EP0052733B1 - Compositions cireuses contenant des microcapsules, leur préparation et utilisation - Google Patents

Compositions cireuses contenant des microcapsules, leur préparation et utilisation Download PDF

Info

Publication number
EP0052733B1
EP0052733B1 EP81108073A EP81108073A EP0052733B1 EP 0052733 B1 EP0052733 B1 EP 0052733B1 EP 81108073 A EP81108073 A EP 81108073A EP 81108073 A EP81108073 A EP 81108073A EP 0052733 B1 EP0052733 B1 EP 0052733B1
Authority
EP
European Patent Office
Prior art keywords
wax
microcapsules
melt
parts
alkali metal
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
EP81108073A
Other languages
German (de)
English (en)
Other versions
EP0052733A1 (fr
Inventor
Dietrich Hoffmann
Wolfgang Dr. Sliwka
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0052733A1 publication Critical patent/EP0052733A1/fr
Application granted granted Critical
Publication of EP0052733B1 publication Critical patent/EP0052733B1/fr
Expired legal-status Critical Current

Links

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
    • 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
    • B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like

Definitions

  • the invention relates to wax compositions containing microcapsules on the basis of microcapsules with a wall material made of melamine-formaldehyde condensates, and to the production and use of these wax compositions.
  • Wax compositions containing microcapsules have long been known from the patent literature. Wax compositions containing microcapsules with melting points between 55 and 175 ° C. are described in US Pat. Nos. 30 16 308 and 30 79 351. The masses can by various methods, e.g. B. applied by printing on paper as a carrier. The solidifying wax binds the microcapsules to the carrier. The dry microcapsules contained by spray drying the emulsions described in the US patent have diameters of 1 to 50 J.1.m and are therefore not suitable for the production of pressure-sensitive recording materials. The large capsules are destroyed when printing or coating with layers approximately 5 ⁇ m thick.
  • JP-A-73 12 255 describes a wax composition containing microcapsules for spot printing.
  • the wax mass is obtained by mixing dry microcapsules with a wax melt in the presence of nonionic surfactants.
  • Capsules are those with wall materials made of gelatin, polymers or melamine-formaldehyde condensates. Paper coated with this mass should not give any discoloration during storage in the form set.
  • DE-A-2719 914 describes pressure-sensitive carbonless copy papers based on wax melts containing microcapsules.
  • the wax composition used for coating is produced by heating the water-insoluble, functional groups-bearing wax-like substances or the non-polar waxes with anionic dispersants to above the melting temperature and dispersing the dry microcapsules in this melt.
  • microcapsules with wall material based on hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, melamine formaldehyde, polyfunctional isocyanates and their prepolymers, polyfunctional acid chlorides, polyamines, polyols, epoxides or mixtures thereof are suitable for these compositions.
  • Microcapsules with wall material made of hydroxypropyl cellulose crosslinked with polyfunctional isocyanates are particularly preferred.
  • the wax composition can also be prepared by adding the aqueous microcapsule dispersion to the wax melt and distilling off the water in vacuo.
  • the aqueous capsule dispersion must be added continuously to the melted wax to the extent that the water distills off, so that the mass is practically free of water.
  • Hydroxypropyl cellulose capsules are not stable at 70 ° C in the presence of water, while dry capsules in the absence of water are said to be stable at approximately 95 ° C for approximately 18 hours.
  • Table I in Example II that the microcapsules based on hydroxypropyl cellulose, crosslinked with polyisocyanate and post-cured with melamine-formaldehyde and gelatin in the wax melt at 90 ° C. are considerably permeable and accordingly have a high degree in thermogravimetric analysis Show loss.
  • DE-A-2818 976 also describes hot-meltable wax compositions containing microcapsules.
  • the wax compositions are prepared by the process already given in DE-OS 2719 914, Example 1, by adding the aqueous microcapsule dispersion to the wax melt and removing the water in vacuo. The dispersion should be added to the extent that the water is removed. In order to achieve a rapid removal of the water, mixing with the wax melt is carried out continuously with stirring in a thin-film evaporator.
  • water-soluble waxes and resins such as polyethylene oxide wax and polyvinylpyrrolidone can also be used as the “suspending medium” (wax).
  • wax water-soluble waxes and resins
  • the carbon-free carbonless papers obtained with the wax compositions produced in this way have a reduced copy performance compared to corresponding papers with wax compositions which were produced with spray-dried microcapsules.
  • the coating compositions of DE-A 28 18 976 and DE-A-2719 914 are more or less lightly colored, the coated side is colored accordingly in the case of white paper. Since opacifiers such as titanium dioxide or clay form lumps in the wax melts and are difficult to disperse, the color of the wax application could not be masked in this way.
  • This problem is solved by DE-A-28 20 600 by adding inorganic pigment to the aqueous microcapsule dispersion and isolating this mixture by spray drying. A flowable powder is obtained, which is then dispersed in the wax melt.
  • microcapsules with secondary capsule walls are known, in which the capsule wall primarily formed from hydroxypropyl cellulose and a di- and polyisocyanate is aftertreated in a subsequent step with phenol and aldehyde. The polymer formed by condensation is deposited on the wall formed first.
  • These capsules are said to have advantages in the manufacture of microcapsule-containing wax compositions, since the capsules are made by Filtration separated from the aqueous phase and can be added to the known wax melts in this form.
  • Example 2 is a coating mixture described. According to the information in Example 3, the particle sizes of the capsules are from 3.1 to above 12.3 ⁇ m (25% are 12.3 ⁇ m), the capsules being in the form of agglomerates.
  • the object of the present invention was to find stable wax compositions containing microcapsules for the application by the hot-melt process.
  • the wax composition it is essential to the invention that it contains microcapsules, the wall material of which 1) consists of melamine-formaldehyde condensates and 2) the wall material has been produced under the conditions specified above.
  • the wax compositions according to the invention are thermally stable even in the presence of water and, after being applied to the carrier material, together with CF layers, give strong, sharp copies.
  • the CF layers are not stained in form sets even after prolonged storage. A discoloration of the CF layer does not occur or practically does not occur if the wax composition containing microcapsules is applied directly to the CF layer.
  • the wax compositions according to the present invention can be applied over the whole or part of the surface simultaneously or after printing on the carrier material by known methods. Clean and distortion-free smooth support materials are obtained even if the wax composition contains up to 20% by weight of water, based on (a + b + c).
  • the microcapsules contained in the wax compositions according to the invention have a wall which consists of highly crosslinked melamine-formaldehyde condensates.
  • the ratio of wall material to core material is 1:15 to 1: 2, preferably 1:10 to 1: 4. The most advantageous ratio depends on the capsule size. The larger the capsule, the more wall material is required.
  • the microcapsules required for the wax compositions according to the invention are obtained by curing the capsules obtained primarily. The curing takes place by heating the aqueous capsule dispersions to 60 to 100, preferably 70 to 90 ° C. for 2 to 10, preferably 3 to 6 hours. This treatment increases the thermal resistance and the resistance to water in the wax melts. In this treatment, the formaldehyde content in the aqueous phase is increased.
  • the resulting formaldehyde can be bound with ammonia, amines or other compounds that react with formaldehyde, such as ethylene urea.
  • the primary wall is obtained by condensation of melamine with formaldehyde, methylolmelamines, methylolmelamine methyl ethers or mixtures thereof at a ratio of melamine to formaldehyde of 1: 2 to 1: 6, preferably 1: 3 to 1: 6.
  • Microcapsules with diameters from 2 to 10, in particular from 2 to 8 ⁇ m are suitable for the intended use of the wax compositions.
  • microcapsules The production of the primary microcapsules is known. All microcapsules with walls made of melamine-formaldehyde condensates which are obtainable by known processes are suitable for curing if they meet the criteria specified above. Preferred are microcapsules which are obtained according to the method of older priority EP-A-26914, which has not been previously published.
  • the wax compositions according to the invention contain - based on (a + b + c) - 20 to 55, preferably 30 to 45% by weight of microcapsules (a).
  • the capsule is protected against destruction as the proportion of wax (b) and pigment (d) increases. Since the viscosity of the liquid wax mass also increases with increasing content of (a), waxes with a high content of (a) which have low viscosity melts will be used for wax masses. It was found that minor Quantities, e.g. B. 2 to 10 wt .-% of water in the melt have a viscosity-reducing effect without disadvantages in use or on the carrier material coated with such wax materials such as paper.
  • waxes are the water-insoluble waxes usually used in wax compositions for hot carbon processes, both on their own and in the form of mixtures of different waxes with a melting point of about 50 to 140 ° C.
  • Bright waxes are preferred for the wax compositions according to the invention.
  • Natural and synthetic waxes can be considered.
  • plant waxes such as candelila wax, carnauba wax; Hydrocarbon waxes such as paraffins, ozokerite and microcrystalline waxes; Montan wax and waxes made from it, such as montanic acids and their esters, polyethylene waxes, oxidized microcrystalline waxes and ester waxes.
  • mixtures can also contain hydrophilic waxes, such as polyethylene glycols, polypropylene glycols or their mixed block copolymers.
  • the intensity of the copy depends on the wax mixture used as a binder, whereby not only the hardness but also the wettability plays a role.
  • the intensity of the copy gets better with paraffins as the melting point of the paraffins increases (e.g. from 52 to 69 ° C.).
  • Ester waxes based on ethylene glycol or butanediol and montanic acids as binders give more intense copies than with paraffins and / or montanic acids.
  • the intensity of the copy can also be improved by adding ethylene oxide adducts.
  • the wax melt contains 1 to 10% by weight, based on (a + b + c), as c) one or more nonionic emulsifiers, at least one Alkali metal salt of montan wax acids or a mixture of (a) at least one nonionic emulsifier and (ß) at least one alkali metal salt of montan wax acids , from C 1o to C zo fatty alcohol sulfates and / or from C 10 to C 20 alkane sulfonates.
  • Suitable nonionic emulsifiers are for (c), mainly water-soluble ethylene oxide adducts of C 12 - to C 20 -alkanols or C 12 - to C 2o -alkenols having from 13 to 30, preferably 15 to 25 moles of EO per mole of alcohol proven.
  • alkali metal salts of montan wax acids also called montan acids
  • fatty alcohol sulfates which are salts of sulfuric acid semiesters of fatty alcohols, e.g.
  • fatty alcohol sulfates which are salts of sulfuric acid semiesters of fatty alcohols, e.g.
  • lauryl alcohol diodecanol-1
  • tetradecanol-1 tetradecanol-1
  • hexadecanol-1 palmityl alcohol
  • octadecanol-1 stearyl alcohol
  • the sodium, potassium and lithium salts are to be mentioned as alkali metals, of which the sodium and potassium salts are preferred.
  • the alkali metal salts of montan wax acids are obtained by neutralizing the montan wax acids obtained by chromic acid oxidation of montan wax with the corresponding bicarbonates, carbonates or also hydroxides.
  • the alkali metal salts of montan wax acids can be prepared in isolation or previously in the wax melt to be used.
  • water-soluble emulsifiers (c) adducts of stearyl alcohol, tallow fatty alcohol or partially unsaturated C 16/18 alkanol mixtures and 15 to 25 moles of EO per mole of alcohol are particularly preferred.
  • alkali metal salts of montan wax acids and mixtures of (a) are nonionic emulsifying agents, especially those mentioned above and (ß) alkali metal salts of montan wax acids, of C lo - C 20 -Fettalkoholsulfaten and / or of C 1o - to C 2o - Alkanesulfonates are particularly preferred.
  • alkali metal salts of montan wax acids and mixtures of these alkali metal salts and EO adducts of 15 to 25 moles of ethylene oxide per mole of alcohol in stearyl alcohol, tallow fatty alcohol and / or in mixtures of partially unsaturated C 16/18 alkanols are very special because of the particularly good dispersing action prefers.
  • the microcapsules in the wax are largely or almost completely in the form of individual particles.
  • the amount of (c) is - based on (a + b + c) - 1 to 10, preferably 3 to 10% by weight, in particular 4 to 9% by weight.
  • fillers or mixtures thereof such as are also added to aqueous coating colors containing microcapsules, can be added to the wax composition.
  • These funds are intended for the premature unintentional destruction of capsules, for. B. prevent when rubbing the leaves against each other.
  • pigments come e.g. B. titanium dioxide, barium sulfate, Blancfixe and as fillers z.
  • the wax melt can contain up to 60, preferably 0 to 20% by weight, based on (a + b + c), of water as volatile component (s).
  • the water content has an advantageous influence on the viscosity of the wax mass, which is reduced and on the dispersion of microcapsule agglomerates during incorporation.
  • agents (f) which are customary in wax compositions for the hot-melt process are those for regulating the viscosity.
  • the viscosity of the mass can be increased by adding polyethylene waxes, oxidized polyethylene or by adding petroleum jelly, mineral oil, stearylamide, stearic acid esters, sodium stearate, potassium stearate, barium stearate, sodium palmitate, potassium palmitate, sodium oleate, potassium oleate, calcium stearate, zinc stearate, A-wax, in which Melt soluble polymers or mixtures thereof can be reduced.
  • the dispersion of the dry capsules can be made considerably easier by adding a little water to the wax melt.
  • microcapsules isolated by spray drying are preferably dispersed in the wax melt in the presence of alkali metal salts of montan wax acids or of mixtures of (a) nonionic emulsifiers and (ß) alkali metal salts of montan wax acids , of C 10 to C 20 fatty alcohol sulfonates and / or C 10 - C zo alkanesulfonates as dispersants (c) and in the presence of 1 to 15, preferably 5 to 15% by weight, based on (a + b + c), water (e).
  • alkali metal salts of montan wax acids or of mixtures of (a) nonionic emulsifiers and (ß) alkali metal salts of montan wax acids , of C 10 to C 20 fatty alcohol sulfonates and / or C 10 - C zo alkanesulfonates as dispersants (c) and in the presence of 1 to 15, preferably 5 to 15% by weight, based on (a + b
  • wax compositions containing microcapsules are (c) alkali metal salts of montan wax acids and mixtures of adducts of 15 to 25 mol ethylene oxide with stearyl alcohol, tallow fatty alcohol and / or with partially unsaturated C 1s / C 18 alkanol mixtures and alkali metal salts of montan wax acids.
  • the amount of water is also based on (a + b + c) - 1 to 15, preferably 5 to 15 wt.%.
  • microcapsule dispersion is concentrated with thorough mixing until the residue is in the form of a pasty mass.
  • concentration can be carried out under normal pressure in vacuo or under pressure, if appropriate with the passage of air or inert gas.
  • dispersant (c) water-soluble waxes and optionally low-melting or liquid agents are added to the residue, which are required to adjust the viscosity of the wax melt.
  • Such means are e.g. B. Vaseline and mineral oil.
  • the water can be largely or almost completely removed, the temperature should not exceed 120 ° C.
  • the water can be removed more quickly than with the method in which the microcapsule dispersion is added to the wax melt and the water is removed from the wax melt.
  • Foam caused by the presence of (c) can be defoamed, e.g. B. those based on silicone, easily destroyed.
  • a melt of wax and the components still required can then be immediately added to the viscous dispersion thus obtained, a homogeneous melt being formed by stirring and containing the microcapsules in dispersed form. But you can also proceed that one enters the components one after the other and mixes the melt homogeneously.
  • the solid, non-melting components e.g. B. pigments and spacers are added last.
  • melts obtained in 1) to 5) contain the microcapsules essentially as individual capsules in addition to agglomerates.
  • the proportion of agglomerates is lowest in most cases if there is some water in the melt from the beginning.
  • the method according to 3.1) is preferred for the industrial production of wax compositions containing microcapsules, since this easily provides wax compositions which are practically free of agglomerates.
  • the intensity of the copy of the carbonless reaction papers containing wax as a binder is generally somewhat less than that of carbonless paper coated with dispersions containing aqueous microcapsules. This applies in the event that the wax compositions containing the microcapsules are on the paper surface (i.e. practically no wax has penetrated the paper yet). If you work with the coating so that the wax can penetrate the paper, you get intensively copying coatings.
  • the following exemplary embodiments are intended to explain the invention in addition.
  • the parts and percentages given below refer to the weight.
  • the room parts are related to the parts by weight like liters to kilograms.
  • a solution made up of pH 4.0 from 120 parts of a partially methylated precondensate which is clearly soluble in water (contains about 2.3 CH 3 O groups per melamine molecule) of melamine and formaldehyde (ratio 1: 5.25 mol) in 132 parts of water at 40 ° C. while maintaining the pH at 4.0.
  • the capsule formation can be determined in a sample under the microscope: the emulsion droplets no longer run together on the slide.
  • the dispersant is switched off and the microcapsule dispersion formed is cured with stirring (propeller stirrer) at the temperatures and times given in the table.
  • the capsule dispersion is then cooled and adjusted to pH 8 to 9 with ammonia.
  • the dispersion is then sieved through a 40 J.1.m sieve.
  • the dispersions obtained are colorless, milky and, after measurement in the Coulter Counter TF, contain individual capsules with a most common particle diameter of 5.6 ⁇ m.
  • the solids content is 40.0%.
  • the 40% dispersion is post-cured for 2 hours at 95 ° C. and pH 4.0.
  • the dispersion contains individual capsules with a common diameter of 3.4 ⁇ m (measured in the COULTER Counter TF).
  • the dispersion is prepared as indicated under 1.1, but a solution of 180 parts of a water-soluble, partially methylated precondensate (contains approx. 5 OCH 3 groups per melamine molecule) made of melamine and formaldehyde (1: 6 mol) in 200 parts of water added in 4.5 h. Post-curing takes place at pH 4.0 and 70 ° C; Duration: 5 hours. Solids content: 38.9%; most common capsule diameter: 5.4 ⁇ m.
  • the dispersion is prepared according to 1.4, but the same amount of a partially methylated precondensate made of melamine-formaldehyde (1: 5.7 mol) with 2.3 CH 3 0 groups per melamine molecule is used. Solids content: 38.4%; most common capsule diameter: 5.9 ⁇ m.
  • the wax compositions produced were tested as follows.
  • a drop of the wax melt containing microcapsules is spread on a hot slide and the microcapsules are assessed under the microscope.
  • Approx. 1 ml of the melt produced is poured onto the active side of a CF sheet. This position is called «Approach.
  • the wax melt is then quickly pulled out with a card sheet, so that a thin coating that does not penetrate into the paper is created (“layer”). After 24 hours of storage, the sheet is assessed on the "batch and in the" layer "in the coloring.
  • the viscosity was determined in a ®Rotovisko from Gebr. Haake, Berlin, with a fluted measuring cylinder and beaker at a shear rate of 428 sec- 1 and 85 and 95 ° C.
  • 80 parts of a paraffin with a melting point of 52 to 54 ° C. and 40 parts of an ester wax composed of montanic acid and 1,4-butanediol (melting point 80 to 83 ° C.; melting point of the mixture 71 to 78 ° C.) are placed in a heatable stirred tank with anchor stirrer and distillation attachment. melted at 95 ° C.
  • 27 parts of petroleum jelly and 21.5 parts of an adduct of 23 moles of ethylene oxide are added to a partially unsaturated C 16 / C 18 alcohol mixture and, after dissolution, 280 parts of the capsule dispersion specified below are added all at once with stirring.
  • a homogeneous dispersion is formed, from which all water is slowly distilled off using a vacuum (up to 200 mm Hg) at a bottom temperature of 90 to 95 ° C (duration: 3 hours). Then the stirred tank is aerated and the melt is poured into a foil trough to solidify.
  • microcapsule dispersions are used:
  • the assessment of the discolouration of CF paper at the "approach” point is more significant than in the "layer”, since capsules are often destroyed when they are brushed on with the edge sheet, which can be recognized by colored lines in the direction of the stroke.
  • microcapsule dispersion 3 (produced according to 1.1) is in a spray dryer (gas inlet temperature rature 120 ° C) to a free-flowing powder (residual moisture: 4%). 112 parts of the powder are introduced into the wax melt from paraffin, ester wax, petroleum jelly and oxethylation product specified in Example 1 and stirred at 90 ° C. for 1 h.
  • microcapsule dispersion 5 is centrifuged in a centrifuge for 1/2 h at 600 g.
  • the microcapsules settle on the surface and can be removed as a solid cake (water content: 39%).
  • microcapsule dispersion 2 is used instead of microcapsule dispersion 5
  • a wax mass (residual moisture: 6.4%) is obtained which, in the test according to II. B1), colors the CF layer a strong greenish-gray.
  • Grade 4 ( «approach and « layer »). The copies obtained with this wax mass are still quite legible (grade 3-4).
  • Example 1 In the apparatus described in Example 1, 28.8 parts of paraffin (mp. 52 to 54 ° C), 14.4 parts of the ester wax specified in Example 1, 4.9 parts of petroleum jelly (white) and 4.8 parts of the ethylene oxide adduct are Example 1 melted at 80 ° C. At this temperature, 62 parts of microcapsule dispersion 6 are added to the homogeneous melt with stirring, and 35 parts of water are distilled off at a bottom temperature between 82 and 73 ° C. while the pressure is slowly falling. As a result of the water evaporating too quickly, the melt must not locally fall below the solidification point, since this can form agglomerates that can no longer be broken up. The wax composition obtained has a viscosity of 139 mPas at 85 ° C and 131 mPas at 95 ° C. Solids content according to II d): 98.2%.
  • microcapsule dispersion 7 39.1 parts of microcapsule dispersion 7 are mixed with 2.2 parts of the ethylene oxide adduct from Example 1 and 5.95 parts of petroleum jelly (white) with stirring at 90 ° C. and 15.3 parts of water are distilled off from this mixture under reduced pressure. To prevent foam, a small amount of a defoamer (base: silicone) is added.
  • base silicone
  • microcapsule dispersion 8 64 parts are mixed with 3.23 parts of the ethylene oxide adduct from Example 1 and 5.95 parts of petroleum jelly (white) at 80 ° C. and 33.2 parts of water are distilled off from this mixture under reduced pressure within 4 h (bottom temperature: 50 up to 80 ° C). The residue is heated to 80 ° C and a 90 ° C warm melt of 17.6 parts of paraffin (mp. 52 to 54 ° C), 8.8 parts of the ester wax specified in Example 1 and 1.5 parts of the above Added ethylene oxide adduct and dispersed the mixture at 90 ° C for 2.5 h. Viscosity of the mass at 85 ° C: 120 mPas. Solids content: 93.1%.
  • a homogeneous melt is obtained which contains 50% capsules, based on solids.
  • the solids content is 82.0%.
  • the melt contains individual capsules.
  • microcapsule dispersion 8 (from 1.5) are mixed with 43 parts of an adduct of 23 mol EO of partially unsaturated C 16 - / C 18 alcohol mixture and 208 parts of water are drawn off from the mixture at 90 ° C. under reduced pressure in 3.5 h . Then a melt of 98 parts of paraffin (mp. 69-73 ° C.) and 196 parts of the ester wax from Example 1 is slowly added and the mixture is stirred for a further 3 hours at 90 ° C. under reduced pressure. 107 parts of water are still transferred. 46 parts of a spherical starch (special starch K from Amylum) are then slowly introduced into the melt and homogenized for 1 h. A thin melt is formed. Viscosity: 319 mPas (85 ° C); 226 mPas (95 ° C); Solids content: 92.2%.
  • This sheet can e.g. B. can be used as carbon paper.
  • coated paper is stored for 2 hours at 120 ° C., paper soaked with wax is obtained, which gives copies with a grade of 1-2.
  • microcapsule dispersion 8 750 parts of microcapsule dispersion 8 are mixed with 385 parts of a dispersion which contains 35% of a montanic acid esterified with ethylene glycol and 5% of an adduct of 23 mol of EO with tallow fatty alcohol, and is dried by spraying (gas inlet temperature 120 ° C., outlet temperature 70 ° C.) .
  • the diameter of the wax particles in the wax dispersion is well below 1 ⁇ m, so that the particles can no longer be seen under the light microscope.
  • melt was diluted with 10% petrol. Rating: 1 (coating: 3, 7 g / m 2).
  • microcapsule dispersion 3 (produced according to 1.1) is dried in a spray dryer (gas inlet temperature: 120 ° C.) to a free-flowing powder. Residual moisture: 4%.
  • microcapsule powder 15.2 90 parts of microcapsule powder are introduced as in 15.1 into a melt of 87 parts of paraffin, 60 parts of the ester wax specified in 15.1 and 9 parts of sodium salt of the montan wax acid specified in 15.1 in the form of a 26.5% strength aqueous paste and stirred homogeneously.
  • the melt contains individual capsules, as well as some agglomerates. Solids content: 92.8%, viscosity: 130 mPas (85 ° C); 110 mPas (95 ° C).
  • Example 16.1 The procedure is as in Example 15.2, but the wax melt additionally contains 1 part of an ethylene oxide adduct of 23 moles of ethylene oxide with a partially unsaturated C 16 / C 18 alcohol mixture.
  • the melt contains practically only individual capsules. Solids content: 92.8%; Viscosity: 243 mPas (85 ° C), 150 mPas (95 ° C).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Color Printing (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paper (AREA)

Claims (7)

1. Masses cireuses contenant des microcapsules, consistant en - par rapport à (a + b + c) -
a) 20 à 55 % en poids de microcapsules,
b) 79 à 30 % en poids de cire ou d'un mélange de plusieurs cires dont le point de fusion va d'environ 50 à 140°C,
c) 1 à 10 % en poids d'au moins un agent émulsionnant non-ionique, au moins un sel de métal alcalin d'acides de la cire de lignite, ou d'un mélange de (a) au moins un agent émulsionnant non ionique et (β) au moins un sel de métal alcalin d'acides de cire de lignite, de sulfates d'alcools gras en C 10-C 20 et/ou d'alcane-sulfonates en C 10-C 20,
d) 0 à 20 % en poids de pigments et/ou matières de charge,
e) 0 à 60 % en poids de fractions volatiles, et le cas échéant,
f) d'autres produits usuels dans ces masses cireuses, la matière de paroi des microcapsules (a) consistant en un condensat polymère mélamine-formaldéhyde qui a été obtenu par condensation de la mélamine avec du formaldéhyde, de méthylolmélamines et/ou de leurs éthers méthyliques avec un rapport mélamine/formaldéhyde de 1 : 2 à 1 : 6 à un pH de 3,5 à 5,5 et à des températures de 60 à 100 °C et durcissement final de 2 à 10 heures à une température de 60 à 100°C, le rapport matière de noyau/matière de paroi dans la capsule allant de 1 : 15 à 1 : 2 et les microcapsules présentant un diamètre de 2 à 10 microns.
2. Masses cireuses selon la revendication 1, caractérisées en ce qu'elles contiennent en tant que composant (c) au moins un sel de métal alcalin d'acides de la cire de lignite et d'au moins un produit de réaction de l'alcool stéarylique, des alcools gras de suif et/ou d'un mélange d'alcanols partiellement insaturés en C 16-C 18 avec 13 à 30 moles d'oxyde d'éthylène par mole d'alcool.
3. Masses cireuses selon la revendication 1 ou 2, caractérisées en ce qu'elles contiennent de 3 à 10 % en poids du composant (c) par rapport à (a + b + c).
4. Procédé de préparation des masses cireuses contenant des microcapsules selon la revendication 1, par mélange des composants avec une cire à l'état fondu, caractérisé en ce que l'on utilise en tant que composant (a) des microcapsules qui ont été obtenues par atomisation d'une dispersion aqueuse de microcapsules contenant - par rapport aux microcapsules - de 15 à 70 % en poids d'une cire solide à l'état de dispersion aqueuse et de 0 à 10 % en poids d'au moins un agent émulsionnant non ionique, d'un sel de métal alcalin d'acides de la cire de lignite ou d'un mélange de (a) au moins un agent émulsionnant non ionique et (ß) un sel de métal alcalin d'acides de la cire de lignite, de sulfates d'alcools gras en C 10-C 20 et/ou d'alcane-sulfonates en C 10-C 20.
5. Procédé de préparation des masses cireuses contenant des microcapsules selon la revendication 1, par mélange des composants à l'état fondu, caractérisé en ce que l'on homogénéise les microcapsules (a) isolées par atomisation dans une masse fondue de (b) et d'un sel de métal alcalin d'acide de cire de lignite ou d'un mélange de (a) un agent émulsionnant non-ionique et (p) un sel de métal alcalin d'acides de cire de lignite, de sulfates d'alcools gras en C 10-C 20 et/ou d'alcane-sulfonates en C 10-C 20 en tant que composant (c) et en présence de 1 à 15 % en poids d'eau (e) par rapport à (a + b + c).
6. Procédé de préparation des masses cireuses contenant des microcapsules selon la revendication 2, par mélange des composants à l'état fondu, caractérisé en ce que l'on homogénéise les microcapsules (a) isolées par atomisation dans une masse fondue de (b) et d'un sel de métal alcalin d'acides de cire de lignite ou d'un mélange de sel de métal alcalin d'acides de cire de lignite et d'un produit de réaction de l'alcool stéarylique, des alcools gras de suif et/ou d'un mélange d'alcanols partiellement insaturés en C 16-C 18 avec 13 à 30 moles d'oxyde d'éthylène par mole d'alcool en tant que composant (c) en présence de 1 à 15 % en poids d'eau par rapport à (a + b + c).
7. Utilisation des masses cireuses contenant des microcapsules selon les revendications 2 ou 3, pour la préparation de papiers à copier réactifs ou de papiers à copier revêtus de microcapsules.
EP81108073A 1980-11-24 1981-10-08 Compositions cireuses contenant des microcapsules, leur préparation et utilisation Expired EP0052733B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803044113 DE3044113A1 (de) 1980-11-24 1980-11-24 Mikrokapseln enthaltende wachsmassen
DE3044113 1980-11-24

Publications (2)

Publication Number Publication Date
EP0052733A1 EP0052733A1 (fr) 1982-06-02
EP0052733B1 true EP0052733B1 (fr) 1984-06-13

Family

ID=6117378

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108073A Expired EP0052733B1 (fr) 1980-11-24 1981-10-08 Compositions cireuses contenant des microcapsules, leur préparation et utilisation

Country Status (4)

Country Link
US (1) US4371634A (fr)
EP (1) EP0052733B1 (fr)
JP (1) JPS57117337A (fr)
DE (2) DE3044113A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855403A (en) * 1983-02-22 1989-08-08 Union Carbide Corporation Connected branch copolymers, methods for their production, and copying materials including same
US4946824A (en) * 1983-02-22 1990-08-07 Union Carbide Chemicals And Plastics Company Inc. Connected branch copolymers, methods for their production, and copying materials including same
US4533567A (en) * 1983-05-24 1985-08-06 Ncr Corporation Carbonless paper coating formulation
JPS60149489A (ja) * 1984-01-17 1985-08-06 Kureha Chem Ind Co Ltd 部分感圧紙
JPS6155159A (ja) * 1984-08-25 1986-03-19 Nippon Oil Co Ltd 塗膜保護用水性組成物
US4594370A (en) * 1985-03-29 1986-06-10 The Mead Corporation Amine-formaldehyde microencapsulation process
US4822769A (en) * 1985-06-12 1989-04-18 Nashua Corporation High solids content coated back paper
DE3531123A1 (de) * 1985-08-31 1987-03-12 Schramm Lacke Gmbh Verfahren zum lackieren bahnfoermiger oder tafelfoermiger substratmaterialien
DE3544379A1 (de) * 1985-12-14 1987-06-19 Basf Ag Wachs- oder kohlepapiermassen sowie eine schicht aus diesen massen enthaltende kohle- oder vervielfaeltigungspapiere
IN166848B (fr) * 1987-06-17 1990-07-28 Business Forms Limited
US4992502A (en) * 1989-08-14 1991-02-12 The Gillette Company Solid correction compositions
DE4103966A1 (de) * 1991-02-09 1992-08-13 Basf Ag Farbbildner-zubereitungen
DE19736435C2 (de) 1997-08-21 1999-09-09 Sto Ag Fassadenabdeckung
CN115748297A (zh) * 2021-05-26 2023-03-07 刘兴发 一种具有阻燃性能的复写纸

Family Cites Families (14)

* 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
US3079351A (en) * 1958-11-26 1963-02-26 Moore Business Forms Inc Copying materials and emulsions
NL301306A (fr) * 1961-03-29
FR1318519A (fr) * 1961-03-29 1963-02-15 Kemi As Feuille copiante
US3516941A (en) * 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
DE1568663A1 (de) * 1966-12-30 1970-03-19 Hoechst Ag Verfahren zur Herstellung von Kohlepapierwachsen
JPS4812255B1 (fr) * 1969-11-26 1973-04-19
US4143890A (en) * 1976-05-07 1979-03-13 The Mead Corporation Pressure-sensitive carbonless transfer sheets using hot melt systems
GB1570042A (en) 1976-05-07 1980-06-25 Mead Corp Producing manifold carbonless forms
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
CA1104881A (fr) 1977-06-24 1981-07-14 Yu-Sun Lee Methode de production de microcapsules a paroi d'encapsulage secondaires, et microcapsules ainsi obtenues
US4201404A (en) * 1978-05-17 1980-05-06 Minnesota Mining And Manufacturing Company Pressure-sensitive marking materials
US4235458A (en) * 1979-01-08 1980-11-25 The Mead Corporation Process for the production of hot melt coating compositions containing microcapsules

Also Published As

Publication number Publication date
US4371634A (en) 1983-02-01
DE3044113A1 (de) 1982-07-15
DE3164205D1 (en) 1984-07-19
JPS57117337A (en) 1982-07-21
EP0052733A1 (fr) 1982-06-02

Similar Documents

Publication Publication Date Title
EP0026914B1 (fr) Procédé de fabrication de microcapsules, microcapsules obtenues selon ce procédé, utilisation des microcapsules pour la préparation de papiers d'enregistrement sensibles à la pression et système d'enregistrement sensible à la pression
EP0052733B1 (fr) Compositions cireuses contenant des microcapsules, leur préparation et utilisation
EP0218887B2 (fr) Procédé continu de production de dispersions aqueuses de microcapsules avec des parois formées par les produits de condensations de mélamine-formaldéhyde
EP1246693B1 (fr) Dispersions de microcapsules de resines de melamine-formaldehyde, presentant une faible viscosite et une faible teneur en formaldehyde
DE3783806T2 (de) Verfahren zur herstellung von dispersionen von polymerverkapselten farbstoffen bzw. pigmenten.
EP0974394B1 (fr) Dispersion de microcapsules pauvre en formaldéhyde à partir de résines mélamine-formaldehyde
EP0321750B2 (fr) Procédé de fabrication de microcapsules, les microcapsules ainsi préparées et leur utilisation
DE2529427C3 (de) Verfahren zum Herstellen kleiner Polymerkapseln
DE69304990T3 (de) Verfahren zur Herstellung von Mikrokapseln
CH630269A5 (de) Verfahren zum herstellen kleiner polymerkapseln.
DE3346601A1 (de) Loesungsmittelgemisch fuer mikrokapseln
DE1955542C3 (de) Druckempfindliches Blattmaterial
DE1569561A1 (de) Verfahren zum Herstellen von teilchenfoermigen Harzen durch Spruehtrocknen
DE2820600A1 (de) Verfahren zur herstellung von mikrokapsel-beschichtungskompositionen mit pigmentartikeln und daraus hergestellten kompositionen
DE2818976C2 (fr)
DE2926860C2 (de) Verfahren zum Überziehen von dispergierten, feinen Tröpfchen mit einer Membran
DE3131899C2 (fr)
DE1939624B2 (de) Verfahren zur Herstellung von ölhaltigen Mikrokapseln
DE1769932A1 (de) Mikrokapseln und Verfahren zu ihrer Herstellung
DE2135721A1 (de) Wasserbeständiges mikrokapselartiges, hchtundurchlassiges System
DE2233428A1 (de) Verfahren zur einkapselung von in einer fluessigkeit fein verteilten substanzen nach dem spruehkondensationsverfahren
EP0147726A2 (fr) Anti-mousse pour des dispersions aqueuses et des solutions de résines synthétiques
DE4132338C2 (fr)
DE2101156C3 (fr)
DE69502409T2 (de) Verfahren zur herstellung von mit duftstoffen gesättigten oder beschichteten mikroverkapselten trägern

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19811008

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT SE

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB IT LI SE

REF Corresponds to:

Ref document number: 3164205

Country of ref document: DE

Date of ref document: 19840719

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890911

Year of fee payment: 9

Ref country code: CH

Payment date: 19890911

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19890912

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890925

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19891019

Year of fee payment: 9

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19891031

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19901008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19901009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19901016

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19901031

Ref country code: CH

Effective date: 19901031

Ref country code: BE

Effective date: 19901031

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19901031

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910628

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 81108073.8

Effective date: 19910603