLostog ^ ₀ coated in a thickness of 0.05 mm; dmld> daoa ', . I ! ι i η di ■> 0 if the tenipefatur is moderately increased, dry thoroughly. Ke ^ SeWchtaäas: ■ the: second: the solution was wufsrsdcf eisten “pushes; in. approximately glfeieJiet -_, Stäikßi auSge-j RaünU «rnperaiur, Das · 'dnaekeae: sheet:
dl wftd'milde ifcä · Was, and delivered good results from the original wonijgcdruekten, dfeaa -theraoH grapÜBchea! Method. The participants in Reaskiiqiisteii immediately "an inlensively deep red color, vs. ^! . '/ 1 ;, Wänneerapßndiiches KaptesMaäat das
¥ «iwmdiBBg with thermögeas ^ iischeii procedures t. d ä byc Ji. gekea jr ieich ή. e.-t -, · «its thin, visible heat-sensitive -ή: Visibility contains intimately connected ^ reaction conditions, which", from ^^ änsr Aäskiipplungs ^ πι; faarapcBieatSi'and a firm; . at n up to ^ etvra 15Q ° € ^! non-volatile: die-following StraltarfonneThat T ■■■ '■ - ivys ^ 'i- ^ werin'Ar ^^ an aromatic R ^ st, R an orgafliseher - ~ 57Rest or "Wasserstctf und R ^ allei" betcachten ·, i'jb is an Efgaiiischer residue, whereby the? 3Kupp «Higs ⁱ - ^ JiüÄHpbnente. And xlas; iFria / eri furthermore enable them to react visibly to each other immediately if they are mixed in a test solution for glacial acetic acid and -Tj: <ether oil..:; Ί: oii. - isriu ^ i / Wjäfaieerripfindliches Kopierfeiatt after Ah- »A'jSfttttA'i ', ·' characterized in that the ^: Tri» - ■ jbiäzen is a tetra * - bm ^ zotiettes o ^ Diariisjdin.:; ' ^: ->.: - ^ .. -yj πj3i Heat-sensitive copy aiisttl aach an rjasppbchu ': Met%' gekemizEiehhet that the coupling component is an aromatic hydroxy compound, ~ ..; 4. Heat sensitive. Copy copy after Anw & firathV, 24Sder "-3," dadtarch geleflMzeicIniet that D'j'idie ¹ KepplufigskomponeÄe · ai 'Airyiamid' der ; 'io§R is hydroxy-2-naphthoic acid. 'ί ^u ''-■' ■ '- -vmi: i $ l heat-sensitive copi ^ sheet after AtI * - "iti' ^ prtich 1 / ioder 3, dadastii marked that ι c / the visibly warm, sensitive layer is a poiy - -! '^ mere * film-forming picture medium eeöiäh, ί ^; r'i'jrfüi) - ?. -IvlJDiTi-i.5-r'irJn-ji / rf-j nf> / 'H'.u - "> I'" iriio πι ft ^ b'iu «ino '■ Knj-ir / ii'ji'in-'. ;: - o! '. iu iorio / i! :: ./ riiA y. (M πι! Ϊ́-πν: υ. '!! / ίί' ^ ί '/ ί -'Ϊ ^! Ίί bi! [(L |, f !! rini; i!'YO'lfyV! I- /; -: r; .l ^ ^ / if, ;; -'.- ;; / 'tj / in nry / uii it'n'ji' / Λ fiohiu // -'ü; jüoqiao ^ .- ^ niii'- 'nu Ά 2 UH rri ifr'v;: iri! 7f; ivy! i> ^c i 2'. '! ^r r <. ·. / zr ·; j <i> _ ["r-jfti ^ vü?" ! -JbI- ""! -.;! L'jT ji '? I -)! I>Π'.-; ιί) 'Ίjf.y ¹ ! ^ I'irf' .- ^ 'ijiv-.r. 'j ^ n'H'.UrlVlflilv'jj ^1. ! ίU) j .lii ^ 'üfmi'V fi; .i / iil // ■■ ijV.O \> ^l . <<,'i> T _l fmr./ "" ir , ^ ^r ! -j'fui: br!?; q! r! 'jr) frri: · .'-- gnubliH "(OHiU no'trv 01? iiorniGü ?! .rrjii-ü« i ^r '^> itri no / ;; ■. . i Vi ','! i ' ¹ * - ■ ".