CA1212021A - Tagging means for finely dispersed systems - Google Patents
Tagging means for finely dispersed systemsInfo
- Publication number
- CA1212021A CA1212021A CA000445420A CA445420A CA1212021A CA 1212021 A CA1212021 A CA 1212021A CA 000445420 A CA000445420 A CA 000445420A CA 445420 A CA445420 A CA 445420A CA 1212021 A CA1212021 A CA 1212021A
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- oxide
- tagging
- quantities
- salt
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/008—Tagging additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor
Abstract
ABSTRACT
A tagging means containing ferromagnetic con-stituents, optionally fluorescent pigments, microanalytically detectable quantities of soluble and insoluble fluorescent materials, colored pigments, oxides and/or salts of rare metals as well as oxides and/or poorly soluble salts of rare earths embedded in an uncured thermoplastic resin poly-acrylates, polyester or polymer epoxide powder varnish base, are produced by homogeneously incorporating the components into the melting thermoplastic resin, cooling and pulverizing the mixture to a fine particle size.
A tagging means containing ferromagnetic con-stituents, optionally fluorescent pigments, microanalytically detectable quantities of soluble and insoluble fluorescent materials, colored pigments, oxides and/or salts of rare metals as well as oxides and/or poorly soluble salts of rare earths embedded in an uncured thermoplastic resin poly-acrylates, polyester or polymer epoxide powder varnish base, are produced by homogeneously incorporating the components into the melting thermoplastic resin, cooling and pulverizing the mixture to a fine particle size.
Description
The present invention relates to a tagging means, specifically for the tagging of finely dispersed systems, allowing an identification of the material used with res-pect to its origin and its composition and, optionally, with the aid of microanalytical methods, the date of its production In other aspects, the invention relates to the process for the production of such tagging means and their use, specifically for the tagging of finely dispersed substances.
The increase in thefts and illegal use of explosives has led to the necessity of being able to offer clear proof of the type and, optionally, of the date of production of explosives. A number of tagging means have already been proposed or put on the market. Tagging means for explosives are described, for example in U.S. patents 4,053,4~3, 3,772,200; 3,897,28~, 4,131,064; 4,197,10~, ~,961,106;
3,967,9gO and 3,993,838. Canadian Patent Application S.~.
420,563 filed January 31, 1983, Wolfgang Weller et al, describes further improved tagging means, which are ferro-magnetic components as well as, optionally, fluorescent pigments, soluble and insoluble fluorescent materials, colored pigments, oxides and/or salts of rare earth elements as well as oxides and~or only soluble salts of rare earths in micro-analytically readily detectable quantities embedded in high molecular, thermoplastically processible polymers produced by the homogeneous melting of the components, granulation and pulverization.
It has now been found that a widespread need for tagging means exists not only for explosives but also for a number of other substances. Finely dispersed systems, specifically finely pulverized substances of high effectiveness or high value and, --1-- ~s~
~6,i specifically, of high quality standards, should be tagged in such a way that it is possible to determine at a later date whether they are the original substances. In a number of instances, it is even desirable to be able later to deter-mine, as in the case of explosives, not only the manufacturer, but also the dates of production and packing. finely pulverized substances of this type are, e.g., herbicides, pesticides, fertilizers and even finely dispersed systems such as high-quality special varnishes, etc.
The tagging means used for explosives are unsuit-able for such purposes since they are too coarsely grained and cannot, even with the aid of special technologies, such as pulverization using liquid nitrogen or by solution/pre cipitation processes, be dispersed with adequate fineness.
The plastics taught as tagging means for explosives, such as polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoxymethylenes or acrylonitrile-butadiene-styrene copolymers, cannot be pulverized even at extremely low temperatures, e.g. under liquid nitrogen, to the desired granulation magnitudes of less than 50 em, preferably less than 20 em.
The problem to be solved is the making of tagging means for finely dispersed systems, which can be both readily and economically produced and pulverized to homogeneous particles of less than 50 em in size and preferably smaller than 20 em. The tagging means must also be resistant to water and moisture, yet should be capable of being easily separated from the finely powdered substances and of being unequivocally identified by microanalysis.
It has now been found that the uncured polymer com-ponents of powder varnishes having a polyacrylate, polyester ~z~
or polymer epoxide base are excellently suited for use as materials which can be thermoplastically processed so as to disperse and/or embed in their melt iron or ferromagnetic alloy powder as well as the other substances easily identified by microanalysis. The melt, containing the ore substances, after cooling can be pulverized to particle sizes of less than 50 em, preferably even to less than 20 em.
The tagging means of the present invention consists essentially of a) at least 1 weight percent of iron or ferro-magnetic alloy/powder, and microanalytically detectable quantities of at least two of the following substances:
b) fluorescent pigments, c) organic solvent soluble, water insoluble fluorescent material, d) colored pigment, e) difficultly soluble oxide cr salt of a rare metal and f) oxide or difficultly soluble salt of a rear earth;
homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide base powder varnish.
In the process for the production of the tagging means according to the invention, the polyacrylate, polyester or polymer epoxide uncured powder varnish, a material capable of being thermoplastically processed, is heated and substances a) through f) are introduced into the resultant melt and homo-geneously mixed, the mixture cooled and granulated, finely pulverized and, optionally, the finer grains separated from the coarser grained material by air classification.
The iron powder and/or powder of ferromagnetic alloy must be present in quantities of at least 1%, so that the tagging means can be extracted from the finely pulverized substances with the help of magnets. As a general rule, quantities of 3-20 weight percent of ferromagnetic material are employed. Quantities of 5-12 weight percent have proven to be particularly effective.
For unequivocal coding and decoding of the tagging means according to the invention, at least two of the follow-ing substances: fluorescent pigments, fluorescent materials, colored pigments, oxides and/or salts of rare metals as well as oxides and/or rare earth salts of very low solubility must be present. The greater the number of substances used, the greater is the variability and the greater the ease with which an unequivocal determination of the producer, date and com-position of the tagged material mixture can be made. To enable good microanalysis of these substances in the tagging means according to the invention, these should be present in the following quantities:
b) fluorescent pigments, of from 0.1 to 8 weight percent, preferably 2 to 5 weight percent, c) fluore.scent materials, of from 0.1 to 5 weight percent, preferably 1 to 3 weight percent, d) colored pigments, of from 0.5 to 8 weight percent, preferably 1 to 5 weight percent, e) oxides and/or salts of rare metals, of 0.5 to 8 weight percent, preferably 1 to 5 weight percent, f) oxides and/or salts of rare earths, of 0.5 to 5 weight percent, preferably 1 to 3 weight percent.
The fluorescent pigments should be insoluble in water and organic solvents9 while the fluorescent materials, though insoluble in water, should be soluble in organic solvents. This allows these different substances to be separated readily from each other and to be analytically determined independently of one another. The colored pigments, oxides and/or salts of rare metals and oxides and/or difficultly solubLe salts or rare earths should be insoluble in water and in organic solvents so that they rernain as a residue in all instances and can be analytically identified side by side without equivocation.
To distribute the various substance groups homo-geneously in the tagging medium according to the invention, they must be introduced into the melt of the polymers and intensively mixed. For this purpose, mixing devices with extremely good shearing and kneading effect have proven effective. Single-screw extruders are less suitable for the purpose. Twin-screw extruders are suitable if they develop high shearing forces. What haveproved effective are, e.g., the twin-screw kneader, Model ZSK of the firm of Werner &
Pfleiderer of Stuttgart or the planetary rolling extruder, Model EKK of the firm of Battenfelt in ~ochum. The batch operating positive mixer of the Banbury type also appears to be suitable. The homogeneous mixtures were then granulated along a cooling conveyor and breaker. The fragmented granulates should preferably exhibit diameters of less than 15 mm.
The granulates should exhibit edge lengths of pre-ferably 2 to 6 mm. Granulates of this type can be pulverized without difficultly to powders with a grain size of less than 50 em, preferably even smaller than 20 em. Only such finely ground powders which can optionally be freed from coarser grains by air classification, can, e.g. be sprayed with powdered herbicides and insecticides in the form of suspensions from pressure containers, without leading to dissociation or even clogging the spraying systems. Since herbicides and insecticides generally have a particle size range of 50 em, preferably even less than 20 em, the tagging material accord-ing to the invention, must also be of the same fine particle size. For the tagging of varnish systems also9 it is necessary that extremely finely ground particles be used, since varnish systems partially exhibit layer thicknesses of 20 em. Of course7 the constituents of the tagging means must also be correspondingly fine grained; thus the iron powder should exhibit a maximal grain size of lO em. The other components as well should be correspondingly finely pulverized and be worked into the mixture with fine dis-tribution.
Exhaustive tests have shown that none of the common thermoplastic materials suitable for the production of` tagging means for explosives, are suitable for tagging means of finely dispersed systems. The high molecular plastics such as poly-ethylenes, polypropylenes, polyamides, po~ycarbonates, poly-esters, polyoxymethylenes and acrylonitrile butadiene styrene-copolymers cannot, either at normal temperatures or under liquid nitrogen, be pulverized to tagging means of such fine granulation as would be required.
Surprisingly, however, powder varnishes with an uncured polyacrylate, polyester or polymer epoxide base are suitable both for thermoplastic processing and Jo incorporate at the same time all of the components of the tagging means into a homogeneous mixture and to permit extremely fine pul-verization of the rehardened mixture. The uncured polymer components of powder varnishes with a polyacrylatel polyester or polymer epoxide base, while they can be procured as such from their manufacturers, are normally used only together with a second or crosslinking component. Such crosslinking com-ponents should not be present in the compositions of the pre-:12~LZ~21 sent invention since they convert the thermoplastic polymers on heating into duromers. Also, these relatively low mole- ¦
cularly crosslinking components can react with the finely pulverized substances to be tagged to give undesired by-pro-ducts. Thus, using uncured polymer components of powder varnishes having a polyacry]ate, polyester or polymer epoxide base for the production of tagging means for finely dispersed systems constitutes a totally unusual and seemingly inappro-priate use of these polymers.
Testing of the polymers, and the tagging means pro-duced from them according to the invention, indicated, through differential thermoanalysis, that these polymers all exhibit a distinct vitreous transition point in the range of 50-80C.
In addition, these thermoplasts having melting points in the range between 90 and 130C. They are, therefore, individually and collectively with the other components, easily extruded, and, after solidification at room temperature, easily and simply pulverized to extremely fine powders.
The characteristic data of the polymer used under the conditions of the differential thermoanalysis can be cited as an additional criterion for the identification and decoding of the tagging means.
The abundantly present ferromagnetic components serve, as discussed above, for locating and separating the proposed tagging means according to the invention from the finely dispersed systems. Iron powders with a maximal particle size of less than 10 em have been shown to be parti-cularly effective as ferromagnetic materia]s. Iron powders of this type are commercially available, e.g., from the firm of E. MERCK, Darmstadt. In principle, however, all other ferromagnetic alloys are suitable if available in 12~ZIL~21 sufficently fine powder form. If these allows should contain relatively rare alloy components, they can also, in principle, still be used for identification and decoding.
In principle, all pigments can be used as fluorescent pigments which can be clearly distinguished from each other by their fluorescence spectrum and their inherent color. Examples oF suitable fluorescent pigments are those of the firm of Industrial Colours Ltd., of England under the designation FLARE* 910, orange, green and yellow commercial pigments or the LUMILUX* C-luminescent pigments of the firm of Riedel-de Haen AG. As fluorescent materials, all types can be employed which can be dissolved from the tagging means with the aid of organic solvents. The fluorescent materials should preferably be insoluble in water so that they cannot be dis-solved away in advance from the tagging means by water.
Examples of suitable fluorescent materials are the products sold by the Ciba firm under the designations UVITEX*
OB, UVITEX* 127 and UVITEX* OB-P and by the ICI firm under the designations FLUOLITE* XNR and FLUOLITE* XMP. As colored pigments, all adequately insoluble and heat-stable pigments can be employed, whose emission spectrum can be clearly identified. Suitable colored pigments are, e.g. Sicoplast*
Yellow 12-0190 and Sicoplast* Red 32-0300, as well as the pig-ments sold by the ICI firm under the designation Waxoline*, with the colors blue, ruby-red, green and yellow.
As difficultly soluble and heat-stable oxides and/or salts of rare metals, e.g., titanium oxide, copper oxide, zinc oxide, strontium carbonate, cadmium sulfide, antimony trioxide, barium sulfate, lanthanum trioxide and bismuth tri-oxide can be used. As oxides and/or difficultly soluble salts* trade marks ~z~
of the rare earths, cerium (IV) oxide as well as the other oxides or oxalates, of the lanthanides can be used.
Additionally, heat-stable oxides of low solubility and/or salts of al7 metals were used sing7y or in combination, as long as they could be identified unequivocally 'Dy micro-analysis, e.g., by X-ray fluorescence spectroscopy.
In the following examples a number of typical embodiments of the tagging means according to the invention are described. All indications of percentage herein are 10 weight percentages.
Example 1 15.2 kg acrylate resin ~74.9%) 1.5 kg iron powder (10.0%) 1.2 kg fluorescent pigment ( 8.0%) 0.5 kg lanthanum (III) oxide ( 3.5%) 006 kg antimony trioxide ( 3.6%) are introduced as dry powders in a fluid mixer of the ~enschel type with a volume of 75 L and an rpm of the mixing device of 1600 and mixed for 1 minute. This mixture is poured into the charging container of a twin-screw kneader of the type Werner & Pfleiderer ZDK 57 M 50 and homogenized at a screw rpm of 250 and a mass temperature range of 110-130C. The homogenized product is discharged and granulated along a conveyor cooling installation with a crusher. The fragmented granulate is pul-verized in a pulverization apparatus of the type Micropul ACM
60 at a carrier gas temperature of maximally 35C quantitatively to a maximal particle size of 60 em. The product has a particle size distribution of` from 30 to 60 em with a mean weight value of 12 em and a percentile of 86% 20 em. After subsequent air classification in a Walther-Industrie vortex-type separator of the Model 250, 70% of product with a clean L
upper particle limit of 20 em is separated.
The ingredients used in Example 1 were:
Acrylate re _ :
L.umitol LR 8655, an acrylate resin containing hydroxyl groups, with a DSC temperature of 62 - 64~C and a hydroxyl number of 78.2 mg KOG/g. Lumitol is a trademark of the BASF firm, West Germany.
Iron powder:
3819 with a maximal grain size of 10 mm and a purity of 99.5%. 3819 is a type designation of the MERCK
firm, West Germany.
Fluorescent pigment:
Flare 910 yellow 27, yellow inherent color. Flare is a trade mark of the firm of Industrial Colours Ltd., England.
Cerium (IV) oxide:
A product of the firm of MERCK, West Germany, with a purity of 99.9%.
TIMGNOX - WHITE STAR with a purity of 99%. TIMONOX
WHITE STAR is a trade mark of the firm of ASSOCIATED LEAD
Manufacturers Ltd., England.
Example 2 The following dry, powdered components were intro-duced into a plough bar mixer of the model Leodige FM 130 D
with a volume of 130 L and an rpm of the mixer of 1,000, mixed for 3 minutes and then poured into the charging con-tainer of a planetary roller extruder of the type Battenfeld -EKK PDE 100 EV, subsequently homogenized at a screw rpm of 30 and a mass temperature of 90 - 120C and extruded and granu-lated along a cooling belt with a crusher.
22.4 kg acrylate resin (74.9%) 3.0 kg iron powder ~10.0%)
The increase in thefts and illegal use of explosives has led to the necessity of being able to offer clear proof of the type and, optionally, of the date of production of explosives. A number of tagging means have already been proposed or put on the market. Tagging means for explosives are described, for example in U.S. patents 4,053,4~3, 3,772,200; 3,897,28~, 4,131,064; 4,197,10~, ~,961,106;
3,967,9gO and 3,993,838. Canadian Patent Application S.~.
420,563 filed January 31, 1983, Wolfgang Weller et al, describes further improved tagging means, which are ferro-magnetic components as well as, optionally, fluorescent pigments, soluble and insoluble fluorescent materials, colored pigments, oxides and/or salts of rare earth elements as well as oxides and~or only soluble salts of rare earths in micro-analytically readily detectable quantities embedded in high molecular, thermoplastically processible polymers produced by the homogeneous melting of the components, granulation and pulverization.
It has now been found that a widespread need for tagging means exists not only for explosives but also for a number of other substances. Finely dispersed systems, specifically finely pulverized substances of high effectiveness or high value and, --1-- ~s~
~6,i specifically, of high quality standards, should be tagged in such a way that it is possible to determine at a later date whether they are the original substances. In a number of instances, it is even desirable to be able later to deter-mine, as in the case of explosives, not only the manufacturer, but also the dates of production and packing. finely pulverized substances of this type are, e.g., herbicides, pesticides, fertilizers and even finely dispersed systems such as high-quality special varnishes, etc.
The tagging means used for explosives are unsuit-able for such purposes since they are too coarsely grained and cannot, even with the aid of special technologies, such as pulverization using liquid nitrogen or by solution/pre cipitation processes, be dispersed with adequate fineness.
The plastics taught as tagging means for explosives, such as polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoxymethylenes or acrylonitrile-butadiene-styrene copolymers, cannot be pulverized even at extremely low temperatures, e.g. under liquid nitrogen, to the desired granulation magnitudes of less than 50 em, preferably less than 20 em.
The problem to be solved is the making of tagging means for finely dispersed systems, which can be both readily and economically produced and pulverized to homogeneous particles of less than 50 em in size and preferably smaller than 20 em. The tagging means must also be resistant to water and moisture, yet should be capable of being easily separated from the finely powdered substances and of being unequivocally identified by microanalysis.
It has now been found that the uncured polymer com-ponents of powder varnishes having a polyacrylate, polyester ~z~
or polymer epoxide base are excellently suited for use as materials which can be thermoplastically processed so as to disperse and/or embed in their melt iron or ferromagnetic alloy powder as well as the other substances easily identified by microanalysis. The melt, containing the ore substances, after cooling can be pulverized to particle sizes of less than 50 em, preferably even to less than 20 em.
The tagging means of the present invention consists essentially of a) at least 1 weight percent of iron or ferro-magnetic alloy/powder, and microanalytically detectable quantities of at least two of the following substances:
b) fluorescent pigments, c) organic solvent soluble, water insoluble fluorescent material, d) colored pigment, e) difficultly soluble oxide cr salt of a rare metal and f) oxide or difficultly soluble salt of a rear earth;
homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide base powder varnish.
In the process for the production of the tagging means according to the invention, the polyacrylate, polyester or polymer epoxide uncured powder varnish, a material capable of being thermoplastically processed, is heated and substances a) through f) are introduced into the resultant melt and homo-geneously mixed, the mixture cooled and granulated, finely pulverized and, optionally, the finer grains separated from the coarser grained material by air classification.
The iron powder and/or powder of ferromagnetic alloy must be present in quantities of at least 1%, so that the tagging means can be extracted from the finely pulverized substances with the help of magnets. As a general rule, quantities of 3-20 weight percent of ferromagnetic material are employed. Quantities of 5-12 weight percent have proven to be particularly effective.
For unequivocal coding and decoding of the tagging means according to the invention, at least two of the follow-ing substances: fluorescent pigments, fluorescent materials, colored pigments, oxides and/or salts of rare metals as well as oxides and/or rare earth salts of very low solubility must be present. The greater the number of substances used, the greater is the variability and the greater the ease with which an unequivocal determination of the producer, date and com-position of the tagged material mixture can be made. To enable good microanalysis of these substances in the tagging means according to the invention, these should be present in the following quantities:
b) fluorescent pigments, of from 0.1 to 8 weight percent, preferably 2 to 5 weight percent, c) fluore.scent materials, of from 0.1 to 5 weight percent, preferably 1 to 3 weight percent, d) colored pigments, of from 0.5 to 8 weight percent, preferably 1 to 5 weight percent, e) oxides and/or salts of rare metals, of 0.5 to 8 weight percent, preferably 1 to 5 weight percent, f) oxides and/or salts of rare earths, of 0.5 to 5 weight percent, preferably 1 to 3 weight percent.
The fluorescent pigments should be insoluble in water and organic solvents9 while the fluorescent materials, though insoluble in water, should be soluble in organic solvents. This allows these different substances to be separated readily from each other and to be analytically determined independently of one another. The colored pigments, oxides and/or salts of rare metals and oxides and/or difficultly solubLe salts or rare earths should be insoluble in water and in organic solvents so that they rernain as a residue in all instances and can be analytically identified side by side without equivocation.
To distribute the various substance groups homo-geneously in the tagging medium according to the invention, they must be introduced into the melt of the polymers and intensively mixed. For this purpose, mixing devices with extremely good shearing and kneading effect have proven effective. Single-screw extruders are less suitable for the purpose. Twin-screw extruders are suitable if they develop high shearing forces. What haveproved effective are, e.g., the twin-screw kneader, Model ZSK of the firm of Werner &
Pfleiderer of Stuttgart or the planetary rolling extruder, Model EKK of the firm of Battenfelt in ~ochum. The batch operating positive mixer of the Banbury type also appears to be suitable. The homogeneous mixtures were then granulated along a cooling conveyor and breaker. The fragmented granulates should preferably exhibit diameters of less than 15 mm.
The granulates should exhibit edge lengths of pre-ferably 2 to 6 mm. Granulates of this type can be pulverized without difficultly to powders with a grain size of less than 50 em, preferably even smaller than 20 em. Only such finely ground powders which can optionally be freed from coarser grains by air classification, can, e.g. be sprayed with powdered herbicides and insecticides in the form of suspensions from pressure containers, without leading to dissociation or even clogging the spraying systems. Since herbicides and insecticides generally have a particle size range of 50 em, preferably even less than 20 em, the tagging material accord-ing to the invention, must also be of the same fine particle size. For the tagging of varnish systems also9 it is necessary that extremely finely ground particles be used, since varnish systems partially exhibit layer thicknesses of 20 em. Of course7 the constituents of the tagging means must also be correspondingly fine grained; thus the iron powder should exhibit a maximal grain size of lO em. The other components as well should be correspondingly finely pulverized and be worked into the mixture with fine dis-tribution.
Exhaustive tests have shown that none of the common thermoplastic materials suitable for the production of` tagging means for explosives, are suitable for tagging means of finely dispersed systems. The high molecular plastics such as poly-ethylenes, polypropylenes, polyamides, po~ycarbonates, poly-esters, polyoxymethylenes and acrylonitrile butadiene styrene-copolymers cannot, either at normal temperatures or under liquid nitrogen, be pulverized to tagging means of such fine granulation as would be required.
Surprisingly, however, powder varnishes with an uncured polyacrylate, polyester or polymer epoxide base are suitable both for thermoplastic processing and Jo incorporate at the same time all of the components of the tagging means into a homogeneous mixture and to permit extremely fine pul-verization of the rehardened mixture. The uncured polymer components of powder varnishes with a polyacrylatel polyester or polymer epoxide base, while they can be procured as such from their manufacturers, are normally used only together with a second or crosslinking component. Such crosslinking com-ponents should not be present in the compositions of the pre-:12~LZ~21 sent invention since they convert the thermoplastic polymers on heating into duromers. Also, these relatively low mole- ¦
cularly crosslinking components can react with the finely pulverized substances to be tagged to give undesired by-pro-ducts. Thus, using uncured polymer components of powder varnishes having a polyacry]ate, polyester or polymer epoxide base for the production of tagging means for finely dispersed systems constitutes a totally unusual and seemingly inappro-priate use of these polymers.
Testing of the polymers, and the tagging means pro-duced from them according to the invention, indicated, through differential thermoanalysis, that these polymers all exhibit a distinct vitreous transition point in the range of 50-80C.
In addition, these thermoplasts having melting points in the range between 90 and 130C. They are, therefore, individually and collectively with the other components, easily extruded, and, after solidification at room temperature, easily and simply pulverized to extremely fine powders.
The characteristic data of the polymer used under the conditions of the differential thermoanalysis can be cited as an additional criterion for the identification and decoding of the tagging means.
The abundantly present ferromagnetic components serve, as discussed above, for locating and separating the proposed tagging means according to the invention from the finely dispersed systems. Iron powders with a maximal particle size of less than 10 em have been shown to be parti-cularly effective as ferromagnetic materia]s. Iron powders of this type are commercially available, e.g., from the firm of E. MERCK, Darmstadt. In principle, however, all other ferromagnetic alloys are suitable if available in 12~ZIL~21 sufficently fine powder form. If these allows should contain relatively rare alloy components, they can also, in principle, still be used for identification and decoding.
In principle, all pigments can be used as fluorescent pigments which can be clearly distinguished from each other by their fluorescence spectrum and their inherent color. Examples oF suitable fluorescent pigments are those of the firm of Industrial Colours Ltd., of England under the designation FLARE* 910, orange, green and yellow commercial pigments or the LUMILUX* C-luminescent pigments of the firm of Riedel-de Haen AG. As fluorescent materials, all types can be employed which can be dissolved from the tagging means with the aid of organic solvents. The fluorescent materials should preferably be insoluble in water so that they cannot be dis-solved away in advance from the tagging means by water.
Examples of suitable fluorescent materials are the products sold by the Ciba firm under the designations UVITEX*
OB, UVITEX* 127 and UVITEX* OB-P and by the ICI firm under the designations FLUOLITE* XNR and FLUOLITE* XMP. As colored pigments, all adequately insoluble and heat-stable pigments can be employed, whose emission spectrum can be clearly identified. Suitable colored pigments are, e.g. Sicoplast*
Yellow 12-0190 and Sicoplast* Red 32-0300, as well as the pig-ments sold by the ICI firm under the designation Waxoline*, with the colors blue, ruby-red, green and yellow.
As difficultly soluble and heat-stable oxides and/or salts of rare metals, e.g., titanium oxide, copper oxide, zinc oxide, strontium carbonate, cadmium sulfide, antimony trioxide, barium sulfate, lanthanum trioxide and bismuth tri-oxide can be used. As oxides and/or difficultly soluble salts* trade marks ~z~
of the rare earths, cerium (IV) oxide as well as the other oxides or oxalates, of the lanthanides can be used.
Additionally, heat-stable oxides of low solubility and/or salts of al7 metals were used sing7y or in combination, as long as they could be identified unequivocally 'Dy micro-analysis, e.g., by X-ray fluorescence spectroscopy.
In the following examples a number of typical embodiments of the tagging means according to the invention are described. All indications of percentage herein are 10 weight percentages.
Example 1 15.2 kg acrylate resin ~74.9%) 1.5 kg iron powder (10.0%) 1.2 kg fluorescent pigment ( 8.0%) 0.5 kg lanthanum (III) oxide ( 3.5%) 006 kg antimony trioxide ( 3.6%) are introduced as dry powders in a fluid mixer of the ~enschel type with a volume of 75 L and an rpm of the mixing device of 1600 and mixed for 1 minute. This mixture is poured into the charging container of a twin-screw kneader of the type Werner & Pfleiderer ZDK 57 M 50 and homogenized at a screw rpm of 250 and a mass temperature range of 110-130C. The homogenized product is discharged and granulated along a conveyor cooling installation with a crusher. The fragmented granulate is pul-verized in a pulverization apparatus of the type Micropul ACM
60 at a carrier gas temperature of maximally 35C quantitatively to a maximal particle size of 60 em. The product has a particle size distribution of` from 30 to 60 em with a mean weight value of 12 em and a percentile of 86% 20 em. After subsequent air classification in a Walther-Industrie vortex-type separator of the Model 250, 70% of product with a clean L
upper particle limit of 20 em is separated.
The ingredients used in Example 1 were:
Acrylate re _ :
L.umitol LR 8655, an acrylate resin containing hydroxyl groups, with a DSC temperature of 62 - 64~C and a hydroxyl number of 78.2 mg KOG/g. Lumitol is a trademark of the BASF firm, West Germany.
Iron powder:
3819 with a maximal grain size of 10 mm and a purity of 99.5%. 3819 is a type designation of the MERCK
firm, West Germany.
Fluorescent pigment:
Flare 910 yellow 27, yellow inherent color. Flare is a trade mark of the firm of Industrial Colours Ltd., England.
Cerium (IV) oxide:
A product of the firm of MERCK, West Germany, with a purity of 99.9%.
TIMGNOX - WHITE STAR with a purity of 99%. TIMONOX
WHITE STAR is a trade mark of the firm of ASSOCIATED LEAD
Manufacturers Ltd., England.
Example 2 The following dry, powdered components were intro-duced into a plough bar mixer of the model Leodige FM 130 D
with a volume of 130 L and an rpm of the mixer of 1,000, mixed for 3 minutes and then poured into the charging con-tainer of a planetary roller extruder of the type Battenfeld -EKK PDE 100 EV, subsequently homogenized at a screw rpm of 30 and a mass temperature of 90 - 120C and extruded and granu-lated along a cooling belt with a crusher.
22.4 kg acrylate resin (74.9%) 3.0 kg iron powder ~10.0%)
2.4 kg fluorescent pigment ( 8.0%~
1.0 kg lanthanum (III) oxide ( 3.5%) 1.2 kg antimony trioxide ( 3.5%) The fragmented granulate obtained in this way waspulverized in accordance with Example 1 to an end fineness of 50 em, a means weight value of 8.5 em and a percentage of 88%
below 15 em. By air classification with a Donaldson air classifier of the model Accucut C-24, 70% of a powder with clean upper grain limit of 15 em was separated out.
The materials used in Example 2 were:
Epoxy resin:
Epikote 1004, an epoxy resin with a DSC peak temperature of 62 and an epoxy equivalent weight of 805 -940 g. Epikote is a trade mark of the firm of SHELL, Chemistry, England.
Iron powder, fluorescent pigment lanthanum ~III) oxide, antimony trioxide:
-Materials as in Example 1.
Example 3 Using essentially the process of Example 2 (maximumextruder temperature of 135C), a fragment granulate is pro-duced from the following dry, powdered components and pul-verized to an upper grain limit of 80 em. The product has a mean weight value of 18 em and a percentage of 84% 30 em. 77%
of a powder with a clean upper grain limit of 30 em is separated out:
2~
15.0 polyester resin (74.9%) 2.0 kg iron powder (10.0%~
1.6 kg fluorescent pigment ( 8.0%~
0.7 kg lanthanum (III~ oxide ( 3.5%~
0.7 kg antimony trioxide ( 3.6%~
The materials used in Example 3 were:
Polyester resin:
Crylcoat 280, a polyester resin containing hydroxyl groups and having a flow rate/ASTM D 1238, A of 10 g/min, and a hydroxyl number of 50 mg KOH/g. Crylcoat is a brand name of the UCB, Specialties Chemical Division, Belgium.
Iron powder, fluorescent pigment, lanthanum (III~ oxide, antimony trioxide:
_ Materials as in Example 1.
The yield in Examples 1, 2 and 3 can be increased by mixing the coarse grains precipitated during air classifi-cation with the next batch of granulate so that it undergoes pulverization once again.
1.0 kg lanthanum (III) oxide ( 3.5%) 1.2 kg antimony trioxide ( 3.5%) The fragmented granulate obtained in this way waspulverized in accordance with Example 1 to an end fineness of 50 em, a means weight value of 8.5 em and a percentage of 88%
below 15 em. By air classification with a Donaldson air classifier of the model Accucut C-24, 70% of a powder with clean upper grain limit of 15 em was separated out.
The materials used in Example 2 were:
Epoxy resin:
Epikote 1004, an epoxy resin with a DSC peak temperature of 62 and an epoxy equivalent weight of 805 -940 g. Epikote is a trade mark of the firm of SHELL, Chemistry, England.
Iron powder, fluorescent pigment lanthanum ~III) oxide, antimony trioxide:
-Materials as in Example 1.
Example 3 Using essentially the process of Example 2 (maximumextruder temperature of 135C), a fragment granulate is pro-duced from the following dry, powdered components and pul-verized to an upper grain limit of 80 em. The product has a mean weight value of 18 em and a percentage of 84% 30 em. 77%
of a powder with a clean upper grain limit of 30 em is separated out:
2~
15.0 polyester resin (74.9%) 2.0 kg iron powder (10.0%~
1.6 kg fluorescent pigment ( 8.0%~
0.7 kg lanthanum (III~ oxide ( 3.5%~
0.7 kg antimony trioxide ( 3.6%~
The materials used in Example 3 were:
Polyester resin:
Crylcoat 280, a polyester resin containing hydroxyl groups and having a flow rate/ASTM D 1238, A of 10 g/min, and a hydroxyl number of 50 mg KOH/g. Crylcoat is a brand name of the UCB, Specialties Chemical Division, Belgium.
Iron powder, fluorescent pigment, lanthanum (III~ oxide, antimony trioxide:
_ Materials as in Example 1.
The yield in Examples 1, 2 and 3 can be increased by mixing the coarse grains precipitated during air classifi-cation with the next batch of granulate so that it undergoes pulverization once again.
Claims (12)
1. Tagging means consisting essentially of a) at least 1 weight percent of iron or ferromagnetic alloy powder, and microanalytically detectable quantities of at least two of the following substances:
b) fluorescent pigment, c) organic solvent soluble, water insoluble, fluorescent material, d) colored pigment, e) difficultly soluble oxide or salt of a rare metal, f) oxide or difficultly soluble salt of a rare earth;
homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide based powder varnish.
b) fluorescent pigment, c) organic solvent soluble, water insoluble, fluorescent material, d) colored pigment, e) difficultly soluble oxide or salt of a rare metal, f) oxide or difficultly soluble salt of a rare earth;
homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide based powder varnish.
2. Tagging means in accordance with claim 1, wherein the homogeneous mixture is granulated and finely pulverized.
3. Tagging means in accordance with claim 2, wherein the particle size after pulverization is smaller than 50 µm.
4. Tagging means in accordance with claim 3, wherein the particle size is less than 20 µm.
5. Tagging means in accordance with claim 1, wherein a) the iron or ferromagnetic alloy powder is present in quantities of between 3 to 20 weight percent, and the other substances, when present, are present in the following quantities:
b) fluorescent pigment of 0.1 to 8 weight percent, c) fluorescent material 0.1 to 5 weight percent, d) colored pigment 0.5 to 8 weight percent, e) oxide or salt of rare metal 0.5 to 8 weight percent, and f) oxide or salt of rare earth, 0.5 to 5 weight percent.
b) fluorescent pigment of 0.1 to 8 weight percent, c) fluorescent material 0.1 to 5 weight percent, d) colored pigment 0.5 to 8 weight percent, e) oxide or salt of rare metal 0.5 to 8 weight percent, and f) oxide or salt of rare earth, 0.5 to 5 weight percent.
6. A process for the production of tagging means con-sisting essentially of a) at least 1 weight percent of iron or ferromagnetic alloy powder and microanalytically quantities of at least two of the following substances:
b) fluorescent pigment, c) organic solvent soluble, water insoluble, fluorescent material, d) colored pigment, e) difficultly soluble oxide or salt of a rare metal, f) oxide or difficultly soluble salt of a rare earth homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide powder varnish base, which com-prises melting the thermoplastic varnish base dispering sub-stances a) through f) in the melt to form a homogeneous mixture, cooling the mixture, granulating the cooled mixture, and finely pulverizing the granulate.
b) fluorescent pigment, c) organic solvent soluble, water insoluble, fluorescent material, d) colored pigment, e) difficultly soluble oxide or salt of a rare metal, f) oxide or difficultly soluble salt of a rare earth homogeneously mixed in an uncured thermoplastic polyacrylate, polyester or polymer epoxide powder varnish base, which com-prises melting the thermoplastic varnish base dispering sub-stances a) through f) in the melt to form a homogeneous mixture, cooling the mixture, granulating the cooled mixture, and finely pulverizing the granulate.
7. A process in accordance with claim 5, wherein the particle size after pulverization is smaller than 50 µm.
8. A process according to claim 7, wherein the coarser grains after pulverization are separated by air classification.
9. A process in accordance with claim 6, wherein a) the iron or ferromagnetic alloy powder is present in quantities of from 3 to 20 weight percent and, the following substances, when present, are present in the indicated quantities:
b) fluorescent pigment 0.1 to 8 weight percent, c) fluorescent material 0.1 to 5 weight percent, d) colored pigment, 0.5 to 8 weight percent, e) oxide or salt of rare metal 0.5 to 8 weight percent, and f) oxide or salt of rare earth in quantities of 0.5 to 5 weight percent.
b) fluorescent pigment 0.1 to 8 weight percent, c) fluorescent material 0.1 to 5 weight percent, d) colored pigment, 0.5 to 8 weight percent, e) oxide or salt of rare metal 0.5 to 8 weight percent, and f) oxide or salt of rare earth in quantities of 0.5 to 5 weight percent.
10. A tagging composition particulate consisting essen-tially of a homogeneous mixture of a) at least 1 weight percent of iron or ferromagnetic alloy powder; and b) microanalytically detectable quantities of at least two of the following substances:
(1) an organic solvent-insoluble, water-insoluble fluorescent pigment, (2) an organic solvent-soluble, water-insoluble fluorescent material, (3) a colored pigment, (4) a difficultly soluble oxide or salt of a metal selected from the group consisting of titanium, copper, zinc, strontium, cadmium, antimony, barium, lanthanum, and bismuth, and (5) an oxide or difficultly soluble salt of a rare earth c) in a thermoplast polymer having a vitreous transi-tion point of 50° to 80°C, a melting point of 90° to 130°C, and selected from the group consisting of an uncured thermo-plastic polyacrylate varnish, an uncured polyester varnish, and an uncured polymer epoxide-based powder varnish, wherein components a) and b) are homogeneously mixed in a melt of said polymer and the resulting composition is cooled, granulated, and finely pulverized to give a tagging composi-tion particulate having a particle size smaller than 50 µm.
(1) an organic solvent-insoluble, water-insoluble fluorescent pigment, (2) an organic solvent-soluble, water-insoluble fluorescent material, (3) a colored pigment, (4) a difficultly soluble oxide or salt of a metal selected from the group consisting of titanium, copper, zinc, strontium, cadmium, antimony, barium, lanthanum, and bismuth, and (5) an oxide or difficultly soluble salt of a rare earth c) in a thermoplast polymer having a vitreous transi-tion point of 50° to 80°C, a melting point of 90° to 130°C, and selected from the group consisting of an uncured thermo-plastic polyacrylate varnish, an uncured polyester varnish, and an uncured polymer epoxide-based powder varnish, wherein components a) and b) are homogeneously mixed in a melt of said polymer and the resulting composition is cooled, granulated, and finely pulverized to give a tagging composi-tion particulate having a particle size smaller than 50 µm.
11. The tagging composition particulate of claim 10 having a particle size smaller than 20 µm.
12. The tagging composition particulate of claim 10 wherein said iron or ferromagnetic alloy powder a) is present in a quantity of 3 to 20 weight percent and the other components, when present, are present in the follow-ing quantities:
b) (1): 0.1 to 8 weight percent, b) (2): 0.1 to 5 weight percent, b) (3): 0.5 to 8 weight percent, b) (4): 0.5 to 8 weight percent, and b) (5): 0.5 to 5 weight percent.
b) (1): 0.1 to 8 weight percent, b) (2): 0.1 to 5 weight percent, b) (3): 0.5 to 8 weight percent, b) (4): 0.5 to 8 weight percent, and b) (5): 0.5 to 5 weight percent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3301357.8 | 1983-01-18 | ||
| DE3301357A DE3301357C1 (en) | 1983-01-18 | 1983-01-18 | Marking agents, processes for their preparation and their use for marking finely dispersed systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1212021A true CA1212021A (en) | 1986-09-30 |
Family
ID=6188458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000445420A Expired CA1212021A (en) | 1983-01-18 | 1984-01-17 | Tagging means for finely dispersed systems |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0118667B1 (en) |
| JP (1) | JPS59155756A (en) |
| AT (1) | ATE24060T1 (en) |
| AU (1) | AU570025B2 (en) |
| BR (1) | BR8400194A (en) |
| CA (1) | CA1212021A (en) |
| DE (2) | DE3301357C1 (en) |
| ES (1) | ES8503713A1 (en) |
| FI (1) | FI74721C (en) |
| IL (1) | IL70692A (en) |
| NO (1) | NO840161L (en) |
| PT (1) | PT77968B (en) |
| ZA (1) | ZA84335B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470502A (en) * | 1989-10-11 | 1995-11-28 | Basf Aktiengesellschaft | Fluorescent pigments |
| US6097291A (en) * | 1996-01-19 | 2000-08-01 | 3M Innovative Properties Company | Electronic article surveillance markers for direct application to optically recorded media |
| WO2005054132A1 (en) * | 2003-12-05 | 2005-06-16 | Orica Australia Pty Ltd | Tagged polymeric materials and methods for their preparation |
| AU2004294360B2 (en) * | 2003-12-05 | 2011-06-09 | Duluxgroup (Australia) Pty Ltd | Tagged polymeric materials and methods for their preparation |
| US8575240B2 (en) | 2009-12-18 | 2013-11-05 | Construction Research & Technology Gmbh | Method for qualitatively and quantitatively identifying bulk goods |
| US10807304B2 (en) | 2008-11-20 | 2020-10-20 | Eos Gmbh Electro Optical Systems | Method for identifying laser sintering powders |
| EP3714020B1 (en) * | 2017-11-24 | 2023-09-06 | Tesa Se | Producing a pressure-sensitive adhesive mass on the basis of acrylonitrile-butadiene rubber |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6099150A (en) * | 1983-11-03 | 1985-06-03 | Mitsubishi Rayon Co Ltd | Resin composition containing rare earth element and its manufacture |
| JPS6422987A (en) * | 1987-07-20 | 1989-01-25 | Sinloihi Co Ltd | Light-emitting material |
| DE4242992B4 (en) * | 1992-12-18 | 2004-01-29 | Meto International Gmbh | Arrangement for securing an article, in particular a recording disk such as a CD disk |
| DE19907697A1 (en) | 1999-02-23 | 2000-08-24 | Giesecke & Devrient Gmbh | Security element with optically variable material for documents of value additionally comprises at least one machine readable distinguishing material which does not impair the effect of the optically variable material |
| AU7904200A (en) * | 1999-09-15 | 2001-04-17 | Dynamit Nobel Gmbh | Munition |
| DE19962953B4 (en) * | 1999-12-24 | 2006-01-26 | Bundesdruckerei Gmbh | Method for coding thermoplastic products |
| JP2002332414A (en) * | 2001-03-06 | 2002-11-22 | Masaya Fukui | Polymer material, and method, system and device for identifying the same |
| GB0228421D0 (en) * | 2002-12-05 | 2003-01-08 | Exosect Ltd | Lipid carriers |
| DE10350024A1 (en) * | 2003-10-27 | 2005-05-25 | Metallwerk Elisenhütte GmbH | Cartridge with detection-relevant doping |
| DE102006031534A1 (en) * | 2006-07-07 | 2008-01-10 | Fachhochschule Münster | Process for the identification of plastics |
| ITMO20100165A1 (en) * | 2010-06-08 | 2011-12-09 | Eugenio Cavallini | ANTI-COUNTERFEITING METHOD APPLIED TO PLASTIC AND PLASTIC PRODUCTS INGLOBANTE AN ANTI-COUNTERFEITING CODE OF AUTHENTICATION. |
| RU2609224C1 (en) * | 2012-06-06 | 2017-01-31 | Акционерное общество "СИПЕКС" | Explosive marking method |
| JP6054255B2 (en) * | 2013-06-10 | 2016-12-27 | アラム株式会社 | Rubber or synthetic resin moldings and food processing plants |
| CN105403607B (en) * | 2015-11-28 | 2017-12-01 | 浙江大学 | A kind of New Carbon Paste Electrode for adulterating Polyferric Sulfate and its preparation method and application |
| RU2637334C2 (en) * | 2016-05-16 | 2017-12-04 | Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" | Marking additive |
| DE102017103780A1 (en) | 2017-02-23 | 2018-08-23 | Tailorlux Gmbh | Method for identifying a material or material mixture |
| DE102019219469A1 (en) * | 2019-12-12 | 2021-06-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing a labeled polymer, marker, use of the marker and labeled polymer |
| DE102020120318A1 (en) | 2020-07-31 | 2022-02-03 | Ruag Ammotec Ag | Identifiable projectile and method of manufacture |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897284A (en) * | 1971-04-30 | 1975-07-29 | Minnesota Mining & Mfg | Tagging explosives with organic microparticles |
| US4131064A (en) * | 1977-07-15 | 1978-12-26 | Westinghouse Electric Corp. | Tagging particles which are easily detected by luminescent response, or magnetic pickup, or both |
| ATE18818T1 (en) * | 1982-02-02 | 1986-04-15 | Coathylene Sa | MARKING AGENTS, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN MARKING EXPLOSIVES. |
-
1983
- 1983-01-18 DE DE3301357A patent/DE3301357C1/en not_active Expired
-
1984
- 1984-01-14 AT AT84100349T patent/ATE24060T1/en not_active IP Right Cessation
- 1984-01-14 EP EP84100349A patent/EP0118667B1/en not_active Expired
- 1984-01-14 DE DE8484100349T patent/DE3461569D1/en not_active Expired
- 1984-01-16 IL IL70692A patent/IL70692A/en not_active IP Right Cessation
- 1984-01-17 PT PT77968A patent/PT77968B/en unknown
- 1984-01-17 BR BR8400194A patent/BR8400194A/en unknown
- 1984-01-17 CA CA000445420A patent/CA1212021A/en not_active Expired
- 1984-01-17 AU AU23542/84A patent/AU570025B2/en not_active Expired - Fee Related
- 1984-01-17 FI FI840172A patent/FI74721C/en not_active IP Right Cessation
- 1984-01-17 NO NO840161A patent/NO840161L/en unknown
- 1984-01-17 JP JP59006995A patent/JPS59155756A/en active Pending
- 1984-01-17 ZA ZA84335A patent/ZA84335B/en unknown
- 1984-01-17 ES ES528912A patent/ES8503713A1/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470502A (en) * | 1989-10-11 | 1995-11-28 | Basf Aktiengesellschaft | Fluorescent pigments |
| US6097291A (en) * | 1996-01-19 | 2000-08-01 | 3M Innovative Properties Company | Electronic article surveillance markers for direct application to optically recorded media |
| WO2005054132A1 (en) * | 2003-12-05 | 2005-06-16 | Orica Australia Pty Ltd | Tagged polymeric materials and methods for their preparation |
| AU2004294360B2 (en) * | 2003-12-05 | 2011-06-09 | Duluxgroup (Australia) Pty Ltd | Tagged polymeric materials and methods for their preparation |
| US10807304B2 (en) | 2008-11-20 | 2020-10-20 | Eos Gmbh Electro Optical Systems | Method for identifying laser sintering powders |
| US8575240B2 (en) | 2009-12-18 | 2013-11-05 | Construction Research & Technology Gmbh | Method for qualitatively and quantitatively identifying bulk goods |
| EP3714020B1 (en) * | 2017-11-24 | 2023-09-06 | Tesa Se | Producing a pressure-sensitive adhesive mass on the basis of acrylonitrile-butadiene rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2354284A (en) | 1984-07-19 |
| DE3461569D1 (en) | 1987-01-15 |
| PT77968A (en) | 1984-02-01 |
| FI74721C (en) | 1988-03-10 |
| JPS59155756A (en) | 1984-09-04 |
| EP0118667B1 (en) | 1986-12-03 |
| FI74721B (en) | 1987-11-30 |
| DE3301357C1 (en) | 1984-08-16 |
| EP0118667A1 (en) | 1984-09-19 |
| IL70692A0 (en) | 1984-04-30 |
| ES528912A0 (en) | 1985-03-01 |
| ES8503713A1 (en) | 1985-03-01 |
| BR8400194A (en) | 1984-08-21 |
| ATE24060T1 (en) | 1986-12-15 |
| AU570025B2 (en) | 1988-03-03 |
| FI840172A0 (en) | 1984-01-17 |
| PT77968B (en) | 1986-04-21 |
| NO840161L (en) | 1984-07-19 |
| IL70692A (en) | 1987-03-31 |
| ZA84335B (en) | 1984-09-26 |
| FI840172A (en) | 1984-07-19 |
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