EP0064204B1 - Herstellung von Reaktionsdurchschreibepapieren mittels Flexodruck - Google Patents

Herstellung von Reaktionsdurchschreibepapieren mittels Flexodruck Download PDF

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Publication number
EP0064204B1
EP0064204B1 EP82103255A EP82103255A EP0064204B1 EP 0064204 B1 EP0064204 B1 EP 0064204B1 EP 82103255 A EP82103255 A EP 82103255A EP 82103255 A EP82103255 A EP 82103255A EP 0064204 B1 EP0064204 B1 EP 0064204B1
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EP
European Patent Office
Prior art keywords
microcapsules
printing
production
diisocyanate
solvents
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.)
Expired
Application number
EP82103255A
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German (de)
English (en)
French (fr)
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EP0064204A1 (de
Inventor
Ulrich Dr. Nehen
Manfred Dr. Dahm
Artur Dr. Haus
Gert Dr. Jabs
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
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
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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
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor

Definitions

  • Reaction copy papers are known (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, pages 242-277; G. Baxter in Microencapsulation, Processes and Applications, edited by JE Vandegaer, Plenum Press, New York, London, pages 127-143 They preferably consist of two or more sheets of paper laid loosely on top of one another, the upper one on the back side containing a donor layer and the lower one on the front side containing a receiver layer, ie a donor layer and a receiver layer are in contact with each other contains microcapsules, the core material 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. When writing, the capsules are destroyed under the pressure of the writing instrument, and the leaking core material hits the receiver layer, so that a copy is made t.
  • the receiver layer usually contains binders and pigments, e.g. active absorbents such as kaolin, attapulgite, montmorillonite, bentonite, acidic bleaching earth or phenolic resins. You can e.g. Use acid-activated dyes on the donor layer and acid-reacting components in the receiver layer.
  • active absorbents such as kaolin, attapulgite, montmorillonite, bentonite, acidic bleaching earth or phenolic resins.
  • 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 color precursor, generally in the form of microcapsules, and at the same time the color developer. If pressure is now applied, e.g. using a typewriter or other writing tool, the capsule containing the color precursor is torn open and the color precursor reacts with the color developer surrounding it (see US Pat. No. 2,730,456).
  • the paper substrates are generally used to manufacture these carbon-free copy systems. Fully coated in a known manner with an aqueous coating composition, as described in German Offenlegungsschriften 1 934 457 and 1 955 542. After that, the water must be evaporated, which requires a considerable amount of energy and complex and costly equipment.
  • microcapsules containing dye precursors from e.g. Have polyurethanes are suspended in solvents such as benzene, chlorobenzene, trichlorodiphenyl, trichlorethylene and hexane, which can contain a small amount of polystyrene dissolved in chlorobenzene (Examples 3 and 8).
  • solvents such as benzene, chlorobenzene, trichlorodiphenyl, trichlorethylene and hexane, which can contain a small amount of polystyrene dissolved in chlorobenzene (Examples 3 and 8).
  • a flexographic printing process is also not mentioned in US Pat. No. 3,432,327.
  • DE-A-25 41 001 describes a process in which aqueous or solvent-containing microcapsule dispersions are printed without the use of binders. As a result, after drying, the microcapsules are not sufficiently bonded to the paper, so that they are blurred or removed when the paper is used, thereby losing the write-through effect of the paper.
  • the invention relates to a process for the production of pressure-sensitive, carbon-free carbonless papers by means of flexographic printing, which is characterized in that a preparation containing optionally chlorinated hydrocarbons or ethers which are liquid at 20 ° C. and has a boiling point of 50-180 ° C. as Solvent, a content of polymeric binders soluble in these solvents, and a content of dye precursor-containing microcapsules with an average diameter of 5-20 11 m partially or over the whole area using the technique of flexographic printing using a printing form which does not swell in the solvents of the preparation, is printed on paper and then the solvent is removed.
  • a preparation containing optionally chlorinated hydrocarbons or ethers which are liquid at 20 ° C. and has a boiling point of 50-180 ° C. as Solvent, a content of polymeric binders soluble in these solvents, and a content of dye precursor-containing microcapsules with an average diameter of 5-20 11 m partially or over the whole area
  • the preparation preferably contains 2 to 30 parts by weight of the polymeric binder - in particular cyclo rubber, polyamides, copolymers of styrene with alkyl (meth) acrylates, certain soluble polyurethanes or mixtures thereof, 2 to 30 parts by weight of microcapsules, preferably those whose walls are made of Polyurethanes, polyurethane-polyurea or polycarbodiimide consist and 96 to 40 parts by weight of the solvent.
  • spacers (2 to 20 parts by weight per 100 parts by weight of preparation) and further auxiliaries and additives (up to 50 parts by weight per part by weight of preparation) can be present.
  • microcapsules to be used according to the invention A large number of the microcapsules to be used according to the invention and processes for their production are known.
  • microcapsules can be used which are made of gelatin and gum arabic by coacervation or complex coacervation, as well as gelatin and other inorganic and organic polyanions have been produced. Appropriate methods are described in M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation 1972.
  • microcapsules are used, the walls of which consist of polymers, polycondensation and polyaddition products.
  • Microcapsules with walls made of special poly (meth) acrylates e.g. described in DE-OS 237 545, 2119 933 and 2 920 846 can be used.
  • 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, butyten-1,2-diisocyanate, ethylidene diisocyanate, cyclo-hexyl-1,2-diisocyanate, cyclohexyl-1,4-diisocyanate, polyisocyanate prepolymers, for example adduct of hexamethylene diisocyanate and hexanetriol, adduct of 2,4-tolylene diisocyanate with pyrocatechol, addition product of tolylene diisocyanate with hexanetriol, addition product of tolylene diisocyanate with trimethylolpropane or suitable polyisocyanates which
  • 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 production of which is evident from DE-AS 1 101 304 and 1 543178, 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 ethanediol, 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 ethanediol, 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 can be used, such as those produced by carbodiimidization of hexamethylene-1,6-diisocyanate containing biuret groups with organic phosphorus catalysts, 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.
  • Examples of the encapsulated color formers are triphenylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds and spiropyran compounds.
  • diphenylmethane compounds are 4,4'-bis-dimethylaminobenzhydrylbenzylether, N-halophenylleucolamine, N-ß-naphthylleucolamine, N-2,4,5-trichlorophenylleucolamine and N-2,4-dichlorophenolleucolamine.
  • xanthene compounds are rhodamine- ⁇ -anilinolactam, rhodamine- ⁇ - (p-nitroaniline) lactam, rhodamine- ⁇ - (p-chloroaniline) lactam, 7-dimethylamine-2-methoxifluorane, 7-diethylamine-3- methoxifluorane, 7-diethylamine-3-methyl-fluorane, 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) -fluoro-ran, 7-diethylamine-3- (methylbenzylamine
  • thiazine compounds are N-benzoyl-leucomethylene blue, o-chlorobenzoylleucomethylene blue, p-nitrolbenzoylleucomethylene blue.
  • spiro compounds are 3-methyl-2,2'-spirobis (benzo (f) chromium), 3-ethyl-spirodinaphthopyran.
  • Solvents that dissolve these color formers are e.g. chlorinated diphenyl, chlorinated paraffin, cottonseed oil, peanut oil, silicone oil, phthalate ester, phosphate ester, sulfonate ester, monochlorobenzene, furthermore partially hydrogenated terphecyle, alkylated naphthalenes, 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-benzyl-hydroxibiphenyl, 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 made. Capsules with diameters of 2 to 20 ⁇ m 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 are generally obtained as an aqueous suspension. You can e.g. isolate the microcapsules as agglomerate-free powder by spray drying.
  • the components - microcapsule powder, solvent and binder - can be mixed in conventional mixing units.
  • the binder dissolves in the solvent and the microcapsules are distributed homogeneously in this mixture. It is surprising that a stable and uniform distribution of the microcapsules can be achieved in this way, since the non-polar solvents and the polar microcapsules are inherently incompatible.
  • the solvent and the binder can also be introduced into the aqueous suspension of the microcapsules and the water can then be drawn off in a vacuum (flushing process).
  • the solvent may already contain one or more components of the printing ink.
  • the amount of microcapsules that is incorporated into the formulation depends on the requirements that must be placed on the finished printing ink.
  • the amount of capsules is set according to the method of the invention as high as is reasonable considering the rheology of the finished printing ink, in order to apply an optimal amount of microcapsules with the lowest possible coating weight.
  • the flexographic printing inks can normally be produced with simple stirrers, high-speed stirrers and / or high-performance stirrers.
  • the incorporation of the individual components of the printing inks can be carried out in any order.
  • binders can be used according to the method according to the invention, which binders are used according to the known prior art for producing a printing ink which can be processed in flexographic printing.
  • binders are used according to the known prior art for producing a printing ink which can be processed in flexographic printing.
  • Suitable solvents or solvent mixtures are aromatic and aliphatic hydrocarbons, halogenated aromatic and aliphatic hydrocarbons and ethers. They are liquid at 20 ° C and have boiling points between 50 and 180 ° C.
  • Examples include white spirit, white spirit, special gasoline, n-pentane, n-hexane, cyclohexane, ligroin, petroleum ether, light petrol, carbon tetrachloride, perchlorethylene, cumene, chlorobenzene, methyl tert-butyl ether, tert-amyl methyl ether.
  • Suitable materials are isoprene rubber, acrylonitrile-butadiene rubber, and ethylene-propylene-diene rubber.
  • dispersing aids preferably from the group of the cationic surfactants, can be added to the printing ink.
  • spacers are added to the printing ink in amounts of 2-20% by weight.
  • these spacers are also used in the production of the usual carbonless carbonless papers.
  • they can consist of cellulose fiber particles or starch granules, the diameter of which is usually 1.5 to 5 times the microcapsule diameter.
  • Pigments and auxiliaries which have a favorable effect on the opacity of the coating can be added as further additives.
  • drying retarders When using slow-running printing presses, oversized plate cylinders or particularly strongly absorbent "print carriers”, drying retarders can also be used. Fast dryers and accelerators are used when extremely high printing speeds are to be achieved.
  • a 30% aqueous microcapsule dispersion was prepared, the microcapsule walls of which consisted of a polyaddition product of the oxadiazinetrione of hexamethylene diisocyanate and a polyamine.
  • the capsule contents were a solution of 2.7% crystal violet lactone and 0.9% N-benzoyl leukomethylene blue in diisopropyl diphenyl.
  • the core / wall ratio of the microcapsules was 83:17.
  • the 30% capsule dispersion was converted into a largely agglomerate-free capsule powder by spray drying, the mean capsule diameter of which was determined to be 7.3 ⁇ m.
  • the printing ink produced in this way containing 12% by weight of microcapsules, was printed on the back of a commercially available CF paper (Jeset-CF from Feldmühle) in the form of a square of 12 cm edge length using a flexographic printing machine.
  • the application weight of the coating was up to 2.6 g / m 2 after drying, which corresponded to an amount of capsules of approximately 1.6 g / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
EP82103255A 1981-04-30 1982-04-19 Herstellung von Reaktionsdurchschreibepapieren mittels Flexodruck Expired EP0064204B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813117242 DE3117242A1 (de) 1981-04-30 1981-04-30 Flexodruckfarben fuer die herstellung von reaktionsdurchschreibepapieren
DE3117242 1981-04-30

Publications (2)

Publication Number Publication Date
EP0064204A1 EP0064204A1 (de) 1982-11-10
EP0064204B1 true EP0064204B1 (de) 1986-07-23

Family

ID=6131223

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82103255A Expired EP0064204B1 (de) 1981-04-30 1982-04-19 Herstellung von Reaktionsdurchschreibepapieren mittels Flexodruck

Country Status (4)

Country Link
EP (1) EP0064204B1 (enrdf_load_stackoverflow)
JP (1) JPS57185185A (enrdf_load_stackoverflow)
DE (2) DE3117242A1 (enrdf_load_stackoverflow)
ZA (1) ZA822923B (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61273985A (ja) * 1985-05-30 1986-12-04 Japan Synthetic Rubber Co Ltd 感圧複写紙用塗布組成物
US5022545A (en) * 1990-08-03 1991-06-11 Continental White Cap, Inc. Tamper evident closure
DE4132796C2 (de) * 1991-10-02 1994-02-24 Andre Nuyken Verwendung einer chemisch druckanzeigenden Beschichtung auf einem Trägermaterial zur Herstellung von Fußabdrücken

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US3432327A (en) * 1964-03-13 1969-03-11 Pilot Pen Co Ltd Pressure sensitive copying sheet and the production thereof
DE2541001A1 (de) * 1975-09-13 1977-03-17 Eupaco Papier Vertrieb Gmbh & Verfahren zur herstellung von zonenweise durchschreibenden farbreaktionspapieren
JPS532108A (en) * 1976-06-28 1978-01-10 Fuji Photo Film Co Ltd Method of producing pressure sensitixed copy sheets
DE2930408A1 (de) * 1979-07-26 1981-02-12 Bayer Ag Reaktionsdurchschreibepapier

Also Published As

Publication number Publication date
JPS57185185A (en) 1982-11-15
DE3272101D1 (en) 1986-08-28
EP0064204A1 (de) 1982-11-10
ZA822923B (en) 1983-03-30
JPH0359836B2 (enrdf_load_stackoverflow) 1991-09-11
DE3117242A1 (de) 1982-11-18

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