CN1964995A - method of marking material - Google Patents
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- CN1964995A CN1964995A CNA200580018047XA CN200580018047A CN1964995A CN 1964995 A CN1964995 A CN 1964995A CN A200580018047X A CNA200580018047X A CN A200580018047XA CN 200580018047 A CN200580018047 A CN 200580018047A CN 1964995 A CN1964995 A CN 1964995A
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- unsaturated monomer
- ethylenically unsaturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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Abstract
The invention relates to a method for marking materials with coded particles, wherein the coded particles are obtainable by: polymerizing at least one water-soluble monoethylenically unsaturated monomer by inverse water-in-oil suspension polymerization in the presence of at least one ethylenically unsaturated monomer having at least two double bonds in the molecule, wherein doped nanoparticles are used as suspension medium, (ii) emulsion polymerization of water-insoluble monoethylenically unsaturated monomers with 0 to 10% by weight, based on the monomer mixture, of at least one ethylenically unsaturated monomer having at least two double bonds in the molecule, wherein doped nanoparticles are used as emulsifiers for stabilizing the disperse phase, (iii) at least one ethylenically unsaturated monomer is polymerized together with a copolymerizable dye having an ethylenically unsaturated double bond, and optionally the particles are aggregated, or (iv) aggregating at least two groups of particles differing in their absorption, emission and/or scattering of electromagnetic radiation to obtain aggregates having an average particle size of from 300nm to 500 μm. The invention also relates to the use of the encoded particulate marking material and to the material marked with the particulate.
Description
The present invention relates to a kind of method with the encoding microsomal marker material.
US-A-3,772,099 discloses by with potassium silicate aqueous solution blended phosphor such as commercially available luminescent material in small, broken bits with the lanthanide-doped luminophore in small, broken bits of at least a periodictable, and with mixture drying, grinding and screening and with the explosive substance Methods for Coding.So the granularity of the aggregation that forms is 0.5-0.7mm, and the granularity of luminescent material is 6-8 μ m.This aggregation for example can mix with explosive substance in the process that reaches explosive is received in preparation carefully.The amount that is low to moderate 0.01 weight % just is enough to the mark explosive substance.Even after blast, based on sample collected, the spectral line of emission that can launch for example be exposed to UV-light the time by the luminescent material of coding and differentiate the explosive substance of mark by this way.Owing to mix, there are a large amount of possible combinations, thereby can determine with manufacturer, production year, the moon and the week of multiple adulterated luminescent material with the explosive substance of suitable method mark by different luminescent materials.
US-A-4,390,452 disclose and have been used to review the encoding microsomal of differentiating the material that comprises this encoding microsomal.According to DE-A-26 51 528 instructions, this encoding microsomal is used visually differentiable color layers by basad film in succession, and obtain on the surface of mixture, to produce extremely thin layer by diazotisation methods, wherein owing to be exposed to the UV-light of injecting this layer by the positive that comprises micro-data (microdata), but the numerical value and the symbol of microscopic evaluation have appearred after developing.Produced the particulate that is not more than 1000 μ m and has two flat parallel surfaces by coating, described surface comprises numerical value and the symbol of using.Particulate is used for mark substance such as explosive substance, to review origin and the production data that detects product.
WO-A-03/044276 relates to a kind of safety paper and security article with at least a safety element, this safety element is based at least a photoluminescence fragment of mixing paper product to small part, and wherein said paper product are made up of dried fiber of 30-99 weight % and 70-1 weight % filler.Safety element for example can be by producing with photoluminescence dye coloring cellulosic fibre base material.If safety element is exposed under the light that wavelength is 200-500nm, then can sees photoluminescence.
WO-A-03/052025 discloses the printing-ink that comprises nano particle that is used for ink-jet printer or piezoelectricity printing press.The diameter of nano particle is 1-1000nm and has crystalline structure.They mainly comprise doped metal salt, for example use the adulterated YVO of euridium
4Nano particle or with the adulterated LaPO of cerium
4Nano particle.The also available multiple element doping of nano particle is for example used cerium and terbium doped LaPO
4Use this printing-ink, for example can be false proof with the banknote of its printing.
WO-A-02/46528 discloses and will be used for safe mark and be applied to base material such as paper, pottery or polymkeric substance as coating, wherein the base-material of coating comprise diameter be the fluorescent particle of 0.2-2 μ m and with it the diameter distinguished of optics be the discrete particles of 10-20 μ m.When detecting by an unaided eye, coating shows uniform color, but when observing under high resolving power, can be the particle of 0.2-2 μ m based on color differentiating discrete particles and diameter.
US-B-6,620,360 disclose the method that a kind of production is used for mark and is used to differentiate the multilayer particulate of the material that comprises these multilayer particulates subsequently.Particulate is produced by use a plurality of thin and visually differentiable mark layers in succession to flat substrates, and before using down one deck, the thickness of mark layer is less than 4.5 μ m to 1 μ m after mark layer becomes solid.Remove flat substrates then and with the mixture grind into powder of mark layer.
US-B-6,455,157 disclose will at least two kinds not on the same group particulate be used for marked product, the particulate of each group comprises a plurality of color layers that form coding.By these particulate graduated encoding products, thereby for example can on marked product, detect manufacturer and product numerical value.
At Chem.Commun., 2002, among the 1435-1441, B.J.Battersby, G.A.Lawrie, A.P.R.Johnston and M.Trau have reported with fluorescence dye, nanocrystal and the metal colloidal suspension liquid of optically encoding.The colloid that so for example with diameter is 3-6 μ m is by mixing fluorescence dye or the mark optically with complex form bonded lanthanon.Mark colloidal another kind method is to mix the zinc sulphide with cadmium selenide nano crystal or be electrochemical deposition of metal ion in the colloid cavity.For example can colloid be distinguished mutually by fluorescent microscope or hematimeter.
The objective of the invention is further provides mark for material.
According to the present invention, this purpose realizes by a kind of method with the encoding microsomal marker material, wherein uses the encoding microsomal that can obtain by the following method:
(i) make at least a water-soluble mono ethylenically unsaturated monomer at least a molecule, have the polymerization by anti-phase water-in-oil suspension polymerization in the presence of the ethylenically unsaturated monomer of at least two two keys, wherein adulterated nano particle be used as suspension medium,
(ii) make the water-insoluble monoene belong to unsaturated monomer and based on monomer mixture be the ethylenically unsaturated monomer letex polymerization that has at least two two keys at least a molecule of 0-10 weight %, wherein adulterated nano particle is used for the stable dispersion phase as emulsifying agent
But (iii) make at least a ethylenically unsaturated monomer with copolymerization dyestuff polymerization with ethylenical unsaturated double bonds, and if suitable these particle aggregations that makes,
Or
(iv) make at least two groups different particles agglomerate aspect its absorption, emission and/or scattered electromagnetic radiation, to obtain the aggregate that median size is 300nm-500 μ m.
For example, will be used for according to (i) and polymerization (ii) with dyestuff or with the adulterated nano particle of compound doped or radioactivity of the rare earth element that is selected from periodictable at least.
The median size of the polymer beads that can obtain by the polymerization according to (i) for example is 0.1-1000 μ m, preferred 0.5-50 μ m.Usually, the median size according to the particulate of (i) preparation is 1-20 μ m.Wherein nano particle is prepared granular polymer as suspension medium by anti-phase water-in-oil suspension polymerization (ISP) method and for example be disclosed in US-A-2, the 982,749, the 1st hurdle the 21st walks in the 6th hurdle the 34th row.It is this that to have low hydrophile-lyophile balance (be that the HLB value is less than 7, preferably less than 4) silica, wilkinite or the clay of the example of the suspension medium silanization that to be each handled with quaternary ammonium compound, and organic nanometer granule such as partly sulfonated polyvinyltoluene or with the chlorovinyl toluene polymkeric substance of dimethylamine reaction.For the definition of HLB value with reference to W.C.Griffin, Journal of the Societyof Cosmetic Chemists, the 1st volume, 311 (1950).
Other nano particle that is suitable as suspension medium is CaCO
3, BaSO
4, barium titanate, SiO
2The oxide compound of alkaline-earth metal and transition metal, sulfide, phosphoric acid salt and pyrophosphate salt, especially zinc oxide, titanium dioxide, ferric oxide (pyrrhosiderite, rhombohedral iron ore), iron sulphide and barium pyrophosphate, and other polymer beads such as polystyrene or polyacrylic ester, and the mixture of the mixture of two or more nano particles such as zinc oxide and titanium dioxide.The median size of nano particle for example is 5-500nm, usually 20-300nm.
For ISP, be disclosed in R.Aveyard with the summary of colloidal solid and other suspension medium stable emulsion, B.P.Binks and J.H.Clint, Advances in Colloid and InterfaceScience, the 100-102 volume is in the 503-546 page or leaf (2003).This External Reference publication: E.Vignati and R.Piazza, Langmuir, the 19th volume, the 17th phase, 6650-6656 (2003), the publication of on Pickeringemulsions.To be used for ISP and before polymerization, use dyestuff, preferred fluorescence dye, the rare earth element of periodictable or its compound, or radioactive compound or radioelement doping with the nano particle for preparing particulate used according to the invention.Even measure considerably less this purpose that also is enough to satisfy, thereby can differentiate the doping particle by absorption, emission or the scattering of measuring electromagnetic radiation.Preferably use the adulterated nano particle of at least a fluorescence dye, for example median size is the polystyrene of 20-300nm and the nano particle of fluorescence dye, and median size is the silica of 20-100nm and the nano particle of at least a fluorescence dye.In addition, has described diameter and be applicable to that with lanthanum and/or terbium and/or the adulterated silica granule of cerium ISP is with stable emulsion.
The example of dyestuff that can be used according to the invention is:
(a) water-insoluble dyestuff:
Fu Luluo (Fluorol) 7GA Lambdachrome No.5550 (Lambda ChromLaser Dyes from Lambda Physik GmbH, Hans-B ckler-Str.12, G ttingen)
Tonka bean camphor 47 CAS registration number 99-44-1
Tonka bean camphor 102 CAS registration number 41267-76-9
Coumarin 6 H CAS registration number 58336-35-9
Tonka bean camphor 30 CAS registration number 41044-12-6
Fluorescent yellow 27 CAS registration number 76-54-0
Uranine (Uranin) CAS registration number 518-47-8
Bis-MSB CAS registration number 13280-61-0
DCM CAS registration number 51325-91-8
Cresol purple CAS registration number 41830-80-2
Phenoxazon9 CAS registration number 7385-67-3
HITCI CAS registration number 19764-96-6
IR125 CAS registration number 3599-32-4
IR144 CAS registration number 54849-69-3
HDITCI CAS registration number 23178-67-8
Carbostyryl?7 LambdachromeNo.4220(Lambda?Physik?GmbH)
Carbostyryl?3 Lambdachrome?No.4350(Lambda?Physik?GmbH)
(b) water-soluble dye
Rhodamine B CAS registration number 81-88-9
Rhodamine 101 CAS registration number 64339-18-0
Rhodamine 6G CAS registration number 989-38-8
Brillantsulfaflavin CAS registration number 2391-30-2
Rhodamine 19 CAS registration number 62669-66-3
Rhodamine 110 CAS registration number 13558-31-1
Sulphonyl rhodamine B CAS Reg.2609-88-3
Nile blue CAS Reg.53340-16-2
piperazine CAS Reg.62669-60-7
piperazine 1 CAS registration number 24796-94-9
HIDCI CAS registration number 36536-22-8
Cryptocyanine CAS registration number 4727-50-8
Furan?1 LambdachromeNo.4260(Lambda?Physik?GmbH)
Stilbene 3 Lambdachrome No.4200 (Lambda Physik GmbH)
DASBTI LambdachromeNo.5280(Lambda?Physik?GmbH)
C) reactive dyestuffs
DACITC
*CAS registration number 74802-04-3
DMACA, SE
*CAS registration number 96686-59-8
5-FAM, SE
*CAS registration number 92557-80-7
FITC ' isomer I '
*CAS registration number 3326-32-7
5-TRITC; The G isomer
*CAS registration number 80724-19-2
*) these dyestuffs for example with the NH radical reaction
The water-insoluble polymer particle (in the solubleness of 20 ℃ of following polymkeric substance in water is＜1g/l in order to prepare in fact by the ISP method, preferably＜0.1g/l), according to i) make the water-soluble mono ethylenically unsaturated monomer with the monomer copolymerization that in molecule, has at least two two keys.The example of water-soluble monomer is the unsaturated C of olefinic
3-C
6Carboxylic acid such as vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid, vinyl lactic acid and ethylacrylic acid, and acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, vinyl toluene sulfonic acid and vinyl phosphonate.Ethylenic unsaturated acid also can with basic metal or alkaline earth metal alkali or with ammonia or ammoniate partially or completely the neutral form use.Preferably sodium hydroxide solution, potassium hydroxide solution or ammonia are used as neutralizing agent.Other suitable water-soluble monomer is acrylamide and Methacrylamide.Monomer can use separately or be mixed together use with the water-insoluble monomer of each other mixture and 20 weight % at the most such as vinyl cyanide, methacrylonitrile or acrylate and methacrylic ester.
The monomeric example that is used as linking agent and has at least two two keys in ISP is N, N '-methylene diacrylamine, Vinylstyrene, divinyl two alkane, at least dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, glycerine, tetramethylolmethane and sorbyl alcohol and molar mass of Mn are the acrylate and the methacrylic ester of the multipolymer of the polyalkylene glycol of 100-3000, especially polyoxyethylene glycol and ethylene oxide and propylene oxide.The preferred linking agent that uses is fourth-1,4-omega-diol diacrylate, fourth-1,4-glycol dimethacrylate, oneself-1, the 6-omega-diol diacrylate, oneself-1,6-glycol dimethacrylate, two of tetramethylolmethane-and triallyl ether or anhydro sorbitol triallyl ether.The consumption of linking agent for example is 0.01-10 weight % based on used monomeric total amount in ISP, preferred 0.5-5 weight %.Certainly two or more linking agents are used for polymerization.
In ISP, preferably the consumption with dye adulterated nano particle for example is 0.01-20 weight %, preferred 0.1-5 weight %, and it is as the stablizer of emulsion.Comprise adulterated nano particle on the particulate preferred surface that in polymerization, forms.For example by broken suspension or by removing volatile solvent from suspension separating particles.
The other method of preparation encoding microsomal comprises: (ii) make the water-insoluble monoene belong to unsaturated monomer and based on monomer mixture be the ethylenically unsaturated monomer letex polymerization that has at least two two keys at least a molecule of 0-10 weight %, the emulsifying agent that wherein is used for the stable dispersion phase is similarly adulterated nano particle, and its amount is for being used for the amount according to the ISP of (i).Found adulterated nano particle in the surface of gained emulsion polymer or on the surface.Emulsion polymerisation process is known.Here for example make the polymerization and obtain polymeric dispersions in small, broken bits in the presence of radical initiator such as Sodium Persulfate, hydrogen peroxide or redox catalyst of water-insoluble monomer.Be stable emulsion, use the compound of HLB value＞7 usually.This compounds for example is the C of every mol of alcohol and the reaction of 5-50 mole ethylene oxide
12-C
18Alcohol, perhaps sulfonated long chain (＞C
12-) pure an alkali metal salt.If according to (ii) suitable use emulsifying agent.If they are used together, then their amount is based on treating that the polymeric monomer for example is 0.1-10 weight %, preferred 0.5-3 weight %.
The monomeric implication of water-insoluble should refer to that those form the alefinically unsaturated compounds of insoluble polymer.The water solubility of insoluble polymer for example is＜1g/l, and is common＜0.01g/l.The monomeric example of this class is a vinylbenzene, alpha-methyl styrene, vinylformic acid and methacrylic acid and C
1-C
18Monohydroxy-alcohol, preferred C
1-C
4The ester of monohydroxy-alcohol is by C
1-C
20Methacrylamide such as N methacrylamide, N-methyl acrylamide, N-ethyl acrylamide and N-ethyl-methyl acrylamide that AAM and N-replace.
If suitable, the water-insoluble monomer can with the small amounts of water soluble monomer copolymerization, wherein the consumption of water-soluble monomer only makes that resulting polymers is a water-insoluble.If water-soluble monomer is used for the modified water insoluble polymer, the amount that then is used for letex polymerization for example is 0.1-10 weight %, preferred 0.2-5 weight %.Spendable water-soluble monomer for example is above-mentioned monomer, the especially ethylenic unsaturated acid under (i).The modification of polymkeric substance may be essential, for example for functional group is introduced in the polymkeric substance, thereby for example can carry out subsequent reaction.
In some cases, may must reduce polymkeric substance in water solubleness and increase the strength property of polymkeric substance.This purpose realizes by the water-insoluble monomer being comprised carry out polymerization in the presence of the ethylenically unsaturated monomer of two two keys in molecule at least.
This class is also referred to as the monomer of linking agent and mentions under above-mentioned (i).They are identical with the above-mentioned amount that is used for ISP according to the consumption in the letex polymerization (ii).The example of crosslinked emulsion polymer is the polystyrene with Vinylstyrene or the crosslinked mistake of butylene glycol diacrylate, and with pentaerythritol triacrylate and/or crosslinked acrylate and the methacrylic ester of tetramethylol methane tetraacrylate, positive butyl ester of for example crosslinked polyacrylic acid or crosslinked polymethylmethacrylate.
Can for example be 10nm-1000 μ m, preferred 10nm-10 μ m by the median size of the polymkeric substance that obtains according to (ii) polymerization.Be generally 500nm-30 μ m, especially 1 μ m-20 μ m.Comprise with nano-particle doped and be scattered in particulate in the water according to the aqueous polymer dispersion of (ii) preparation.Adulterated particulate can be by centrifugal or add inorganic salt and make the dispersion stabilization removal and obtained by aqueous polymer dispersion.Because particulate uses with discrete form mostly, the importance of separating particles is little from water dispersion.
In addition according to (iii), but the particulate of coding can obtain by making at least a ethylenically unsaturated monomer carry out radical polymerization with the copolymerization dyestuff with ethylenical unsaturated double bonds.The example that comprises the dyestuff of ethylenical unsaturated double bonds is 4-(dicyano vinyl) julolidine (DCVJ) and anti-form-1-(2 '-methoxy-ethylene base) pyrene.These dyestuffs for example can be used for inverse suspension polymerization (i) and letex polymerization (ii), are used to the polymer beads of encoding as comonomer.Especially when resulting polymers particulate median size is 5-500nm, advantageously when using encoding microsomal, particle aggregation become median size for example to be the aggregate of 300nm-500 μ m.
Encoding microsomal also can be according to being 300nm-500 μ m by making at least two groups become median size in particles agglomerate different aspect its absorption, emission and/or the scattered electromagnetic radiation (iv), the aggregate of preferred 400nm-20 μ m and preparing.Therefore, can will be 5-500nm for example with fluorescence dye coding and mean diameter, the silica granule of preferred 20-100 nanometer and crosslinked polystyrene are combined into mean particle size and for example are 300nm-500 μ m, the aggregate of preferred 400nm-20 μ m, wherein said crosslinked polystyrene is with amino modified (for example using 0.5-3 weight % vinylformic acid dimethylamino propyl ester) in polymerizing styrene, its median size is 20-100nm and is the dye adulterated of 96686-59-8 with a kind of above-mentioned reactive dyestuffs such as CAS registration number.
Preferred its coding comprises the encoding microsomal of at least two kinds of different dyes in each case.For increasing quantity of information, for example use the mixture of two group coding particulates, wherein said mixture comprises one group of encoding microsomal and another group that only contains a kind of fluorescence dye and wherein contains two kinds of fluorescence dyes and the mutually different encoding microsomal of fluorescence dye.
Quantity of information can increase by using two groups of mixtures that are used for the encoding microsomal of marker material, and wherein said mixture comprises one group and for example only contains a kind of encoding microsomal of fluorescence dye and the encoding microsomal that another group contains two kinds of mutually different reactive dyestuffs.For example, can also use the mixture of two group coding particulates, wherein said mixture comprises one group of A and contains a kind of encoding microsomal of fluorescence dye and another group B and contain three kinds or more kinds of mutually different and be different from the encoding microsomal of the fluorescence dye of the dyestuff of organizing A.
Another example that is used for marker material is the mixture of two group coding particles A and B, and wherein said mixture comprises a combination the encoding microsomal A of two kinds of different fluorescence dyes and the encoding microsomal B that another group contains two kinds of different fluorescence dyes.
The example that is used for further mark is the mixture of two group coding particles A and B, and wherein said mixture comprises the encoding microsomal B that encoding microsomal A that a combination has two kinds of different fluorescence dyes and another combination have three kinds or more kinds of different fluorescence dyes.Another example is the mixture of two group coding particles A and B, and wherein said mixture comprises the encoding microsomal B that encoding microsomal A that a combination has three kinds of different fluorescence dyes and another combination have three kinds of different fluorescence dyes.
Coding comprise 5 not on the same group another example of particles A-E be the mixture that comprises following particulate:
One group of particulate that comprises three kinds of different dyes D1, D2 and D3 of A,
One group of particulate that comprises dyestuff D1 and D2 of B,
One group of particulate that comprises dyestuff D1 and D3 of C,
One group of particulate that comprises dyestuff D4 and D5 of D, and
One group of particulate that comprises dyestuff D4 of E.
The invention still further relates to the purposes of the encoding microsomal that can obtain by the following method:
(i) make the polymerization and obtain the particulate that median size is 300nm-500 μ m in the presence of dyestuff and/or nano particle of at least a ethylenically unsaturated monomer, if at least a dyestuff of wherein suitable usefulness or with the rare earth doped or radioactivity of the periodictable described nano particle that mixes, or
(ii) make at least two groups different particles agglomerate aspect its absorption, emission and/or scattered electromagnetic radiation, to obtain the aggregate that median size is 300nm-500 μ m, wherein always at least two groups are used for marker material in the combination of encoding microsomals different aspect its absorption, emission and/or the scattered electromagnetic radiation.
Preferred especially the use with the particulate of fluorescence dye coding and the particulate of encoding with reactive dyestuffs.Further importantly with the particulate of water-soluble dye coding and the particulate of water insoluble dyes coding.
Can come the identifier number particulate by the spectrofluorometer with appropriate filter and/or the commercially available hematimeter of photodetector wherein are housed.The identifier number particulate is for example undertaken by total fluorescence spectrum or the emitted radiation of analyzing each selected wavelength, wherein also can change the incident light wavelength that produces fluorescence.The hematimeter that is fit to the identifier number particulate is for example by Partec GmbH, Otto-Hahn-Str.32, and D-48161 sells.
Above-mentioned encoding microsomal is used for marker material; for example dispersion, coating, lacquer, explosive substance, polymkeric substance, crop protection agents, seed; sheet, capsule, tincture or the preparation of medicament production as containing active substance, makeup are as frost, lotion or shampoo, solution; fuel for example; especially oil fuel, paper, especially paper pack, banknote and safety paper; and have coding, for example all goods of the chassis number of Motor vehicles.
The invention still further relates to and comprise material encoding microsomal and that can obtain by the following method that is used for mark:
(i) make at least a water-soluble mono ethylenically unsaturated monomer at least a molecule, have the polymerization by anti-phase water-in-oil suspension polymerization in the presence of the ethylenically unsaturated monomer of at least two two keys, wherein adulterated nano particle be used as suspension medium,
(ii) make the water-insoluble monoene belong to unsaturated monomer and based on monomer mixture be the ethylenically unsaturated monomer letex polymerization that has at least two two keys at least a molecule of 0-10 weight %, wherein adulterated nano particle is used for the stable dispersion phase as emulsifying agent
But (iii) make at least a ethylenically unsaturated monomer with copolymerization dyestuff polymerization with ethylenical unsaturated double bonds, and if suitable these particle aggregations that makes, or
(iv) make at least two groups different particles agglomerate aspect its absorption, emission and/or scattered electromagnetic radiation, to obtain the aggregate that median size is 300nm-500 μ m.
If with two groups of particulates combinations with different coding, then can be compound or classification marking and obtain composition by it.These mixtures can be by for example they provide the information of wide region by the fluorescent microscope analysis.The information that is present in the mixture can be read by absorption, emission or the scattered spectrum of various fluorescent materials by currently known methods, and these methods for example are described in the described reference of prior art.
Therefore for example can be by making up different encoding microsomals or by using a plurality of fluorescent substances that are used for encoding microsomal to store the information of significant quantity.For example, if the particulate that will encode by this way adds in the product to be marked, then can detect as manufacturer, the place of production, date manufactured and lot number by absorption, emission or the scattered spectrum of the sample of marked product.
When using with the code set compound, encoding microsomal certainly must be compatible with material to be encoded, and promptly the detection property again of the performance of desired product and encoding microsomal all can not suffer damage.
Claims (15)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004027416.9 | 2004-06-04 | ||
| DE200410027416 DE102004027416A1 (en) | 2004-06-04 | 2004-06-04 | Method for marking materials, e.g. pharmaceuticals, packaging or bank notes, uses coded polymer micro-particles containing dye and-or doped nano-particles, or aggregates of different groups of such micro-particles |
| DE102005019980.1 | 2005-04-27 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101813390A Division CN101407560A (en) | 2004-06-04 | 2005-06-02 | Method for marking materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1964995A true CN1964995A (en) | 2007-05-16 |
| CN100567331C CN100567331C (en) | 2009-12-09 |
Family
ID=34970228
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101813390A Pending CN101407560A (en) | 2004-06-04 | 2005-06-02 | Method for marking materials |
| CNB200580018047XA Expired - Fee Related CN100567331C (en) | 2004-06-04 | 2005-06-02 | Method of marking a material |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2008101813390A Pending CN101407560A (en) | 2004-06-04 | 2005-06-02 | Method for marking materials |
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| CN (2) | CN101407560A (en) |
| DE (1) | DE102004027416A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102612649A (en) * | 2009-11-20 | 2012-07-25 | 犹他大学研究基金会 | Sensors and methods for detecting peroxide based explosives |
| CN104411505A (en) * | 2012-07-03 | 2015-03-11 | 德国捷德有限公司 | Value document, method for checking the presence of same and value document system |
| CN112280553A (en) * | 2013-11-27 | 2021-01-29 | 华盛顿大学商业中心 | Coded chromophoric polymer particles |
| CN114901740A (en) * | 2019-12-12 | 2022-08-12 | 弗劳恩霍夫应用研究促进协会 | Method for preparing labelled polymers, labels, use of labels and labelled polymers |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005062027A1 (en) | 2005-12-22 | 2007-06-28 | Basf Ag | Aqueous dispersions of polymers containing a fluorescent dye, process for their preparation and their use for marking materials |
| DE102013016121A1 (en) * | 2013-09-27 | 2015-04-02 | Giesecke & Devrient Gmbh | Value document and method for checking the existence of the same |
| DE102013016134A1 (en) * | 2013-09-27 | 2015-04-02 | Giesecke & Devrient Gmbh | Value document and method for checking the existence of the same |
| DE102014016858A1 (en) * | 2014-02-19 | 2015-08-20 | Giesecke & Devrient Gmbh | Security feature and use thereof, value document and method for checking the authenticity thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059552A (en) * | 1974-06-21 | 1977-11-22 | The Dow Chemical Company | Cross-linked water-swellable polymer particles |
| US4708997A (en) * | 1985-07-22 | 1987-11-24 | The Dow Chemical Company | Suspending agent for the suspension polymerization of water-soluble monomers |
| DE3613081A1 (en) * | 1986-04-18 | 1987-10-29 | Basf Ag | METHOD FOR PRODUCING PEARL-SHAPED POLYMERISATES ON THE BASIS OF WATER-SOLUBLE ETHYLENICALLY UNSATURATED MONOMERS |
| DE19805121A1 (en) * | 1998-02-09 | 1999-08-12 | Basf Ag | Process for the preparation of dye-containing, aqueous polymer dispersions |
-
2004
- 2004-06-04 DE DE200410027416 patent/DE102004027416A1/en not_active Withdrawn
-
2005
- 2005-06-02 CN CNA2008101813390A patent/CN101407560A/en active Pending
- 2005-06-02 CN CNB200580018047XA patent/CN100567331C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102612649A (en) * | 2009-11-20 | 2012-07-25 | 犹他大学研究基金会 | Sensors and methods for detecting peroxide based explosives |
| CN104411505A (en) * | 2012-07-03 | 2015-03-11 | 德国捷德有限公司 | Value document, method for checking the presence of same and value document system |
| CN104411505B (en) * | 2012-07-03 | 2016-06-29 | 德国捷德有限公司 | Value document, for checking the method and value document system that value document exists |
| CN112280553A (en) * | 2013-11-27 | 2021-01-29 | 华盛顿大学商业中心 | Coded chromophoric polymer particles |
| CN114901740A (en) * | 2019-12-12 | 2022-08-12 | 弗劳恩霍夫应用研究促进协会 | Method for preparing labelled polymers, labels, use of labels and labelled polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101407560A (en) | 2009-04-15 |
| DE102004027416A1 (en) | 2005-12-22 |
| CN100567331C (en) | 2009-12-09 |
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