Classifications

• • 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
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
  • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
  • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
  • Y10T428/277—Cellulosic substrate

Definitions

• the present invention relates to a sheet-like or web-shaped recording material with improved shelf life. It relates in particular to that part of such recording materials which contains the dye precursor by creating a novel binder which can be used with a large number of known dye precursors.
• a unit of the pressure-sensitive recording material is formed on the support material and forms a pressure-sensitive recording material according to the invention when combined with a large number of known units containing dye acceptor material.
• Pressure-sensitive recording papers are referred to as chemical recording papers or carbonless papers. They generally consist of a unit carrying a dye precursor or color former or its solution (in sheet or web form, incorporating the dye precursor into the carrier material or layered on the carrier material) and a unit carrying the dye acceptor or color developer in the same way, for Color formation is capable of reacting with the dye precursor if the dye precursor or its solution comes into contact with the dye acceptor through the action of an external physical force, such as, in particular, pressure. In this way, a mark or drawing is generated in accordance with the external force acting on it.
• the unit obtained is referred to as a CF sheet ("Coated Front Sheet") or CF sheet or the method of application as a CF application.
• the names CB-Sheet (“Coated-Back-Sheet") or CB-Bahn or CB-order result.
• a web or sheet-like carrier material that has the one active ingredient (e.g. dye precursors or color formers) on one side can be coated on the other surface with the other active ingredient (dye acceptor material), which is then combined on both sides with correspondingly coated web or sheet-like carrier materials results in three-sheet recording material with which two copies can be made simultaneously. Multi-page sets for simultaneous production of an even larger number of copies can also be put together in this way.
• Both dye precursors and dye acceptor material can be layered onto the web or sheet-shaped carrier material in both the CB and the CF application.
• the dye precursor or color former is generally applied to the web-like or sheet-like carrier material in the form of microcapsules containing a solution of a solvent-resistant plastic and a suitable binder for this purpose.
• the capsules are applied in the form of capsule dispersions and the carrier material is dried after the application.
• such a procedure requires a large number of process steps and complicated manufacturing devices.
• a considerable amount of energy is required for drying after the capsule dispersions have been applied.
• the capsule papers have the considerable disadvantage that the solvents necessary for dissolving the dye precursors are generally harmful high-boiling solvents which are released when the unit of the pressure-sensitive recording material carrying the color former is printed.
• the binder must not change the properties of the paper in such a way that it loses its durability and tensile strength, such recording materials are generally used for machine labeling in high-speed machines.
• the coating of the paper obtained must also have so little surface adhesion that it does not adhere to the rollers used here in the machines. Due to this large number of required properties, the application of the dye precursors to the web or sheet-shaped carrier material has not been a substitute for the expensive and less environmentally friendly ones Capsule papers appeared on the market.
• the pressure-sensitive recording material consists not only of these two units but of one or more intermediate units which are coated on one side with the dye precursor and on the other side with the dye acceptor material.
• the pressure-sensitive recording materials according to the invention not only have the improved shelf life and light fastness and can not only be considerably more energy-efficient and use simpler machines.
• the colored areas produced by applying pressure to the recording material remain sharp even over extended periods of time, ie the characters formed do not run, as is generally the case with the recording materials known from the literature, in which the dye precursor is applied to the carrier material with a wax-like binder.
• the colors formed also have the long-term stability required for documents, so that copies obtained in this way keep the characters thus produced perfectly legible even over the multi-year period necessary for numerous types of documents.
• the binders for the dye precursors used according to the invention can be used with particularly good results for coating the CB side of the carrier materials. They can be coated in amounts of 1 to 10 g / m 2 on the carrier material of the unit containing the dye precursor.
• the binder / dye precursor mixture is preferred an amount of 2 to 4 ' g / m 2 piled up.
• the binder / dye precursor mixture used in accordance with the invention can also be applied to the CF side of the carrier material of the unit of the pressure precursor containing the dye precursor, recording materials. In this case, however, amounts which are somewhat smaller than in the case of application are generally piled up on the CB side, and amounts of 1 to 2 g / m 2 for the binders used according to the invention.
• pressure-sensitive recording materials are to be produced which are used under tropical climatic conditions, it is advantageous to improve the properties of the unit of the pressure-sensitive recording materials containing the dye precursor in that the layer containing the dye precursor with a vinylpyrrolidone-vinyl acetate copolymer in an amount of at most 0 , 5 g / m 2 and / or with a polyvinylpyrrolidone in an amount of at most 0.2 g / m 2 by spraying the two products from suitable solvents and drying the coated units obtained.
• the vinylpyrrolidone-vinyl acetate copolymer which is preferably made from 20% vinylpyrrolidone and 80% vinyl acetate, can be sprayed from a 50% ethanolic solution and the polyvinylpyrrolidone can be sprayed from a 40% aqueous solution.
• dye precursors or color formers Numerous chromogenic products known for use in pressure-sensitive recording materials can be used as dye precursors or color formers.
• dye precursors of the phthalide and Pluoran type e.g. Crystal violet lactone, also indole-substituted promellitides, leucoauramines, benzospiropyrans (see e.g. DE-PS 1 421 393), benzofuran derivatives (see e.g. DE-PS 1 421 394) or pyridinecarbons aurelactones (see e.g. DE-PS 2 412 640).
• dye precursors of the phthalide and fluoran type or mixtures of both types which is why the use of such dye precursors in the recording materials according to the invention is particularly preferred.
• the dye precursors can optionally be used in a mixture with benzoyl leucomethylene blue.
• fillers for products of this type can be used as fillers, for example CaC0 3 , BaS0 4 or Ti0 2 , CaC0 3 being preferred.
• the unit containing the dye precursor for such pressure-sensitive recording materials are sheet-like or web-shaped units in which the carrier material is coated on one of its surfaces with the binder / dye precursor mixture described.
• Such units can be combined with the dye acceptor material-containing unit to create the complete writing set of the pressure-sensitive recording material, wherein the unit containing the dye precursor can be combined with practically all currently known dye acceptor-containing units for the formation of writing sets with the described advantageous properties.
• Particularly favorable results are achieved with the units containing dye acceptor material, as are described in German patent applications P 30 09 754.2-45 and P 30 09 806.7-45 of March 14, 1980.
• the carrier material of this unit is on one of its surfaces with the dye precursor / binder mixture described and on the other hand with a customary dye acceptor material in the usual way, e.g. coated as described in the two German patent applications mentioned. It is a particular advantage of the dye precursor / binder combination used according to the invention that it does not penetrate into and through the carrier material, which is generally made of paper, and thus causes a premature reaction with the dye acceptor material, even if the writing sets produced according to the invention are in larger stacks, i.e. stored on each other with considerable pressure.
• the pressure-sensitive recording materials according to the invention or the units of pressure-sensitive recording materials containing dye precursors according to the invention can be produced in a particularly simple manner by melting a part of the wax components or all wax components of the mixture, ie the various esters of higher aliphatic carboxylic acids and / or higher aliphatic alcohols or alkane diols are melted with heating, the remaining components of the mixture are added and the mixture is ground until a sufficient fineness of the parts of the mixture is achieved, the mixture obtained is then melted on one side of the carrier material of the unit containing the dye precursors in an amount of 1 to 10 g / m 2 are coated, if desired, the above-described solution of the vinylpyrrolidone-vinyl acetate copolymer and / or polyvinylpyrrolidone is sprayed on and dried, and the unit thus obtained, containing dye precursors, is cooled t.
• this unit is not a commercial product itself, it can be processed as usual. So can Production of units containing dye precursors for writing sets with multiple copies can be piled up on the reverse side of dye acceptor material in the usual manner, or the unit containing dye precursors with the unit containing dye acceptor material can be arranged by arranging the surface containing dye precursors of one unit adjacent to the unit containing dye acceptor material from the other surface pressure-sensitive recording material according to the invention can be combined.
• these process steps are well known to the person skilled in the art and are described in detail in the relevant technical literature. Reference is made to such specialist literature.
• Product I cerotic acid myricylic ester (n-hexacosanic acid 1-triacontanol or hentriacontanol ester with a free tetracosanoic acid content of less than 1%)
• Product II ester mixture with a predominant proportion of nonacosanoic acid esters of higher aliphatic alcohols with a melting point of 86 ° C, a solidification point of 78 ° C according to DGF-M-III-4a, a penetration number of 1 according to DIN 51579, an acid number of 32 according DGF-M-IV-2 and a saponification number of 92 according to DGF-M-IV-2
• Product III ester mixture with a predominant proportion of ethylene and 1,4-butylene glycol esters of straight-chain dotriacontanoic acid with up to 10% by weight of the corresponding esters of straight- or branched-chain carboxylic acids with a total number of carbon atoms in the carboxylic acid in the range of C 28 - C34 where the ester mixture has a dropping point of 81 to 86 ° C according to DGF-M-III-3, an acid number of 20 to 30 according to DGF-M-IV-2, a saponification number of 130 to 150 according to DGF-M-IV-2 and has a penetration number of 1 according to DIN 51579,
• Product IV polyethylene wax with a dropping point of 103 to 107 ° C according to DGF-M-III-3, a freezing point of 90 to 94 ° C according to DGF-M-III-4a, an acid number of
• Product V low-pressure polyethylene with a dropping point of 118 to 128 ° C according to DGF-M-III-3, a freezing point of 104 to 108 ° C according to DGF-M-III-4a, an acid number of 0 according to DGF-M-IV- 2, a saponification number of 0 according to DGF-M-IV-2 and a penetration number of 2 to 4 according to DIN 51579
• Product VI mixture of phenol and cresol pentadecane sulfonates, the mixture having a density d20 / 4 of 1.030 to 1.070 g / cm 3 according to DIN 51757, a refractive index nD of 14,970 to 15,000 according to DIN 53491, a pour point ⁇ -15 ° C according to DIN 51583 and a volatility 0-72h / 90 ° C ⁇ 2.0% according to Brabander
• Product VII phthalic acid polyester of higher alkane diols with a density d20 / 4 of 1.035 to 1.045 g / cm 3 according to DIN 51757, a refractive index nD of 1.502 to 1.504 according to DIN 53491, a pour point ⁇ -35 ° C according to DIN 51583 and a volatility of 0 -72h / 90 ° C ⁇ 1.1% according to Brabander
• Product VIII phthalic acid polyester of essentially ethylene glycol in addition to higher alkane diols with a density d20 / 4 of 1.090 to 1.100 g / m 3 according to DIN 51757, a refractive index nD of 1.503 to 1.505 according to DIN 53491, a pour point ⁇ -20 ° C according to DIN 51583 and a volatility 0-72h / 90 ° C ⁇ 2.0% according to Brabander
• the melted waxes are placed in a pearl mill, which is heated to approx. 110 ° C. Then all other components of the mixture are added and the entire mixture is ground until a fineness of approx. 6 ⁇ m is reached.
• the finished mixture is coated from the melt by means of a spreading, spot or printing process on the underside (CB side) of a sheet or web-shaped paper carrier material of 17 to 80 g / m 2 over the entire surface or in part in an amount of 4 g / m 2 Surface applied.
• the product mixture according to Example 12 was also used for an application on the front side (CF side) of a paper sheet, the coating being carried out in an amount of 2 g / m 2 of coated area.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Color Printing (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Conductive Materials (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

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ID=6126048

Family Applications (1)

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• 1981
  • 1981-02-28 DE DE3107707A patent/DE3107707C2/de not_active Expired
• 1982
  • 1982-02-03 EP EP82710005A patent/EP0059679B1/de not_active Expired
  • 1982-02-03 AT AT82710005T patent/ATE17456T1/de not_active IP Right Cessation
  • 1982-02-08 US US06/346,746 patent/US4417752A/en not_active Expired - Fee Related
  • 1982-02-09 IE IE284/82A patent/IE52668B1/en unknown
  • 1982-02-09 CA CA000395850A patent/CA1171277A/en not_active Expired
  • 1982-02-11 GR GR67296A patent/GR75528B/el unknown
  • 1982-02-15 AU AU80490/82A patent/AU547476B2/en not_active Ceased
  • 1982-02-26 DK DK84182A patent/DK148839C/da not_active IP Right Cessation
  • 1982-02-26 JP JP57029138A patent/JPS57159686A/ja active Pending

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