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 compositions can be applied as supports by various methods, for example by printing on paper. The solidifying wax binds the microcapsules to the carrier. The dry microcapsules contained by spray-drying the emulsions described in U.S. Patents have diameters of 1 to 50 / um and are therefore not suitable for the production of pressure-sensitive recording materials. The large capsules / destroyed by thick layers when printing or-in coating with about the fifth Large capsules are also partially destroyed in the manufacture of the wax compositions containing microcapsules by the relatively high temperatures and by the shear forces required for homogenization.
• JP-AS 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. Coat with this mass Paper should not discolor during storage in the form set.
• DE-OS 27 19 914 describes pressure-sensitive carbonless copy papers based on wax melts containing microcapsules.
• the wax mass 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 molten wax as 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 about 95 ° C for about 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 'show a high loss in the thermographic analysis.
• DE-OS 28 18 976 also describes hot-meltable wax compositions containing microcapsules.
• the wax compositions are prepared by the process already given in DE-OS 27 19 914, 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.
• DE-OS 28 18 976 and 27 19 914 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.
• DE-OS 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 production of wax compositions containing microcapsules, since the capsules can be separated from the aqueous phase by filtration and 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 application to the carrier material, give strong, sharp copies together with CF layers.
• the CF layers are ormular arrangementsn in F not stained 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 masses according to the present Er Invention can be applied over the whole or part of the surface at the same time or after printing on the substrate by known methods. Clean and distortion-free smooth carrier materials are obtained even if the wax mass 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, of methylolmelamines, of 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. Microcapsules which are obtained by the process of EP-A-26914 are preferred.
• 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 with an increasing proportion of wax (b) and pigment (d). Since the viscosity of the liquid wax composition also increases with increasing content of (a), wax compositions with high contents of (a) take such waxes that provide low-viscosity melts. It was found that small amounts, e.g. 2. up to 10% by weight of water in the melt have a viscosity-reducing effect without disadvantages in use or on the support material such as paper coated with such wax compositions.
• 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. In particular, e.g. to name: 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 improves 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 ( ⁇ ) at least one nonionic emulsifier and (ß) at least one alkali metal salt of montan wax acids, of C 10 - to C 20 fatty alcohol sulfates and / or C 10 - to C 20 alkanesulfonates in the form of the alkali metal salts.
• Suitable nonionic emulsifying agents especially water-soluble ethylene oxide adducts of C 12 have for (c) - to C 20 -Alkano- en l, or C 12 - to C 20 -A l kenolen having from 13 to 30, preferably. 15 to 25 moles of EO per mole of alcohol have been proven.
• alkali metal salts of montan wax acids also called montan acids
• Fatty alcohol sulfates which are salts of the sulfuric acid half-esters of fatty alcohols, include, for example, those derived from decanol, lauryl alcohol (dodecanol-1), tetradecanol-1, hexadecanol-1 (palmityl alcohol), octadecanol-1 ( stearyl alcohol) or technical C. Derive 10/22 , C 12/14 , C 14/28 alkanol mixtures.
• the C 10 - to C 20 -alkanesulfonates are the alkali metal salts of e.g. Decane, dodecane, tridecane, tetradecane, hexadecane and octadecanesulfonic acid or mixtures of C 10/12 -, of C12 / 16-alkanesulfonic acids into consideration.
• 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 emulsifying agents (c) adducts of stearyl alcohol tallow fatty alcohol or partially un- are questionedtigt s s C 16/18 -Alkanolgemischen and 15 to 25 moles of EO per mole of alcohol are particularly preferred.
• (c) are alkali metal salts of montan wax acids and mixtures of ( ⁇ ) nonionic emulsifiers, in particular the abovementioned ones, and ( ⁇ ) alkali metal salts of montan wax acids, of C 10 to C 20 fatty alcohol sulfates and / or C 10 to C 20 alkanesulfonates 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 C16 / 18 alkanols are very particularly preferred because of the particularly good dispersing action .
• 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 agents are intended to prevent the premature unintentional destruction of capsules, for example when the leaves are rubbed against one another.
• pigments for example titanium dioxide, barium sulfate, blanc fixe and as fillers, for example, starch or protein come in the form of granules or spherical particles of urea-formaldehyde condensates having particle diameters from 2 to 20 / to be considered.
• 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.
• Further agents (f) which are customary in wax compositions for the hot-melt process are those for regulating the viscosity. So 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 the 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 ( ⁇ ) nonionic emulsifiers and ( ⁇ ) alkali metal salts of montan wax acids, from C 10 to C 12 fatty alcohol sulfonates and / or C 10 to c 12 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).
• wax compositions containing microcapsules are (c) alkali metal salts of montan wax acids and mixtures of adducts of 15 to 25 moles of ethylene oxide with stearyl alcohol, tallow fatty alcohol and / or on partially unsaturated C 16 / 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. 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. those based on silicone, can be 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.
• one can also proceed in such a way that the components are introduced one after the other and the melt is mixed homogeneously.
• the solid, non-melting components e.g. 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 microcapsules-containing wax compositions, since this provides wax compositions which are practically agglomerate-free in a simple manner.
• 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 masses containing 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. The parts and percentages given below relate 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 approx. 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 for 10 minutes 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 sieve with a mesh size of 40 ⁇ m.
• 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 I.1, but a solution of 180 parts of a water-soluble, partially methylated precondensate (containing approx. 5 OCH 3 groups per melamine molecule) is made from 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 I.4, but the ' same amount of a partially methylated precondensate of melamine-formaldehyde (1: 5.7 mol) with 2.3 CH 3 O groups per melamine molecule is used. Solids content: 38.4%; most common capsule diameter: 5.9 ⁇ m.
• 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.
• a heatable stirred vessel with anchor stirrer and distillation head 80 portions are of a paraffin with a melting point 52 to 54 ° C and 40 parts of a Esterwachses of montanic acid and 1,4-butanediol (melting point 80 to 83 0 C; melting point of the mixture 71 to 78 ° C ) melted at 95 ° C. Then 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 with a vacuum (up to 200 mm Hg) at a bottom temperature of 90 to 95 ° C (duration: 3 h). 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 from the colored lines in the stroke direction.
• Microcapsule dispersion 3 (produced according to I.1) is dried in a spray dryer (gas inlet temperature 120 ° C.) to a free-flowing powder (residual moisture: 4%). 112 parts of the powder are introduced into the wax melt of paraffin, ester wax, petroleum jelly and oxethylation product specified in Example 1 and stirred at 90 ° C. for 1 h.
• 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. Bl), 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 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 under stirring at 90 ° C with 2, 2 parts of the ethylene oxide adduct of Example 1 and 5.95 parts Vaseline (white) and distilled water from 15.3 parts of 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 sample melted and smeared on a slide shows predominantly individual capsules under the microscope.
• 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 I.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 from the mixture at 90 ° C. under reduced pressure in 3.5 h le water withdrawn.
• a melt of 98 parts of paraffin (mp. 69-73 ° C.) and 196 parts of the ester wax from Example 1 is then 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 0 C); Pest content: 92.2%.
• This sheet can e.g. 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.
• microcapsule dispersion 3 (produced according to I.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% aqueous paste and stirred homogeneously.
• the melt contains individual capsules, as well as - some agglomerates. Solid content: 92.8%, viscosity: 130 mPas (85 0 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.
• Example 5.1 71 parts of the powdery microcapsules obtained according to Example 5.1 are slowly poured into a melt of 72 parts of paraffin (mp. 52 to 54 ° C.), 60 parts of ester wax (from montan wax acid and ethylene glycol), 22.5 parts of a 40% aqueous solution of C15 Paraffin sulfonate / sodium salt ( ⁇ 9 g dry), 1 part of the ethylene oxide adduct specified in Example 16.1 and 10 parts of water and stirred in at 90 ° C. for 3 h until homogeneous.
• the melt contains practically only individual capsules. Solids content: 92.8%; Viscosity: 243 mPas (85 ° C), 150 mPas (95 0 C).
• Solids content 93.1% viscosity: 307 mPas (85 ° C); 258 mPas (95 0 C).

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

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• 1980
  • 1980-11-24 DE DE19803044113 patent/DE3044113A1/de not_active Withdrawn
• 1981
  • 1981-10-08 DE DE8181108073T patent/DE3164205D1/de not_active Expired
  • 1981-10-08 EP EP81108073A patent/EP0052733B1/fr not_active Expired
  • 1981-11-09 JP JP56178480A patent/JPS57117337A/ja active Pending
  • 1981-11-16 US US06/321,709 patent/US4371634A/en not_active Expired - Fee Related

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