EP0085346A2 - Procédé pour la préparation de papier copiant partiellement enduit - Google Patents

Procédé pour la préparation de papier copiant partiellement enduit Download PDF

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Publication number
EP0085346A2
EP0085346A2 EP83100383A EP83100383A EP0085346A2 EP 0085346 A2 EP0085346 A2 EP 0085346A2 EP 83100383 A EP83100383 A EP 83100383A EP 83100383 A EP83100383 A EP 83100383A EP 0085346 A2 EP0085346 A2 EP 0085346A2
Authority
EP
European Patent Office
Prior art keywords
paper
microcapsules
coating
heat treatment
paper carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP83100383A
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German (de)
English (en)
Other versions
EP0085346B1 (fr
EP0085346A3 (en
Inventor
Gert Dr. Jabs
Ulrich Dr. Nehen
Walter Dipl.-Phys. Simm
Jörg Michael Dr. Söder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT83100383T priority Critical patent/ATE18521T1/de
Publication of EP0085346A2 publication Critical patent/EP0085346A2/fr
Publication of EP0085346A3 publication Critical patent/EP0085346A3/de
Application granted granted Critical
Publication of EP0085346B1 publication Critical patent/EP0085346B1/fr
Expired legal-status Critical Current

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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
    • B41M5/1246—Application of the layer, e.g. by printing

Definitions

  • the invention relates to a partially coated carbonless paper and a method for its production, in which microcapsules provided with a meltable coating are deposited electrostatically on a paper carrier and then fixed.
  • Reaction carbon papers preferably consist of two or more sheets of paper laid loosely on top of one another, the upper one on the back containing a donor layer and the lower one on the front containing a receiver layer.
  • a donor layer and a receiver layer are in contact with each other.
  • the donor layer contains microcapsules, the core of which is a solution of a color former in an organic solvent, and the receiver layer contains a material that develops the dye former into a dye.
  • the receiving layer usually contains binders and pigments, for example active absorbents such as kaolin, attapulgite, montmorillonite, bentonite, acidic bleaching earth or Phenolic resins.
  • active absorbents such as kaolin, attapulgite, montmorillonite, bentonite, acidic bleaching earth or Phenolic resins.
  • acid-activatable dyes can be used on the donor layer and acid-reacting components in the receiver layer.
  • reaction copy papers A further development of these reaction copy papers are the "one-component" reaction copy papers.
  • one side of a single sheet of paper carries the dye precursor, generally in the form of microcapsules, and at the same time the color developer. If pressure is now applied, e.g. by means of a typewriter or other writing tool, the capsule containing the dye precursor is torn open and the dye precursor reacts with the color developer surrounding it (see US Pat. No. 2,730,456).
  • the coating of the paper substrate for the production of the carbon-free copying systems is generally carried out over the entire area with an aqueous coating composition, such as e.g. in DE-OS 1 934 457 and 1 955 542.
  • the wax-like coating changes the character of the paper, since relatively large amounts of the waxes have to be applied in order to obtain satisfactory copies with a microcapsule content of at most 40% by weight.
  • This invention is based on the finding that dry microcapsules provided with fusible coatings can be deposited electrostatically in any form onto a paper carrier and fixed there by heat treatment, so that a partially coated carbonless carbonless paper is obtained.
  • the invention therefore relates to a partially coated, carbon-free carbonless paper which is produced by electrostatic deposition of microcapsules provided with a meltable coating on a paper carrier and subsequent heat treatment, and a method for the production thereof.
  • the microcapsules are provided with a coating which melts through brief heat treatment and thus fixes the microcapsule on the paper carrier.
  • Heat treatment is understood to mean the action of heat which, on the one hand, must not be so high that the microcapsule is damaged, and, on the other hand, should not be so deep that there is no melting.
  • a suitable temperature is e.g. from 50 to 150, preferably from 60 to 120 ° C.
  • the thermal energy deployed at these temperatures corresponds to that which is used in conventional dry copiers when baking the toner powder.
  • the duration of exposure also depends on this thermal energy in such a way that the higher the energy, the shorter the treatment time. It can be quickly determined by a person skilled in the art by simple experiments and depends on the meltability of the coating, its binding capacity and the setting time of the coating. A treatment of approx. 5-30 seconds may be mentioned as an example.
  • thermoelectric radiators Conventional heating elements, IR radiators or microwave devices can be used as heat sources.
  • Suitable materials for encapsulating the capsules are, for example, wax compositions, thermoplastics or hot-melt adhesives, all with softening temperatures of 60-120 ° C., preferably from 70 to 90 ° C.
  • Paraffin waxes Paraffin waxes, ester waxes, polyethylene waxes, stearates and carnauba waxes may be mentioned as examples of wax compositions.
  • thermoplastics are, for example, polymers and copolymers of ethylene, vinylidene, vinyl acetate, in particular partially saponified ethylene-vinyl acetate copolymers.
  • Polyamides for example, can be used as hot-melt adhesives.
  • Preferred wrapping materials are: carnauba waxes and partially saponified ethylene-vinyl acetate copolymers.
  • microcapsules can advantageously be coated with the materials mentioned in such a way that they are stirred into the aqueous capsule dispersions in the form of an aqueous, finely divided dispersion or emulsion and this mixture is then converted, for example by spray drying, into agglomerate-free powders.
  • the spray drying of microcapsules belongs to the known state of the art. Other known drying techniques can also be used to manufacture the capsule powder.
  • the coating compositions can also be dissolved in a suitable solvent, the dry capsules stirred in and the solvent then removed.
  • the amount of wrapping material is about 5-50% by weight, preferably 10-30% by weight, based on the microcapsule.
  • microcapsules coated in this way are then applied to the paper support in any form using electrostatic processes and subjected to a heat treatment.
  • Usual wood-containing or wood-free paper qualities with basis weights of 40-200 g per m 2 can be used as paper supports.
  • paper supports which are usually not suitable for the production of carbon-free carbonless papers can also be used in the process according to the invention.
  • the electrical field between two electrodes generates an ion current, which in turn electrically charges the coated microcapsules introduced into the electrical field.
  • the microcapsules charged in this way beat on the paper carrier if it lies on one of the electrodes.
  • FIGS. 1 to 5 Examples for carrying out the precipitation process for dry capsule material are shown in FIGS. 1 to 5.
  • Both the field and the ion current are generated by a voltage between the electrodes 1 and 2, which is maintained by a DC voltage source 7.
  • the capsules are pressed by the force K onto the surface of the paper 5 which covers the counterelectrode. At the same time, an electrical current constantly flows through the paper layer onto the electrode 2.
  • a prerequisite for the functioning of the method according to the invention is sufficient permeability of the paper for the electric current.
  • this condition is met when the resistivity of the paper is less than 10 14 ohms. m is forthcoming to 4 gt 10 -10 14 Ohm. m, particularly preferably 10 to 10 13 Oh m. m. Under the conditions described, a uniformly dense layer of the capsule material is deposited on the paper sheet.
  • the precipitation electrode 2 explains the possibility of specifically depositing the capsules on certain surface parts of the paper carrier. If one conducts the precipitation electrode in such a way that it consists of insulating parts 8 and conductive parts 9 on the surface, the ion current emanating from the corona is distributed in the spray field 6 in such a way that the charge carriers and thus the capsules are located only over the conductive electrode parts separate in a concentrated manner.
  • the paper 5 is not less than a specific resistivity. If the resistance of the paper is too low, capsules are also deposited in the intermediate areas. In the favorable resistance range, the precipitation layer forms in such a way that the structure of the conductor parts is reproduced in a sharply defined manner. This resistance range is explained in more detail above.
  • Fig. 3 shows a more practical variant of the method, according to which the capsule material is deposited on a continuously moving, ribbon-shaped paper carrier.
  • the material is fed through a funnel-like container 10, which is advantageously shaken to support the material outlet.
  • a vibrating screen can also be used at this point.
  • a band-shaped paper web 11 is continuously drawn over the rotatably mounted drum 12, as indicated in the drawing by arrows.
  • the drum 12 is spanned with a support which consists of an insulating layer 13 and a conductor layer 14 which, however, is not continuous, but is in the pattern provided for the capsule separation.
  • a support which consists of an insulating layer 13 and a conductor layer 14 which, however, is not continuous, but is in the pattern provided for the capsule separation.
  • the conductive parts of the support are electrically connected to one another and to the carrier roller.
  • the tip electrode 1 is replaced here by the wire electrode 15, which is stretched parallel to the surface line of the drum.
  • the spray wire receives charge of a few kV, for example 10 kV, from the voltage source 7.
  • the polarity is insignificant, but in this case the positive potential is preferable, since it achieves a more uniformly distributed discharge zone over the wire length.
  • the tape passes through a baking station 17, in which the substance is heated and melted by heat rays.
  • a photoconductor layer on the outer surface of the drum can also be used for the precipitation control instead of the metal coating.
  • the photoconductor layer is an insulator in the dark and a conductor when exposed to light. Limited deposition zones are produced by zonal radiation with an exposure device 20 through the paper.
  • This design has the advantage that the coating distribution can be changed very easily and quickly.
  • Suitable photoconductors are e.g. Zinc oxide, cadmium sulfide and selenium.
  • FIG. 5 shows a variant in which the exposure of the photoconductor 21 takes place from the inside of the drum.
  • the photoconductor is applied to a conductive, transparent, grounded base 22.
  • the can consist of a vapor-deposited film is applied by a transparent hollow cylinder 23 which is illuminated from the inside by means of a lamp 24.
  • the partially transparent template 25 allows partial exposure of the photoconductor, which acts as a conductor in the exposed zones and as an insulator in the unexposed zones.
  • microcapsules to be used to carry out the process according to the invention and processes for their production are known.
  • the long-known microcapsules can be used, which can be produced by coacervation or complex coacervation from gelatin and gum arabic, as well as gelatin and other inorganic and organic polyanions.
  • Various such methods include in M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation 1972.
  • microcapsules are used in the method according to the invention, the walls of which consist of polymers, polycondensation and polyaddition products.
  • Microcapsules with walls made of special polyacrylates such as e.g. described in DE-OS 2 237 545 and DE-OS 2 119 933.
  • phenol or urea-formaldehyde condensates can be used as wall material, optionally also in combination with the capsule wall polymers mentioned above.
  • Microcapsules are preferably used in the process according to the invention, the shells of which consist of polyadducts of polyisocyanates and polyamines.
  • Isocyanates to be used for the production of such microcapsules are diisocyanates such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, Ethylidene diisocyanate, cyclohexyl-1,2-diisocyanate, cyclohexyl-1,4-diisocyanate, polyisocyanate prepolymers, e.g.
  • modified aliphatic isocyanates are those based on hexamethylene-1,6-diisocyanate, m-xylylene diisocyanate, 4,4'-diisocyanatodicyclohexylmethane or isophorone diisocyanate, which have at least two functional isocyanate groups per molecule.
  • Suitable compounds are polyisocyanates based on derivatives of hexamethylene-1,6-diisocyanate with a biuret structure, the preparation of which is evident from DE-AS 1 101 394 and 1 543 178, and from DE-OS 1 568 017 and 1 931 055.
  • the polyisocyanates that can be used can additionally be modified before use for microencapsulation by reaction with di- and trifunctional alcohols such as ethanediols, glycerol or trimethylolpropane or carboxylic acids such as succinic acid, adipic acid, sebacic acid in proportions of 0.01 to 0.5 mol per isocyanate equivalent .
  • di- and trifunctional alcohols such as ethanediols, glycerol or trimethylolpropane
  • carboxylic acids such as succinic acid, adipic acid, sebacic acid in proportions of 0.01 to 0.5 mol per isocyanate equivalent .
  • carbodiimide, uretdione, uretonimine, uretidinedione diimine, 4-imino-oxazolidinone (2), ⁇ -alkylene propiolactone or cyclobutanedione (1,3) groups can also be present as reactive groups.
  • polyisocyanato-polyuretonimines such as those formed by carbodiimidization of hexamethylene-1,6-diisocyanate containing biuret groups with organic phosphorus catalysts, can be used by further reaction of primarily formed carbodiimide groups with isocyanate groups to form uretonimine groups.
  • isocyanates can be used in a mixture with one another and other aliphatic and aromatic isocyanates.
  • the resulting modified polyisocyanate can contain considerable proportions of oxadiazinetrione, triisocyanurate or sym. Triazinedioneimine as a structural element. Such products are also suitable as shell formers.
  • color former examples include triphenylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, spiropyran compounds or the like.
  • Examples of a diphenylmethane compound are 4,4'-bis-dimethylaminobenzhydrylbenzylether, N-halophenylleucolamine, N- ⁇ -naphthyleucolamine, N-2,4,5-trichlorophenylleucolamine, N-2,4-dichlorophenylleucolamine or the like.
  • Examples of a xanthene compound are rhodamine- ⁇ -anilinolactam, rhodamine- ⁇ - (p-nitroaniline) lactam, rhodamine- ⁇ - (p-chloroaniline) lactam, 7-dimethylamine-2-methoxifluorane, 7-diethylamine-3-methoxifluorane , 7-diethylamine-3-methyl-fluoran, 7-diethylamine-3-chlorofluorane, 7-diethylamine-3-chloro-2-methylfluorane, 7-diethylamine-2,4-dimethylfluorane, 7-diethylamine-2,3-dimethylfluorane , 7-diethylamine- (3-acetyl-methylamine) -fluorane, 7-diethylamine-3- (dibenzylamine) -fluoroane, 7-diethylamine-3- (methyl
  • Examples of a thiazine compound are N-benzoylleucomethylene blue, o-chlorobenzoylleucomethylene blue, p-nitrol-benzoylleucomethylene blue or the like.
  • spiro compound examples include 3-methyl-2,2'-spirobis (benzo (f) chromium) or the like.
  • Solvents that dissolve these color formers are e.g. chlorinated diphenyl, chlorinated paraffin, cottonseed oil, peanut oil, silicone oil, phthalate esters, phosphate esters, sulfonate esters, monochlorobenzene, furthermore partially hydrogenated terphenyls, alkylated naphthalenes, alkylated diphenyls, aryl ethers, aryl alkyl ethers, higher alkylated benzene and others which can be used alone or in combination.
  • Diluents are often added to the solvents, e.g. Kerosene, n-paraffins, isoparaffins.
  • the colorants and the isocyanate are first dissolved in the solvents mentioned and this organic phase is emulsified in the continuous aqueous phase, which may contain protective colloid and, if appropriate, emulsifiers.
  • An aqueous polyamine solution is added to the emulsion in a stoichiometric amount to the polyisocyanate in the organic phase.
  • Protective colloids and emulsifying aids are added to the aqueous phase to emulsify and stabilize the emulsion formed.
  • Examples of such products acting as protective colloids are carboxymethyl cellulose, gelatin and polyvinyl alcohol.
  • emulsifiers are ethoxylated 3-benzylhydroxibiphenyl, reaction products of nonylphenol with different amounts of ethylene oxide and sorbitan fatty acid ester.
  • the microcapsules can be produced continuously or batchwise. Dispersing devices which generate a shear gradient are generally used. Examples include blade, basket, high-speed stirrers, colloid mills, homogenizers, ultrasonic dispersers, nozzles, steel nozzles, and Supraton machines.
  • the strength of the turbulence during mixing is primarily decisive for the diameter of the microcapsules obtained. Capsules from 1 to 2000 ⁇ m in size can be produced. Capsules with diameters of 2 to 20 gm are preferred.
  • the capsules do not agglomerate and have a narrow particle size distribution.
  • the weight ratio of core material to shell material is 50 to 90 to 50 to 10.
  • microcapsules were produced according to the example of DE-OS 2 738 509.
  • a 35% aqueous microcapsule dispersion was then produced, the capsule walls of which consisted of a polyaddition product of the oxadiazinetrione of hexamethylene diisocyanate and a diamine.
  • the mean capsule diameter was 6.5 ⁇ m.
  • This mixture was then spray dried (180 ° C. air temperature inlet, 80 ° C. air temperature outlet). An agglomerate-free powder was obtained. The average particle size was 7.0 ⁇ m in diameter. The powder mixture obtained was applied to a paper support.
  • microcapsule dispersion a was spray-dried as under b. 100 parts by weight of the capsule powder obtained were intimately mixed with 20 parts by weight of a finely powdered, partially saponified ethylene-vinyl acetate copolymer (Levasint, Bayer AG).
  • the powder mixture obtained was used for deposition on a paper support.
  • microcapsule dispersion a was spray-dried as under b. 40 parts by weight of carnauba wax were then dissolved in 250 parts of trichloroethane while heating to 40 ° C., and 160 parts by weight of the dry capsules were mixed into this solution. The trichloroethane was then stripped off in vacuo.
  • a free-flowing capsule powder coated with carnauba wax was obtained.
  • the powder mixture obtained was used for deposition on a paper support.
  • a capsule material is used which is covered with carnauba wax (example d).
  • the average size of the capsules is 8 ⁇ m.
  • This material is whirled up in an air stream and in an arrangement according to FIG. 2 in the discharge blown space between a tip electrode and a plate-shaped counter electrode.
  • the surface of the counter electrode is divided into insulating fields 8 and conductive fields 9, the conductive fields being connected to one another and to a voltage source 7.
  • This electrode is covered with a sheet of paper to hold the capsule layer.
  • the paper has a resistivity of 10 8 Ohm.m.
  • the distance between the tip and the plate is 10 cm.
  • the top is positive.
  • a thin, uniform capsule layer forms on the areas of the paper that lie above the conductive parts of the counterelectrode in a fraction of a second.
  • the paper coated in this way is removed from the base and placed in a heating device, where it is heated to 150 ° C. for 10 seconds.
  • the wax shell of the capsules melts onto the paper surface and thus fixes the capsule layer.
  • a functional carbonless reaction paper is obtained.
  • Capsule materials according to Examples a-c) were used in the same way. Functional carbonless copy papers were also obtained.

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  • Color Printing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Paper (AREA)
  • Cultivation Of Plants (AREA)
  • Confectionery (AREA)
  • Game Rules And Presentations Of Slot Machines (AREA)
EP83100383A 1982-01-30 1983-01-18 Procédé pour la préparation de papier copiant partiellement enduit Expired EP0085346B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100383T ATE18521T1 (de) 1982-01-30 1983-01-18 Verfahren zur herstellung von partiell beschichtetem durchschreibepapier.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3203059 1982-01-30
DE19823203059 DE3203059A1 (de) 1982-01-30 1982-01-30 Partiell beschichtetes durchschreibepapier

Publications (3)

Publication Number Publication Date
EP0085346A2 true EP0085346A2 (fr) 1983-08-10
EP0085346A3 EP0085346A3 (en) 1984-01-11
EP0085346B1 EP0085346B1 (fr) 1986-03-12

Family

ID=6154330

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100383A Expired EP0085346B1 (fr) 1982-01-30 1983-01-18 Procédé pour la préparation de papier copiant partiellement enduit

Country Status (5)

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EP (1) EP0085346B1 (fr)
JP (1) JPS58136484A (fr)
AT (1) ATE18521T1 (fr)
DE (2) DE3203059A1 (fr)
FI (1) FI77605C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545574A1 (fr) * 1991-12-05 1993-06-09 Moore Business Forms, Inc. Ensembles de formulaires avec des feuilles CF, CB ou s'imprimant sans carbone et rubans de blockage, quelles annullent la fonction de s'imprimer sans carbone

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6092889A (ja) * 1983-10-27 1985-05-24 Kureha Chem Ind Co Ltd 部分感圧複写紙及びその製造方法
JPS60149489A (ja) * 1984-01-17 1985-08-06 Kureha Chem Ind Co Ltd 部分感圧紙

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO126385B (fr) * 1968-06-18 1973-01-29 Ransburg Electro Coating Corp
US3694243A (en) * 1969-12-22 1972-09-26 Ncr Co Coating of particles and process for manufacturing said coating
US4171981A (en) * 1977-04-29 1979-10-23 The Mead Corporation Process for the production of hot melt coating compositions containing microcapsules
US4162165A (en) * 1977-06-16 1979-07-24 The Mead Corporation Process for the production of microcapsular coating compositions containing pigment particles and compositions produced thereby
US4201404A (en) * 1978-05-17 1980-05-06 Minnesota Mining And Manufacturing Company Pressure-sensitive marking materials

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545574A1 (fr) * 1991-12-05 1993-06-09 Moore Business Forms, Inc. Ensembles de formulaires avec des feuilles CF, CB ou s'imprimant sans carbone et rubans de blockage, quelles annullent la fonction de s'imprimer sans carbone
US5639708A (en) * 1991-12-05 1997-06-17 Moore Business Forms, Inc. Providing a UV curable protection strip on a business form

Also Published As

Publication number Publication date
EP0085346B1 (fr) 1986-03-12
FI77605B (fi) 1988-12-30
EP0085346A3 (en) 1984-01-11
FI830295L (fi) 1983-07-31
DE3362482D1 (en) 1986-04-17
JPH043314B2 (fr) 1992-01-22
JPS58136484A (ja) 1983-08-13
DE3203059A1 (de) 1983-08-04
ATE18521T1 (de) 1986-03-15
FI830295A0 (fi) 1983-01-27
FI77605C (fi) 1989-04-10

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