EP0012579B1 - Systèmes d'enregistrement sensibles à la pression et solutions à utiliser dans ces systèmes - Google Patents

Systèmes d'enregistrement sensibles à la pression et solutions à utiliser dans ces systèmes Download PDF

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Publication number
EP0012579B1
EP0012579B1 EP19790302817 EP79302817A EP0012579B1 EP 0012579 B1 EP0012579 B1 EP 0012579B1 EP 19790302817 EP19790302817 EP 19790302817 EP 79302817 A EP79302817 A EP 79302817A EP 0012579 B1 EP0012579 B1 EP 0012579B1
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Prior art keywords
phenol
radical
promoter
alpha
solvent
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EP0012579A2 (fr
EP0012579A3 (en
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Pierre Jean Allart
Claude Andre Guillaume
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Bayer Agriculture BVBA
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Monsanto Europe NV SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • B41M5/1655—Solvents

Definitions

  • This invention relates to solutions which are useful in the production of pressure-sensitive mark-recording systems and to systems thus produced.
  • the most familiar form of pressure-sensitive mark-recording system is the so-called carbonless copying paper which comprises a two-sheet system in which the under surface of the top sheet has a coating of microcapsules of a solution of a colourless chromogen, while the upper surface of the lower (receiver) sheet has an absorbent coating including a sensitizing agent for the chromogen.
  • a marking instrument is applied to the top sheet, the microcapsules are locally ruptured, thereby releasing the chromogen solution from the affected microcapsules to react with the underlying sensitizing agent and form coloured marks on the receiver sheet corresponding to the marks applied to the top sheet.
  • a successful carbonless copying paper system needs to meet a number of criteria. For example, the marks on the receiver sheet should develop rapidly to a legible intensity of colour, and a legible mark should persist for as long as the sheet is required to be kept. Whether the various criteria are met depends on a number of factors including the nature of the solvent, the sensitizing agent and the chromogen, and many different materials of each category have been proposed.
  • US-A-3 996 405 describes a carbonless copying paper system in which the solvent is ethyldiphenyl- methane.
  • a solution of the invention comprises a liquid solvent comprising an aromatic hydrocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and, dissolved in the solvent, a chromogen and a compound (hereinafter referred to as a promoter) which is an alkylated, aralkylated or cycloalkylated phenol or which contains an alkylated, aralkylated or cycloalkylated hydroxyphenyl radical in its molecule, the structure of the phenol or radical being such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of at least four carbon atoms or by an aralkyl or cycloalkyl group, and the solvent having a low volatility consistent with its use as a chromogen solvent in a system of the invention.
  • a promoter which is an alkylated, aralkylated or cycloalkylated phenol or which contains an alkylated, aral
  • a pressure-sensitive mark-recording system of the invention comprises (a) sheet material, (b) promoted mark-forming components supported by the sheet material and arranged in juxtaposition but in unreactive condition, the said components comprising (i) a chromogen (ii) a sensitizing agent for the chromogen which produces a colour from the chromogen when brought into contact with the chromogen in the presence of a solvent and (iii) a promoter as defined above, and (c) the said solvent, which is a liquid comprising an aromatic hydrocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and in which solvent both the chromogen and the promoter are soluble, supported by the sheet material but separated from the sensitizing agent by a physical barrier which is rupturable on the application of a marking instrument to the sheet material.
  • chromogens, sensitizing agents and the aromatic hydrocarbons useful in the present invention are, in general, materials conventionally employed in the art, and are more fully described below.
  • the or each phenol nucleus may contain from one to three alkyl, aralkyl or cycloalkyl (including alkylcycloalkyl) groups, and preferably contains two or three such groups, each of such groups preferably having up to 12 carbon atoms, with the proviso indicated above regarding occupancy of at least one of the positions ortho to the hydroxy group.
  • An alkyl group occupying such a position is preferably an alkyl group of from 4 to 12 carbon atoms, especially a tertiary alkyl group, for example a t-butyl, t-amyl, 1,1,3,3-tetramethylbutyl or 1,1,3-trimethylhexyl group.
  • Alkyl substituents in other positions can have straight or branched chains, and usually contain from 1 to 12 carbon atoms, examples being methyl, ethyl, isopropyl, n-hexyl, 2-ethylhexyl, nonyl, decyl, and the tertiary alkyl groups named above.
  • An alkyl group in such other position is often preferably an alkyl group containing from one to three carbon atoms, e.g.
  • alkyl group concerned is a third alkyl group in a di-tertiary alkyl phenol, in a diaralkylated phenol or in a dicycloalkyl phenol, or where the alkyl group is present in an orthotertiary alkylated, aralkylated or cycloalkylated hydroxyphenyl nucleus that is linked to other atoms in the molecule of the promoter.
  • An aralkyl substituent in a promoter molecule is preferably a benzyl, alpha-methylbenzyl or alpha, alpha-dimethylbenzyl group. The last two are especially preferred where the substituent occupies a position ortho to a hydroxyl group.
  • a cycloalkyl group occupying such a position is preferably an alpha-alkyl cycloalkyl group, for example an alpha-methylcyclohexyl or alpha-ethylcyclohexyl group.
  • Preferred promoters are mononuclear phenols, substituted in the manner defined; compounds containing two hydroxyphenyl radicals, each substituted in the manner defined, and linked, preferably at the 2- or 4- positions, through a sulphur atom or through an alkylene or alkylidene group, usually a C 1-4 alkylene or alkylidene group; and compounds having the general formula where A represents a hydroxyphenyl radical substituted in the manner defined, preferably linked at the 2- or 4-position to the (CH 2 )p radical, p is an integer of from 1 to 4, m is an integer of from 1 to 4 and R represents a radical derived by the loss of m hydrogen atoms from an alkane of the formula C n H 2n+2 where n is an integer of from 1 to 24, preferably of from m to 24.
  • promoters that are alkylated, aralkylated or cycloalkylated mono-nuclear phenols are ortho (alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol, 2,6-di(alpha-methyl- benzylphenol) and 2,4,6-tri(alpha-methylbenzyl)phenol and mixtures of these mono, di and tri(alpha- methylbenzylated)phenols, 2(alpha-methylbenzyl)-4-methylphenol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amyl-hydroquinone, 4,6-di-nonyl-2-methylphenol, 2,4-dimethyl-6-(a-methylcydohexyl)phenol and 2,6-di(a-methylcyclohexyl)-4-methylphenol.
  • promoters containing two hydroxyphenyl radicals substituted and linked in the manner defined above are 4,4-th iobis(2-t-butyl-5-m ethyl phenol), 4,4'-butylidene-bis(2-t-butyl-5-methylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), and bis[2-hydroxy-3( ⁇ -methylcyclohexyl)-5-methylphenyl]methane.
  • Examples of compounds having the general formula are octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyme,thyllmethane.
  • Such promoters are commercially available materials.
  • the amount of the promoter used in a solution of the invention can be, for example, from 0.05 to 10% by weight of the solvent, but is preferably from 0.1 to 3%. The optimum will vary with the particular solvent and promoter used, but is often in the range 0.5 to 2% by weight of the solvent.
  • the presence of the promoter has been found to increase the solubility of the chromogen in the solvent. This effect could be used to increase the concentration of the chromogen in the solvent and thus obtain darker marks, but is mainly of interest in that it helps to avoid precipitation of the chromogen when the latter is used at conventional concentrations and the solution or system is stored at low temperatures.
  • aromatic hydrocarbons suitable for use in the present invention can be single compounds, but are often mixtures of individual compounds, the aromatic hydrocarbon being such that at least half the carbon atoms in the compound or mixture are benzenoid carbon atoms.
  • Aromatic hydrocarbons which can be used as, or as components of, the solvent in this invention include partially hydrogenated terphenyls, for example hexahydroterphenyls and dodecahydroterphenyls. As normally produced, materials of this type are mixtures containing in various proportions, fully hydrogenated terphenyls, partially hydrogenated terphenyls, and terphenyl itself. The terphenyl which is partially hydrogenated in obtaining such mixtures is itself a mixture of isomers.
  • hydrocarbons include benzylated and alphamethylbenzylated alkylbenzenes, e.g. mono- and dibenzyl ethylbenzene and mono(alpha-methylbenzyl)toluene, alkylnaphthalenes, e.g. dipropylnaphthalene and mono-alpha or -beta(2-hexyl) naphthalene, alkylbiphenyls, e.g. mono- and diisopropylbiphenyls.
  • the solvent can be an aromatic hydrocarbon (provided the hydrocarbon is a liquid at room temperature) or a mixture of aromatic hydrocarbons, or an aromatic hydrocarbon or mixture together with a diluent, a diluent being an inert liquid miscible with the aromatic hydrocarbon(s).
  • suitable diluents include mineral and vegetable oils, such as kerosene, paraffin oil, castor oil, soybean oil, corn oil and (long-chain alkylated)benzenes, for example (C 7 -C l , alkylated)benzenes.
  • the diluent in a solvent of the invention functions to alter physical properties of the solvent, for instance viscosity or vapour pressure, where such alteration may be desired for optimum handling or processing.
  • the solvent preferably contains at least 50% by weight of aromatic hydrocarbon but in some instances, the aromatic hydrocarbon may be diluted with up to, for example, 3 times its own weight of diluent.
  • the solvent is preferably one having a viscosity in the range 5 to 15 centistokes at 38°C.
  • the chromogen used in the present invention is usually an aromatic compound containing a double bond system which is converted to a more highly polarized conjugated and coloured form when reacted with an acidic sensitizing material.
  • a particularly preferred class of chromogens includes compounds of the phthalide type, for instance crystal violet lactone which is 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminonaphthalide, and malachite green lactone which is 3,3-bis(p-dimethylaminophenyl)phthalide.
  • phthalide-derived chromogens include 3,3-bis(p-dipropylaminophenyl)-phthalide, 3,3-bis(p-methylaminophenyl)phthalide, 3-(substituted-phenyl)-3-(indole-3-yl)-phthalides such as 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3,3-bis(methylindol-3-yl)-phthalides such as 3,3-bis(1,2-dimethylindol-3-yl)phthalide, 3-(phenyl)-3-(heterocyclic-substituted)-phthalides such as 3-(p-dimethylaminophenyl)-3-11-methyl-pyrr-2-yl)-6-dimethylaminophthalide, indole and carbazole-substituted phthalides such as 3,3-bis(1,2-dimethylindol-3-
  • chromogens which can be used in the present invention include 3-dialkylamino-6-alkyl-7-alkylaminofluorans, 3-dialkylamino-7-dialkylaminofluorans and 3-methyi-2,2'-spirobi(benzo[f]-chromehéJ.
  • An auxiliary colouring agent can be employed with the above chromogens.
  • crystal violet lactone CVL
  • BLMB benzoyl leuco methylene blue
  • the colouring agent complements the chromogen because on contact with the sensitizing agent the CVL produces an immediate dark blue colouration, but the colour tends to fade over a period of time.
  • the BLMB when in contact with the sensitizing agent produces a somewhat pale initial colour, but the colour gradually intensifies by oxidation of the dye.
  • the sensitizing agent used in a system of the present invention can be, for example, an acid clay, for instance an attapulgite or bentonite clay, or an acidic organic polymer, for example a phenol- aldehyde polymer or a partially or wholly hydrolysed styrene/maleic anhydride or ethylene/maleic anhydride polymer. Particularly good results are obtained in the present invention using an acid clay as the sensitizing agent.
  • a system of the present invention can be prepared according to well known conventional procedures which are adequately described in the literature.
  • a preferred embodiment of this invention comprises a two-sheet system wherein the sensitizing agent is carried by one sheet and a marking fluid comprising a solution of the invention is carried by a second sheet
  • the invention is not limited to such systems alone.
  • the only essential requirement is that the chromogen and the sensitizing agent be maintained in a separate or unreactive condition until pressure is applied to the system, and that upon the application of pressure the chromogen and the sensitizing agent are brought into reactive contact in the presence of the solvent and of the promoter.
  • the concentration of the chromogen in a solution of the invention is usually 0.75-2% by weight of the solution.
  • concentration of the chromogen in a solution of the invention is usually 0.75-2% by weight of the solution.
  • a chromogen and an auxiliary colouring agent are used, their proportions by weight may be, for example, from 40:60 to 80:20, and are preferably within the range 50:50 to 75:25.

Claims (12)

1. Solution à utiliser dans un système d'enregistrement sensible à la pression, ladite solution comprenant un chromogène dissous dans un solvant liquide comprenant un hydrocarbure aromatique dans lequel au moins la moitié des atomes de carbone sont des atomes de carbone du type benzénique, le solvant ayant une faible volatilité compatible avec une telle utilisation, caractérisée par le fait qu'un promoteur se trouve aussi dissous dans le solvant, lequel promoteur est un composé qui est un phénol alcoylé, aralcoylé ou cycloalcoylé ou qui contient un radical hydroxyphényle alcoylé, aralcoylé ou cycloalcoylé dans sa molécule, au moins une des positions en ortho par rapport au groupe hydroxyle du phénol ou du radical étant occupée par un groupe alcoyle d'au moins 4 atomes de carbone ou par un groupe aralcoyle ou cycloalcoyle.
2. Solution selon la revendication 1, caractérisée par le fait que le promoteur est un phénol mononucléaire alcoylé, aralcoylé ou cycloalcoylé; un composé contenant deux radicaux hydroxyphényle alcoylés, aralcoylés ou cycloalcoylés, liés en position 2 ou 4 par l'intermédiaire d'un atome de soufre ou d'un groupe alcoylène ou alcoylidène; ou un composé ayant la formule générale:
Figure imgb0008
où A représente un radical hydroxyphényle alcoylé, aralcoylé ou cycloalcoylé lié en position 2 ou 4 au radical (CHz)p, p est un nombre entier de 1 à 4, m est un nombre entier de 1 à 4 et R représente un radical résultant de la perte de m atomes d'hydrogène d'un alcane de formule C,,H2n+2 où n est un nombre entier de 1 à 24.
3. Solution selon une des revendications 1 et 2, où dans le promoteur, au moins une des positions en ortho par rapport au groupe hydroxyle du phénol ou du radical est occupée par un groupe alcoyle de 4 à 12 atomes de carbone, un groupe alpha-alcoyl-benzyle ou un groupe alpha-alcoyl-cyclohexyle.
4. Solution selon la revendication 3, où le promoteur est le phénol alpha-méthylbenzyle contenant un mélange d'ortho (alpha-méthylbenzyl)phénol et de 2,4-di(alpha-méthylbenzyl)phénol et/ou 2,6-di-(alpha-méthylbenzyl)phénol.
5. Solution selon la revendication 3, où le promoteur est le 4,6-dinonyl-2-méthylphénol.
6. Solution selon la revendication 3, où le phénol ou le radical alcoylé, aralcoylé ou cycloalcoylé contient deux ou trois groupes substituants alcoyle, aralcoyle ou cycloalcoyle, au moins une des positions en ortho par rapport au groupe hydroxyle du phénol ou du radical étant occupée par un groupe alcoyle tertiaire de 4 à 12 atomes de carbone ou par un groupe alpha-méthylcyclohexyle et au moins une autre position dans le noyau du phénol ou du radical est occupée par un groupe alcoyle de un à trois atomes de carbone.
7. Solution selon la revendication 6, où le promoteur est le 2,6-di-t-butyl-4-méthylphénol, le 2,4-diméthyl-6(alpha-méthylcyclohexyl)phénol, le 2,6-di(alpha-méthylcyclohexyl)-4-méthylphénol, le 4,4'-thiobis(2-t-butyl-5-méthylphénol), le 4,41-butylidène-bis(2-t-butyl-5-méthylphénol), le 2,2'-méthylène bis(4-méthyl-6-t-butylphénol), le 2,2'-méthylènebis(4-éthyl-6-t-butylphénol) ou le bis[2-hydroxy-3-(alpha-méthylcyclohexyl)-5-méthylphényl]méthane.
8. Solution selon la revendication 3, où le promoteur est un composé ayant la formule générale:
Figure imgb0009
où A représente un radical hydroxyphényle alcoylé, aralcoylé ou cycloalcoylé lié en position 4 au radical (CH:,)p et ayant un groupe alcoyle tertiaire de 4 à 12 atomes de carbone dans au moins une des positions 3 et 5, et R représente un radical résultant de la perte de m atomes d'hydrogène, d'un alcane de formule: CnH2n+2 où n est un nombre entier de m à 24.
9. Solution selon la revendication 8, où le promoteur est l'octadécyl 3-(3,5-di-t-butyl-4-hydroxy- phényl)propionate ou le tétrakis[3-(3,5-di-t-butyl-4-hydroxyphényl)propionyloxyméthyl]méthane.
10. Solution selon une des revendications 1 a 9, où la quantité de promoteur est comprise entre 0, 1 et 3% en poids de solvant.
11. Solution selon une des revendications 1 à 10, où le chromogène est le lactone cristal violet (LCV) et que la solution contient aussi le bleu de benzoylleucométhylène (BBLM) comme agent de coloration auxiliare, les proportions de LCV et de BBLM étant comprises de 40:60 à 75:25 en poids.
12. Système d'enregistrement sensible à la pression comprenant (a) une feuille, (b) des constituants formant des marques, supportés par la feuille et arrangés en juxtaposition, mais en état non réactivé, lesdits constituants comprenant (i) un chromogène, (ii) un agent sensibilisant le chromogène qui produit une couleur à partir du chromogène quand il est mis en contact avec le chromogène en présence du solvant, et (c) ledit solvant étant un solvant ayant une faible volatilité compatible avec son utilisation dans le système et comprenant un hydrocarbure aromatique dans lequel au moins la moitié des atomes de carbone sont des atomes de carbone de type benzénique, supporté par la feuille mais séparé de l'agent sensibilisant par une barrière physique qui peut être rompue par application d'un instrument de marquage sur la feuille, caractérisé par le fait que la feuille supporte aussi un promoteur qui est soluble dans le solvant et qui est un phénol alcoylé, aralcoylé ou cycloalcoylé ou un composé qui contient dans sa molécule, un radical hydroxyphényle alcoylé, aralcoylé ou cycloalcoylé, au moins une des positions en ortho par rapport au groupe hydroxyle du phénol ou du radical étant occupée par un groupe alcoyle d'au moins quatre atomes de carbone ou par un groupe aral,coyle ou cycloalcoyle.
EP19790302817 1978-12-13 1979-12-07 Systèmes d'enregistrement sensibles à la pression et solutions à utiliser dans ces systèmes Expired EP0012579B1 (fr)

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Publication number Priority date Publication date Assignee Title
US4275905A (en) * 1978-12-29 1981-06-30 Appleton Papers Inc. Pressure-sensitive record material
US4372582A (en) * 1981-03-30 1983-02-08 Minnesota Mining And Manufacturing Company Stabilizer for electron doner-acceptor carbonless copying systems
US4489336A (en) * 1981-06-05 1984-12-18 Kanzaki Paper Manufacturing Co., Ltd. Pressure sensitive manifold paper
FR2637291B1 (fr) * 1988-09-30 1993-04-23 Atochem Nouvelle composition, son application comme isolant electrique et son procede de fabrication

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GB873702A (en) * 1958-08-26 1961-07-26 Caribonum Ltd Improvements in or relating to manifolding
US3996405A (en) * 1973-01-24 1976-12-07 Ncr Corporation Pressure-sensitive record material
US4093278A (en) * 1976-12-27 1978-06-06 Monsanto Company Dye solvents for pressure-sensitive copying systems

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CA1139560A (fr) 1983-01-18
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EP0012579A3 (en) 1980-10-15

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