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
  • B41M5/1243—Inert particulate additives, e.g. protective stilt materials

Definitions

• carbon-free copying systems consist of the top sheet, which is coated on the back with color capsule-containing microcapsules (CB sheet).
• the underlying sheet has a developer layer (CF sheet) on the top.
• CF sheet developer layer
• the microcapsules in the lettering are destroyed, the color former-containing solution runs out and is transferred to the developer layer underneath, in which the color formers develop into color and thus into copy. If several copies or copies are to be obtained, one inserts between these two sheets the microcapsules containing the developer and the color formers on the underside (CFB sheet).
• Self-contained papers contain capsules containing developer and developer in a layer on the surface of the sheet. If capsules containing color balance are destroyed during copying, the color or copy is developed in the same coating.
• the protruding capsules can break and release the color former solution.
• the latter gives a color to the developer layer present and thus leads to the surface of the copy becoming soiled, which can lead to the copy being illegible; i.e. the papers are sensitive to rubbing.
• spacers of the coating containing microcapsules were added at an early stage. The spacers have diameters which are 1.5 to a multiple of the capsule diameter and which therefore protrude from the capsule line and, because of their strength, protect the capsules against unwanted destruction.
• the known spacers have the disadvantage that they also protect the adjacent capsules if they are to be destroyed when they are copied with a pen (ballpoint pen, pencil) or when they are struck with the lathe of the typewriter. It is known that with increasing content of spacing, the copy becomes more difficult to read and its intensity becomes lower. For this reason, a compromise must ultimately be made between the sensitivity to friction of the layer containing the color formers in microencapsulated form and the quality of the copy or the copy intensity.
• the first technically used spacers were short cellulose fibers, also called cellulose fiber cuts. They result in a significant reduction in the sensitivity to friction of the layer containing the encapsulated color formers both in the case of CB and also so-called two-layer papers (self-contained paper).
• the coating compositions containing microcapsules and cellulose fibers were first applied to the paper coating supplements with an air brush as an aqueous coating color on paper and dried.
• This application method has the disadvantage of the lower coating speed.
• doctor blades, roller scrapers and smoothing scrapers are required. It was found that the cellulose fibers to form matted masses e.g. in front of the smoothing scraper and therefore an error-free, even coating of the paper is not possible. At the same time, the cellulose cut accumulates in the Sireich color supply.
• DE-OS 19 15 504 describes the use of particles of starch or starch derivatives as spacers, the size of which is 1.5 to 2 times the size of the microcapsules.
• DE-OS 25 25 901 starch grains with grain sizes from 20 to 75 ⁇ m from different types of peas are suitable as spacers.
• DE-PS 870 837 discloses the use of water-soluble, preferably soy protein particles with 10 to 50% by weight, based on microcapsules.
• EP-A-6599 describes polyolefin powder, optionally together with starch granules, as a spacer for layers containing microencapsulated color formers.
• polyolefins such as polyethylene, polypropylene or polystyrene, and also their copolymers and mixtures with a softening point of at least 70 ° C. in the form of aqueous dispersions, the particles of which have a diameter of 5 to 30 ⁇ m, can be used as spacers will.
• particles of amylose inclusion compounds with diameters of 1.5 to 10 times the microcapsule diameter are suitable as spacers.
• larger microcapsules (3 to 5 ⁇ m), which contain pure solvent, with smaller microcapsules (0.5 to 2.5 ⁇ m), which contain color former solutions, in a ratio of 3: 1 mixed and applied to paper.
• the larger, solvent-only capsules are designed to protect the smaller from accidental destruction. If the larger capsules with the liquid content are destroyed, no discolouration occurs. In the event that all capsules are intentionally destroyed, the color former transfer and thus the development of the color on the CF layer is improved. However, this system has not proven itself. The pressures required to destroy the large capsules are too low, but are usually sufficient to also destroy the color former capsules. In addition, it was found that the additional solvent on middle sheets, i.e.
• the object of the present invention was to provide particles which can be used as spacers and which do not have the disadvantageous properties of the spacers of the prior art.
• microcapsules are used as spacers which contain at least one hydrophobic substance which is solid at room temperature as the core.
• the invention relates to microcapsules which contain in a shell made of a polymer at least one hydrophobic substance which is solid at room temperature and has a melting point of about 40 to 150 ° C.
• microcapsules according to the invention can be used in the form of an aqueous dispersion or as such in the form of powder.
• microcapsules according to the invention can be admixed with the dispersion of the microcapsules containing color formers, a homogeneous dispersion having virtually unchanged rheological properties.
• the microcapsules according to the invention give a significantly to considerably higher color intensity, i.e. a significantly to considerably higher yield of color than when using the same amount of color formers containing microcapsules together with spacers of the prior art.
• microcapsules according to the invention can be used according to all known encapsulation processes . Ren are produced, as far as they can be carried out at temperatures above the melting point of the encapsulated, hydrophobic core material. Examples of suitable processes are: gelatin coacervation, interfacial polycondensation to polyesters or polyamides, interfacial polyaddition to polyureas or polyurethanes, the deposition of polymer films by precipitation from polymer solutions or the homo- and mixed condensation of urea and / or melamine with formaldehyde.
• Encapsulation by polycondensation of melamine with formaldehyde or of precondensates based on melamine-formaldehyde is preferred.
• the suitable water-soluble polymers for example polyvinyl alcohol, salts of polyacrylic acid, copolymers of polymerizable di- or polycarboxylic acids with vinyl isobutyl ether, ethylene and / or (meth) acrylic esters, cellulose derivatives and polymers or copolymers of monomers bearing sulfonic acid groups can be used.
• low molecular weight surface-active substances can also be used to stabilize the resulting capsule dispersion. In some cases you can even do without these water-soluble stabilizers.
• solid hydrophobic sub - punch are those with melting points of about 40 to 150 ° C, preferably those of 50 to 85 ° C, into consideration.
• the hydrophobic substances have penetrometer index values of 0.5 to 200, preferably 1 to 120.
• Waxes or wax-like substances are particularly suitable as solid hydrophobic substances; for example plant waxes that are largely free of higher molecular fatty acids, such as candelilla wax or camauba wax; Hydrocarbon waxes such as paraffins, ozokerite or microcrystalline waxes; higher molecular weight fatty alcohols such as octadecanol or ester waxes, which are free of higher carboxylic acids.
• Wax-like polymers for example polyethylene waxes or preferably polyvinyl ether waxes, can also be used as core material for the microcapsules according to the present invention.
• the waxy substances can be used alone or as a mixture. Mixtures containing low melting substances can also be used. Such mixtures allow the melting point and the penetrometer index, ie the hardness of the wax-like filling, to be varied.
• the hydrophobic substances should be as colorless as possible or only slightly colored.
• the easiest way to determine the plasticity of the waxes is to use the penetrometer index at 20 ° C in accordance with DGF-M-III 3 (standard of the German Society for Fat Science). It should be between 0.5 to 200, preferably between 1 to 120. The values indicate the penetration depth of a needle in 5 seconds in 1/10 mm. The values are identical to those obtained by the needle penetration method according to ASTM-D-1321-61 T.
• the capsules obtained by the above-mentioned processes are isometric or spherical. In terms of shape, they are ideally suited for use on fast-running paper coating systems with e.g. Smooth scrapers can be processed without complications. Due to the fact that the capsules are produced above the melting point of the core material, the wax suffers a considerable volume loss when it cools down and crystallizes out.
• the capsules can be in the form of the aqueous dispersions obtained in the preparation as well as in powder form, e.g. after spray drying or after sieving or centrifuging and drying e.g. in a paddle dryer.
• the application-related advantage of the wax-containing capsules according to the invention is that the capsules are firm and are real spacers due to their firm, waxy consistency of the core at low pressures, such as occur, for example, when stacking papers in a stack or rubbing the papers against one another Act. They protect the microcapsules containing color formers from destruction. At higher pressures, such as occur during writing, the cores of the microcapsules according to the invention can flow or deform or the capsules can be crushed and thus also enable the capsules containing adjacent color formers to be destroyed.
• the size of the spacer capsules in relation to the capsule containing the color former also plays a role.
• the spacer caps reduce the friction sensitivity of the CB layer as the size increases.
• the spacer capsules according to the invention work well when they are 1.5 to 10 times the diameter of the microcapsules containing color formers, ie the distance Switch capsules should have average diameters of 5 to 50 ⁇ m, preferably 6 to 35 ⁇ m and especially 7 to 30 ⁇ m. Spacer capsules that are too large are disadvantageous since they can reduce the sharpness of the copy image.
• the coating color can also be admixed with certain amounts of the hard, non-plastic spacers used hitherto. In this case, one has to accept a decrease in the intensity of the copy or compensate for it by a larger proportion of the capsules containing the color former.
• composition of the coating colors comprising capsules containing binder, binder, spacer capsules and water is not significantly changed by the spacer capsule of the present invention.
• the proportions of the components must be optimized if necessary.
• the previously used coating colors are suitable as binders in the microcapsules: e.g. Polymer dispersions based on homo- and copolymers of vinyl acetate, - (meth) acrylic esters, butadiene, styrene and other ethylenically unsaturated, copolymerizable monomers;
• water-soluble high polymers can be used, optionally together with polymer dispersions.
• the optimal binder can easily be determined by simple series tests.
• the range of the most common capsule diameters is given not according to the microscopic assessment, but the range.
• the mean capsule diameter is the arithmetic mean of the two capsule diameters specified.
• the sheet coated according to A.1) is placed with the coated side on a CF sheet. 2 layers of paper of approx. 40 g / m 2 are placed on top. This stack is clamped in an electric typewriter and with the greatest keystroke a field of 4.2 x 3.4 cm is written with the letter small w, the letters in the line directly next to one another and the lines being arranged one above the other. After 30 minutes of storage, the intensity - (ID) of the copy obtained on the fourth sheet is determined as the difference in the reflection of the blank (Ry o ) and the described (Ry m ) CF sheet. The reflection was measured in a reflection photometer with the filter Y (Elrepho @, from Zeiss).
• the reflection of the blank white CF sheet is generally 85%.
• the sheet coated according to A.1) - minimum length: 29 cm - is placed with the coated side up on a flat surface made of synthetic leather that has been sanded on both sides.
• a CF sheet is placed on top with the slave layer facing down to the capsule-bearing layer.
• a metal disc 50 mm in diameter and 8 mm in thickness is carefully placed on the CF sheet at one end.
• the disc has an equal-sized, 2 mm thick felt cover on the lower side.
• Weight per slice 1000 g.
• the arrangement loads the paper surface with a pressure of 2.1 N / cm2 .
• the CF sheet is now touched at the end and slowly, by hand, together with the weight on it, is pulled exactly 22 cm far over the capsule-bearing paper with the CB layer. The weight is carefully removed. Under the contact surface, the CF paper is more or less discolored depending on the friction sensitivity of the CB line. The intensity (IR) of the discoloration is measured with the reflection photometer as in A2) and given in relative units (%).
• the sharpness of the lettering and the associated legibility of the copy was subjectively determined in comparison with the sharpness of commercially available carbonless papers. It was good in all cases and comparable to the paper available on the market. The sharpness did not become worse with increasing amount of spacer capsules. It is therefore not noted in the examples.
• paraffin melting point 69 to 73 ° C., penetrometer index 9
• the speed of the toothed disk stirrer is slowly increased to the final value of 4500 rpm with increasing filling level.
• 252 g of a clear solution of 120 g of a partially methylated precondensate (containing about 2.3 CH 2 O groups per melamine molecule) of 1 mol of melamine and 5.25 mol of formaldehyde in 132 g of water are then added in one hour .
• the temperature is kept at 76 ° C.
• the dispersion obtained is colorless, milky and, according to microscopic assessment, contains' individual capsules, predominantly 8 to 18 ⁇ m in diameter, individual ones Capsules have a maximum diameter of 40 ⁇ m.
• the solids content is 41.0% (determined by drying a sample at 105 ° C. for 2 hours).
• a capsule dispersion with capsules with a common diameter of 10 to 25 ⁇ m is obtained.
• Individual capsules have a diameter of up to a maximum of 40 .mu.m after microscopic measurement.
• the solids content of the dispersion is 38.0%.
• These capsules also have a large round dent in their spherical surface.
• a capsule dispersion is obtained, the capsules of which have a common diameter of 8 to 18 ⁇ m. Individual capsules have a diameter of up to a maximum of 40 ⁇ m. Solids content: 43.0%. The capsules have a larger dent in their spherical surface.
• the procedure was as in Example 3, but the disk stirrer was set to 2500 rpm.
• the resulting capsule dispersion has a solids content of 45.2%.
• the spherical capsules have a common diameter of 10 to 45 ⁇ m. Their surface is very slightly roughened and has 1 to 2 deep dents in the spherical surface (diameter of the dent 70 to 80% of the sphere diameter, measured on the sphere surface).
• Example 3 The procedure was as in Example 3, but the disk stirrer was set to 6500 rpm. After the pre-condensate had been added, the speed of rotation of the disk stirrer was reduced to 5000 rpm. Then 81.5 g of the 20% solution of poly-2-acrylamido-2-methylpropanesulfonic acid / sodium salt used in Example 1 were added in 2 minutes, and then 252 g of the clear solution containing 120 g of the one given in Example 1 were partially added methylated precondensates from melamine and formaldehyde. The stirrer was then switched off, the dispersion was added to the flask equipped with a propeller stirrer and worked up further as in Example 1.
• a capsule dispersion was obtained, the capsules of which contain twice the amount of wall material and which have a common diameter of 2 to 8 ⁇ m. Individual capsules have a diameter of up to 12 ⁇ m (according to microscopic assessment). Solids content: 41.4%.
• Example 5 The procedure was as in Example 5, but the speed of the disk stirrer during the capsule formation was 5500 rpm. Towards the end of the addition of the precondensate, it was raised to 6000 rpm.
• the mixture was stirred at 2500 rpm.
• microcapsule dispersion containing color formers indicated below was processed to coating compositions without spacers and the spacer capsules of Examples 1 to 6 and with spacers of the prior art according to A1.a) and applied to paper according to A1.b).
• the applied weight was determined on the coated papers obtained, and the intensity of the copy according to A2) and the sensitivity to rubbing according to A3).
• microcapsule dispersion containing color former used was prepared according to EP-B-26 914, Example 1, but a mixture of dodecylbenzene and diisopropylbenzene in a weight ratio of 1: 1 was used as the solvent for the color former.
• the capsule provides blue copies.
• the most common diameter of the capsule is 2 to 5 u.m. Solids content: 40%.
• the spherical spacers with diameters of 2 to 8 microns are only slightly larger than the capsules containing color formers used with 2 to 5 ⁇ m in diameter, so that the spacer capsules cannot protect the latter on the uneven paper surface in all cases from possible destruction when rubbing.
• the comparison of the IR values shows that spacer capsules of 10 to 25 ⁇ m in diameter show the best protective effect. This diameter comes very close to the dimensions of the commercially available spacer cellulose cut with a width of 5 to 15 ⁇ m and a length of 20 to 60 ⁇ m, but above all the special thickness K with a diameter of 20 to 30 ⁇ m.
• the order for microcapsules containing color formers drops to approx. 2/3.
• the capsules according to the invention containing paraffin not only significantly reduce the sensitivity to friction of the CB layer, but also allow the use of smaller amounts of microcapsules containing color formers, with practically the same intensity of copy.
• Microcapsules containing color formers were the same as in C.I. used.
• Microcapsules produced according to Example 2 were used as spacers.
• Capsule lines were prepared from the capsules obtained after both experiments in accordance with A.1). For comparison, a capsule coating was made with cellulose-cut fiber. A capsule containing black copies with a most common diameter of 3 to 6 ⁇ m was used as the capsule containing color formers (produced according to EP-B-26 914, example 6).
• Vaseline (white, DAB, penetrometer index> 200) is encapsulated according to the information in Example 3.
• the speed of rotation of the disc stirrer was 4000 rpm.
• the resulting capsule dispersion has a solids content of 44.4%.
• the capsules are spherical with a single dent from time to time. The most common diameter was 5 to 15 ⁇ m.
• the capsule dispersions and cellulose fiber cut (Arbocel B 600/15) obtained according to Comparative Example 2 and Example 3.1 were used as spacers for the production of CB coating colors according to A.1) and the papers obtained were tested according to A.2) and A.3).
• the microcapsule dispersion specified under C.I was used as the microcapsule containing color formers.
• the values for the sensitivity to friction show that the soft, pasty petroleum jelly in encapsulated form is not able to protect the capsules containing color formers from being destroyed. Your sensitivity to friction is high; IR 31%. In comparison, the paraffin-containing capsule has an IR value: Both capsules resist the destruction of the color former capsules when writing less resistance than the cellulose fiber cut, so that the intensity of the copy is significantly higher than that of the cellulose cut (49 and 50 instead of 45%).
• Example 3 The procedure is as in Example 3, but a mixture of 35 parts of paraffin with a melting point of 69 to 73 ° C. (penetrometer index: 9) and 66 parts of petroleum jelly (white, DAB, penetrometer index> 200) is used.
• the mixture has a melt index of 52 to 54 ° C and a penetrometer index of 100.
• Speed of rotation of the disc stirrer 4000 rpm.
• the result is a dispersion with a solids content of 44.6% and spherical capsules of the most common diameter from 5 to 18 u.m. The capsules show significant dents, 1 to 2 per capsule.
• the capsule coating produced according to A1.a) and A1.b) has a total application weight of 7.4 glm 2 .
• the values correspond to those obtained with cellulose cut as a spacer.
• the feed time of the melamine-formaldehyde precondensate was 30 minutes.
• a mixture of 60 parts of paraffin (melting point 69 to 73 ° C.) and 34 parts of petroleum jelly (white, DAB, penetrometer index> 200) was encapsulated.
• the mixture has a melting point of 55 to 62 ° C and a penetrometer index of 41.
• the resulting dispersion had a solids content of 43.0% and contains spherical capsules with 1, rarely 2 distinct dents with a common diameter of 10 to 30 ⁇ m.
• the capsule (CB) line produced according to A1.a) and A1.b) has an application weight of 7.4 g / m 3 .
• Example 3 The procedure is as in Example 3, but instead of paraffin octadecanol with a melting point of 59 ° C. and a penetrometer index of 2 to 3 is used. So that a melt is present, it was encapsulated at 65 ° C. The disc stirrer runs at 3000 rpm. A capsule dispersion with a solids content of 44.4% was obtained. The spherical capsules have a diameter of 5 to um and have 1 or 2 larger dents in their surface.
• Capsule coats according to A1.a) and Ab) were produced with these capsules using the microcapsules containing color formers specified under CI.
• Total coating weight 7.5 g / m 2.
• a colorless, milky dispersion with a solids content of 46.9% was obtained, which contains spherical capsules with a common diameter of 6 to 18 ⁇ m.
• the capsules have 1 to 2 clear, deep dents in their surface.
• the high-speed stirrer turned at 6000 rpm.
• the spherical capsules had a common diameter of 8 to 30 ⁇ m and at least one significant dent.
• Example 11 The procedure was as in Example 11, but a relatively soft, yellowish microcrystalline hydrocarbon wax (Ozokerit GS 2115) - (melting point 66 to 70 ° C., penetrometer index 24) was encapsulated.
• Ozokerit GS 2115 melting point 66 to 70 ° C., penetrometer index 24
• the colorless, cloudy dispersion has a solids content of 46.3%.
• the spherical capsules have a common diameter between 4 and 24 ⁇ m and all have at least one indentation.
• the spread produced according to A1.a) and A1.b) has a total weight of 7.6 g / m 2 .
• Example 3 The procedure is as in Example 3, but instead of the paraffin a colorless polyvinyl ether wax (M.G. melting point 45 to 48 ° C; penetrometer index from 0 to 1) is encapsulated.
• the disc stirrer rotates at 5000 rpm.
• the resulting colorless, milky dispersion has a solids content of 43.6%.
• the capsules contained therein have a common diameter of 20 to 45 ⁇ m, individual capsules up to 100 ⁇ m.
• the surface of the spherical capsules is rough and shows a small indentation.
• the resulting dispersion is transferred to a glass flask with a propeller stirrer (propeller diameter 1/3 of the cross-section of the container) at a speed of 1200 rpm, in which 360 g of water at 60 ° C. had previously been placed, and the pH slowly became 10% Formic acid reduced to 4.8 within 40 minutes.
• the dispersion is then sieved through a sieve with a mesh size of 1 mm without any significant residue.
• the solids content is 12.0%.
• the paraffin-containing capsules are spherical with a clearly indented surface and have a diameter of 10 to 30 ⁇ m.
• Example 14 The procedure is as in Example 14, but instead of 50 g of pork skin gelatin and 25 g of gum arabic, 29.0 g of pork skin gelatin and 3.2 g of a carboxymethyl cellulose (Tylose C 1000 from Kalle) were used. Instead of the disk stirrer, a Turrax 45 N from Jahnke & Kunkel with a speed of 8000 rpm is used for the dispersion.
• the CB coating produced according to A1.a) and A1.b) with these agglomerated capsules has a total application weight of 7.4 g / m 2 .
• a polyacrylic acid / sodium salt K value according to Fikentscher: 165
• the thin, colorless, milky dispersion has a solids content of 23.8%.
• the spherical, individual microcapsules show dents in the surface and have a common diameter between 12 and 36 ⁇ m.
• the CB coating produced according to A1.a) and A1.b) with this paraffin-containing microcapsule as a spacer has a total coating weight of 7.6 g / m 2 .
• Example 16 is repeated with the following change: 957 g of water and 142 g of the solution of the polyacrylic acid / sodium salt are introduced, then 800 g of molten paraffin are introduced and 252 g of the precondensate solution are used for the encapsulation. A low-viscosity dispersion with a solids content of 44.7% and spherical, slightly indented capsules (most common diameter: 6 to 30 ⁇ m) was obtained.
• Example 17 is repeated, but instead of the solution of 142 g of polyacrylic acid / sodium salt (15%), a solution of 32 g of a copolymer of vinyl methyl ether and maleic anhydride (1: 1 parts by weight; K value according to Fikentscher: 90, corresponding to a molecular weight 100,000) as the sodium salt in 111 g of water.
• the toothed disk stirrer has a rotation speed of 5000 rpm.
• the slightly viscous dispersion obtained has a solids content of 40.3%. It contains spherical, slightly dented capsules with a common diameter of 6 to 24 ⁇ m.
• Example 17 The procedure is as in Example 17, but the solution of the polyacrylic acid / sodium salt is replaced by 83 g of water (i.e. no water-soluble high polymer is used).
• the rotational speed of the. Toothed disk stirrer is 6000 rpm.
• the dispersion obtained was sieved through a sieve with a mesh size of 350 ⁇ m and had a solids content of 43.1%. It contains spherical capsules with slight dents, which have a common diameter of 15 to 45 ⁇ m.
• the CB line made according to A1.a) and A1.b) has a total application weight of 7.3 g / m 2 .
• Example 19 The procedure is as in Example 19, but the pH is adjusted to 4.5 and the precondensate is added at 5000 rpm in the course of an hour.
• the dispersion obtained has a solids content of 45.1% and contains slightly indented spherical capsules with a common diameter of 3 to 12 ⁇ m.
• the CB coating produced according to A1.a) and A1.b) has a total coating weight of 7.5 g / m 2 .
• Example 1 is repeated, but the toothed-disk stirrer was operated at 80 ° C. and 3000 rpm.
• the capsules containing blue color were used as color formers by C.I. used.
• the sensitivity to friction also decreases with all spacers. The decrease is about the same for starch and cellulose pulp, but is enormous for paraffin capsules.
• Table 7 shows the copying intensities and sensitivity to rubbing of CB lines with different capsules containing paraffin as spacers depending on the amount of spacers in the CB line.
• the intensity of the copy obtained drops somewhat as the number of spacers increases.
• Melting point and penetrometer index have a hardly discernible influence.
• With increasing amount of paraffin spacer capsules the sensitivity to friction sometimes decreases very significantly.

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Citations (5)

• 1985
  • 1985-04-06 DE DE19853512565 patent/DE3512565A1/de not_active Withdrawn
• 1986
  • 1986-03-25 FI FI861265A patent/FI861265A/fi not_active Application Discontinuation
  • 1986-03-29 EP EP86104337A patent/EP0197470A3/fr not_active Withdrawn
  • 1986-04-03 BR BR8601503A patent/BR8601503A/pt unknown
  • 1986-04-04 AU AU55661/86A patent/AU5566186A/en not_active Abandoned
  • 1986-04-04 ES ES553746A patent/ES553746A1/es not_active Expired

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