DE102007048070A1 - Method for detecting surface changes - Google Patents

Method for detecting surface changes

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Publication number
DE102007048070A1
DE102007048070A1 DE200710048070 DE102007048070A DE102007048070A1 DE 102007048070 A1 DE102007048070 A1 DE 102007048070A1 DE 200710048070 DE200710048070 DE 200710048070 DE 102007048070 A DE102007048070 A DE 102007048070A DE 102007048070 A1 DE102007048070 A1 DE 102007048070A1
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Prior art keywords
light
surface
microcapsules
characterized
light intensity
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DE200710048070
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German (de)
Inventor
Norbert Donkels
Karl-Heinz Drenker
Hans Jörg Dipl.-Ing. Seiler
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/6456Spatial resolved fluorescence measurements; Imaging
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1003Carbocyclic compounds
    • C09K2211/1007Non-condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1044Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1059Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1088Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14Macromolecular compounds
    • C09K2211/1408Carbocyclic compounds
    • C09K2211/1425Non-condensed systems
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/6456Spatial resolved fluorescence measurements; Imaging
    • G01N2021/646Detecting fluorescent inhomogeneities at a position, e.g. for detecting defects

Abstract

The present invention relates to a method for detecting surface changes and identification of the trigger which has caused the surface modification, as well as suitable means therefor.

Description

  • The The present invention relates to a method for detecting surface changes and the identification of the trigger, the surface modification and appropriate means.
  • Out DE 10257812 It is known to identify surface changes by treating surfaces with an aqueous dispersion containing at least one UV-visible light-emitting substance and a binder, and then to examine the surfaces with UV light for changes that have occurred in the meantime.
  • Out US 6,476,385 For example, a control method is known in which smooth surfaces are treated with a water-soluble agent to determine later, using a UV light source, whether the surfaces thus treated have been sufficiently cleaned.
  • adversely However, in the said method is that although a surface change can be identified, but neither time nor trigger can be determined.
  • Of the The present invention is therefore based on the object, a method to provide for the detection of surface changes, the explanation about the trigger of the surface modification and, where appropriate, an indication of the date the surface change can give.
  • A method has now been found for the detection of surface changes and their cause, which is characterized in that
    • a) a surface treated with an agent and
    • b) the surface thus treated and / or the adjoining untreated surfaces and / or the sources of a force on the thus treated surface irradiated by UV light and the deviation
    • b1) the light intensity of the emitted light of a partial surface to the mean light intensity of the emitted light of the total surface and / or
    • b2) the light intensity of the emitted light of a part of the adjacent, untreated surface to the mean light intensity of the emitted light of the adjacent untreated surfaces and / or
    • b3) the light intensity of the emitted light of the surface after the treatment with the means with the light intensity of the emitted light at a later time and / or
    • b4) the light intensity of the emitted light of the adjacent untreated surface after the treatment of the surface with the means having the light intensity of the emitted light of the adjacent untreated surface at a later time and / or
    • b5) the light intensity of the emitted light of the source of a force after the treatment of the surface with the zero mean or an earlier reference value
    finds
    wherein the agent contains microcapsules containing at least one visible by UV irradiation light emitting substance.
  • to Clarification should be noted that the scope of the invention all below listed, general or preferred Definitions and parameters are included in any combination.
  • in the Frame of the invention are under the term surface modification to understand any changes to materials that are appropriate are the reflection, absorption, or adsorption compared to a to change as stationary assumed UV light source. These include, for example, translations and other changes in the orientation of the surface relative to the UV light source, chemical or physical modifications, as well as superposition with other materials.
  • For example, in a preferred embodiment, surfaces are surfaces of terrain including plant surfaces, exterior and interior surfaces, and traffic routes. Examples include military areas and security areas, military practice areas, public buildings and their immediate surroundings, strategically important transport facilities such as bridges and crossings, locks, boat lifts and shipping routes such as canals, railways and trams, especially high-speed and high-speed trains and magnetic railways, highways and their Surroundings such as intersections and intersection-free facilities such as motorway junctions, as well as strategic important utilities such as nuclear power plants and other electricity producing power plants, electricity facilities such as substation and transformer factories, power lines, telecommunication facilities, waterworks and water pipelines, fixed machinery, pipelines and gas pipelines.
  • In Another preferred embodiment is surfaces For example, surfaces of moving objects. Movable items are for example vehicles and their equipment, furnishings and other valuables, Goods of all kinds, such as industrial goods. there industrial bulk goods are particularly noted. Movable items are still, for example, transport and Storage containers.
  • In In another embodiment, surfaces also surfaces of liquids such as Be water or water surfaces.
  • By the treatment of the surfaces according to step a) the process of the invention are the Surfaces with the invention Medium equipped.
  • This is preferably such that the microcapsules by the application at least partially undamaged, d. H. the nuclear material the microcapsule remains at least partially encapsulated.
  • For example the application is carried out by spraying or spraying with devices according to the prior art. For smaller objects, the application can also by brushing, brushes or rolls are applied.
  • By the application of the agent depends on the composition of the product used and the type of surface treated an at least partially closed, solid film or layer containing microcapsules.
  • He follows now a surface change, this is typical with the action of forces such as pressure, Shear, acceleration or tensile forces connected.
  • by virtue of the action of forces gives at least a part of the Microcapsules free their nuclear material, which then on the immediate Surrounding the microcapsule acts. The immediate area to Time of release of the core material can be both the be equipped with microcapsules surface, as well the source of the force. Is the source of the force a person or a moving object, such as a vehicle or tool can, by the inventive Procedure for subsequent irradiation of the person or the moving object with UV light the contact with the treated Surface be proved beyond doubt.
  • This is particularly advantageous because not only the fact the surface change as such, but also their cause can be identified. Because the nuclear material furthermore after exiting by mechanical action, photodecomposition the visible under UV light emitting substance under irradiation Faded with UV light over time, it is still possible also a clue to the timing of the surface modification to obtain.
  • at treated surface waters it is for example possible to detect the penetration of vessels because the microcapsules typically float on the surface and by the drive means of the watercraft, in particular Ship propellers released nuclear material, what then under Exposure to UV light also detected a long time later can be.
  • The Irradiation with UV light according to step b) of inventive method can, for example using standard UV lamps or UV lasers, due to the short but intense stimulation and the associated Improving the signal-to-noise ratio is the application of UV lasers preferred.
  • The Determination of a deviation according to step b) the process of the invention can, for example with the help of a camera optionally using image processing software done in a conventional manner.
  • From The invention further microcapsules containing at least comprises a visible on UV irradiation light emitting substance.
  • in the The scope of the invention is defined by the term "microcapsules" essentially spherical or spheroidal aggregates with a diameter in the range of about 0.0001 to about 5 mm understand the at least one particular solid or liquid Core enclosed by at least one continuous shell is.
  • For example the microcapsules are film-forming polymers coated finely dispersed liquid or solid phases, in their preparation, the polymers after emulsification and coacervation or interfacial polymerization on the enveloped Precipitate material. By another method are melted Waxes taken in a matrix ("microsponge"), called microparticles additionally encased with film-forming polymers could be.
  • The microcapsules according to the invention can not only monotonous but also polynuclear. Such microcapsules are also known as microspheres and typically contain two or more cores distributed in the continuous wrapping material.
  • The mono- or polynuclear microcapsules can continue from an additional second, third and possibly be enclosed still further covers.
  • The Shell of the microcapsules according to the invention consists essentially of natural, semi-synthetic or synthetic shell materials.
  • natural Shell materials include gum arabic, agar-agar, Agarose, maltodextrins, alginic acid or its salts, such as. Eg sodium or calcium alginate, fats and fatty acids, cetyl alcohol, Collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolysates, Sucrose and waxes.
  • semi-synthetic Shell materials are, for example, chemically modified Celluloses such as cellulose esters and ethers, such as in particular Cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, as well as starch derivatives, in particular Starch ethers and esters.
  • synthetic Shell materials are, for example, polymers such as polyureas, Polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone and mixtures of the materials mentioned.
  • The microcapsules according to the invention contain at least a substance emitting UV radiation when exposed to light.
  • When For example, UV-visible light emitting substance optical brighteners suitable. The for the invention Purpose-usable optical brighteners preferably absorb light at a wavelength of 1 nm to 420 nm, preferably 200 to 380 nm, and preferably emit light in the wavelength interval between 360 and 830 nm. Here is the main absorption peak at a smaller wavelength than the main emission peak.
  • When optical brighteners are suitable for recordings: polystyrylstilbene, Flavonsäurederivate, coumarins or pyrazolines.
  • Polystyrylstilbenes are for example and preferably those which have one or more structural units of the formula (I) Ph-CH = CH- (I) in which Ph represents an optionally substituted phenyl radical.
  • Particularly preferred polysyrylstilbenes are those of the formula (Ia)
    Figure 00060001
    wherein
    R 5 is hydrogen, hydroxyl, SO 3 M, COOM, OSO 3 M, OPO (OH) OM, and M is hydrogen, Na, K, Ca, Mg, ammonium or a primary, secondary, tertiary or quaternary organic ammonium radical, such as for example, N (R 1 R 2 R 3 R 4 ) + may stand, wherein the radicals R 1 to R 4 may each independently be hydrogen, C 1 -C 30 alkyl, C 1 -C 30 -hydroxy
    R 6 and R 7 independently of one another are SO 3 M, COOM, OSO 3 M, OPO (OH) OM and M has the meaning described above,
    x has the value 0 or 1 and
    the structure according to formula (Ia) is trans-coplanar or cis-coplanar.
  • Flavonsäurederivate are, for example and preferably those of the formula (II)
    Figure 00060002
    wherein
    R 8 is hydrogen,
    R 9 is a mono- or disubstituted triazine ring and
    W is SO 3 M, COOM, OSO 3 M, OPO (OH) OM, where M has the meaning described above.
  • Particularly preferred flavonic acid derivatives of the formula (II) are those of the formula (IIa)
    Figure 00060003
    wherein
    R 10 , R 11 and R 12 independently represent phenoxy, mono- or disulfonated phenoxy, phenylamino, mono- or disulfonated phenylamino, phenylamino substituted by C 1 -C 3 alkyl, cyano, halogen, COOR, CONH-R, -NH -COR, SO 2 NH-R, OR, morpholino, piperidino, pyrrolidino, -OC 1 -C 4 -alkyl, -NH (C 1 -C 4 -alkyl), -NH (C 1 -C 4 -alkyl) 2 , -NH-C 2 -C 4 -alkylene-OC 2 -C 4 -alkylene-OR, -NH (C 2 -C 4 -hydroxyalkyl) 2 , -NHC 2 -C 4 -alkylene - = - C 2 -C 4- alkylene-OR, an amino acid residue or an amino acid amide; -NHCH 2 CH 2 OH, -N (CH 2 CH 2 OH) 2 , -N (CH) 3 CH 2 CH 2 OH, -NH 2 , -CH 3 , -SC 1 -C 4 -alkyl, -S- Aryl, -Cl, -NHCH 2 CH 2 SO 3 H, -NH (CH 2 CH 2 SO 3 H) 2 , -N (CH 2 CH 2 OH) or CH 2 CH 2 CONH 2 , where R is H or H C 1 -C 3 alkyl and
    M has the meaning described above.
  • Particularly preferred flavonic acid derivatives of the formula (II) are those of the formula (IIb)
    Figure 00070001
    wherein
    R 13 and R 14 independently of one another are hydrogen, phenyl, monosulfonated phenyl, methyl, ethyl, propyl, methoxy or ethoxy and
    M has the meaning given above.
  • Coumarins are, for example and preferably those of the formula (III)
    Figure 00070002
    wherein
    R 15 is (CH 2 ) 1-4 COOM, (CH 2 ) 1-4 SO 3 M, (CH 2 ) 1-4 SO 4 M or (CH 2 ) 1-4 OPO (OH) OM and M is the has the abovementioned meaning.
    R 16 is hydrogen, phenyl is COO-C 1 -C 30 -alkyl or glucosyl,
    R 17 is OH or OC 1 -C 30 -alkyl and
    R 18 is OH, OC is C 1 -C 30 -alkyl or glycosidically linked sugar residues.
  • Pyrazolines are, for example and preferably those of the formula (IV)
    Figure 00080001
    wherein
    R 19 is hydrogen or chlorine
    R 20 is SO 3 M, COOM, OSO 3 M or OPO (OH) OM, where M has the abovementioned meaning,
    R 21 and R 22 independently of one another are hydrogen, C 1 -C 30 -alkyl or phenyl and
    R 23 is hydrogen or chlorine.
  • In addition to the optical brighteners specified here, which are colorless as substances, it is also possible to use so-called fluorescent dyes, as described, for example, by H., provided this does not disturb the intended use or if the intrinsic color on the corresponding surface is inconspicuous in the visible range. Langhals published in the proceedings: DGMK Coal Refining Division, Symposium "Production and Application of Polynuclear Aromatic and Heteroaromatic Compounds", Nov. 28, 1991 in Bochum, on pages 95 to 118 are described.
  • Very particular preference is given to the flavonic acid derivatives of the formula (IIc) as substance which emits visible light when exposed to UV radiation.
    Figure 00090001
    wherein
    R 24 , R 25 and R 26 independently of one another are -NH 2 , -NH-CH 3 , -NH-ethyl, -NH- (CH 3 ) 2 , -NH- (ethyl) 2 , -NHCH 2 CH 2 OH, -NH-C 2 -C 4 -hydroxyalkyl, -NH (C 2 -C 4 -hydroxyalkyl) 2 , -NHCH 2 CH 2 SO 3 H, -NH-CH 2 CH 2 OCH 2 CH 2 OH, -O-CH 3 , -OCH- (CH 3 ) 2 , -O-CH 2 CH 2 OCH 3 , -N (CH 2 CH 2 OH) 2 , -N (CH 2 CHOH-CH 3 ) 2 , morpholino, -S-CH 3 , -N (CH 2 CH 2 OH) CH 2 CH 2 CONH 2 or a radical of the formulas below
    Figure 00090002
    wherein in the above formulas
    R is hydrogen or C 1 -C 3 -alkyl and
    M has the meaning described above.
  • Also very particularly preferred are the Flavonsäurederivate of formula (IId).
    Figure 00100001
    wherein
    R 27 and R 28 independently of one another represent hydrogen, C 1 -C 3 -alkyl or phenyl.
  • The on UV irradiation visible light emitting substances can in the sheath or core material or in the sheath and core material be included. Preferably, however, they are only in the core material contain the microcapsules of the invention.
  • Provided the visible by UV irradiation light emitting substances is present in the core material, the core material in another Embodiment of the invention further at least one Contain binder and optionally a dispersant.
  • Binders may be, for example, those prepared by aqueous solution polymerization, such as acrylamide homo- and copolymers, which are described in US Pat Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, pages 1178-1191 to be discribed. Examples of suitable comonomers for acrylamide and methacrylamide are: styrene, acrylic acid and (meth) -acrylic acid methyl, -ethyl, -butyl, and -2-ethylhexyl esters, either alone or as a mixture of several comonomers. The use of the comonomers is typically carried out in conditions well known to those skilled in the art.
  • Furthermore, as a binder emulsion polymers are suitable, as in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, pages 1150 to 1155 as products of the copolymerization of (meth) -acrylic acid methyl, -ethyl, -butyl, and -2-ethylhexylester with styrene, acrylonitrile, acrylic acid, acrylamide and methacrylamide are described either alone or as a mixture with a plurality of comonomers.
  • Other suitable binders are copolymers such as water-soluble styrene-acrylic acid or (meth) -acrylic acid methyl, -ethyl, -butyl, and -2-ethylhexyl esters, as described in US Pat Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, page 985 or styrene-maleic acid copolymers which are described in the same place.
  • Preferred binders are polyurethanes as described in US Pat Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 1, pages 1659 to 1681 are described.
  • Particularly preferred polyurethanes are those which are self-dispersible in water and are prepared from:
    • i) diisocyanates containing 4 to 50 carbon atoms,
    • ii) diols having a molecular weight of 500 to 4,000 g / mol
    • iii) Diols and / or di- or triamines as chain extenders having a molecular weight of 62 to 500 g / mol
    • iv) Mono- and polyols and / or mono- and polyamines having primary and / or secondary amino groups, which also have a hydrophilicizing group.
  • When Diisocyanates i) come here z. B. in question: tetramethylene diisocyanate, Hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, Decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, Trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic Diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (Isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-1-methyl-cyclohexane and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate, Tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenylenediisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate or diphenyl ether-4,4'-diisocyanate or mixtures of those mentioned Diisocyanates.
  • preferred Diisocyanates (i) are those customary in polyurethane chemistry technical polyisocyanates such as hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (Isophorone diisocyanate, IPDI), perhydro-4,4'-diphenylmethane diisocyanate, 2,4- and 2,6-toluene diisocyanate and any mixtures of these Isomers, diphenylmethane-4,4'-diisocyanate and mixtures thereof with the corresponding 2,2'- and 2,4'-isomers.
  • Especially preferred are the aforementioned aliphatic polyisocyanates.
  • The Diols (ii) have an average molecular weight of 500 to 4,000 g / mol, preferably from 500 to 3000 and more preferably from 700 to 3,000 g / mol and preferably have a functionality from 2 on.
  • polyester (ii) are usually converted by multi-valued Alcohols made with dibasic carboxylic acids. At Place of carboxylic acids can also be carboxylic anhydrides be used. Both aliphatic and cycloaliphatic, and araliphatic and aromatic dicarboxylic acids usable. In addition, are also heterocyclic, unsaturated or substituted (for example by halogen atoms) can be used. Examples include: malonic acid, Succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, Sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, Undecanedicarboxylic acid, phthalic acid, isophthalic acid, Terephthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, Glutaric anhydride, succinic anhydride, maleic acid, Maleic anhydride, fumaric acid and dimer fatty acids.
  • Prefers are such dicarboxylic acids, taking into account Carboxyl carbons have a carbon number of 2 to 20.
  • When Polyhydric alcohols are for example: ethylene glycol, Propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, butene-1,4-diol, Butyne-1,4-diol, pentane-1,5-diol, neopentyl glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, Polypropylene glycols, dibutylene glycol and also polybutylene glycols.
  • Prefers are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, neopentyl glycol, Octane-1,8-diol and dodecane-1,12-diol.
  • About that In addition, reaction products are also those listed above Diols with phosgene or their transesterification products with carbonic acid esters such as diphenyl carbonate as polyester diols (ii) usable.
  • Also bishydroxyl functional products of ring-opening polymerization cyclic esters such as butyrolactone or caprolactone can be used as polyester diols (ii).
  • polyether (ii) are obtainable, for example, by reaction of Ethylene, propylene, styrene and / or butylene oxide with water or with other low molecular weight starter molecules such as ethylene glycol, Propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, butene-1,4-diol, Butyne-1,4-diol, pentane-1,5-diol, neopentyl glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, Polypropylene glycols, dibutylene glycol and also Polybuylenglykole according to known methods of the prior art.
  • For the case that the field of application is a biodegradable polyester dispersion polyester diols as diols (ii) are preferred.
  • polyols (iii) used as chain extenders, optionally also as Crosslinkers that are suitable are, for example, low molecular weight polyhydric alcohols having a molecular weight range of 62 to 400 g / mol. The following diols can be used: Ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, Butene-1,4-diol, butyne-1,4-diol, pentane-1,5-diol, neopentyl glycol, Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, Dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol and also polybutylene glycols.
  • Prefers are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, neopentyl glycol, Octane-1,8-diol and dodecane-1,12-diol.
  • Should a branching may be desired, so too higher functional polyols such as trimethylolpropane, Glycerol, pentaerythritol, sorbitol or sucrose are used.
  • When Amines (iii) used as chain extenders, optionally can also be used as crosslinkers are di- or Triamine can be used. These preferably have a molecular weight from 60 to 300 g / mol and are used especially in crosslinks and / or Chain extensions used in water. Suitable, for example following: 1,4-diaminobenzene, 2,4- and 2,6-diaminotoluene, 2,4'- and / or 4,4'-diaminodiphenylmethane, 1,4-diaminobutane, 1,6-diaminohexane, Ethylenediamine and its homologues, isophoronediamine, bis (4-aminocyclohexyl) methane, 1,4-diaminocyclohexane, hydrazine, hydrazine hydrate and piperazine.
  • One An example of the trifunctional amines is diethylenetriamine.
  • Especially preferred diamines are aliphatic types such as 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, bis (4-aminocyclohexyl) -methane, 1,4-diaminocyclohexane, ethylenediamine and its homologues and piperazine.
  • To the less preferred diamines include compounds such as 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-Methyl-3,5-diethyl-2,4-diaminobenzene, the technical mixtures thereof with 1-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3 ', 5'-tetraethyl-4,4'- diaminodiphenylmethane, 3,5,3 ', 5'-tetraisopropyl-4,4'-diaminodiphenylmethane or 3,5-diethyl-3,5'-diisopropyl-4,4'-diaminodiphenylmethane.
  • any Mixtures of such diamines can also be used become.
  • polyols and / or polyamines (iv) with primary and / or secondary Amino groups, which also have a hydrophilizing effect Group are used to the water dispersibility of the To ensure polyurethane.
  • The The amount of hydrophilizing groups to be used is the Specialist known; he will always use the amount which one ensures sufficient water dispersibility of the polyurethane.
  • Suitable hydrophilizing groups are for example:
    • a) nonionic structures of the formula (V): R 29 O- (CHX-CHY-O) n -CHX-CHY-Z (V) where n is a number from 3 to 70, X and Y are hydrogen or methyl, where in the event that one of the radicals X or Y represents methyl, the other hydrogen must be R 29 is a straight-chain or branched C 1 -C 6 Alkyl radicals or straight-chain or branched C 1 -C 6 -acyl radicals, where furthermore R 27 can also form a cyclic - (CH 2 ) m -alkylene radical with m = 4, 5, 6 or 7, in which one or two CH 2 - Groups may be replaced by O and / or NH and / or one or two CH 2 groups may be substituted by methyl, and Z is O, S or NH and ensures the connection to the polyurethane.
    • b) cationic structures of the formula (VI): R 30 R 31 [NXY] + (VI) wherein X and Y are hydrogen or methyl and R 30 and R 31 represent straight-chain or branched alkyl radicals, via which the connection to the cationic polyurethane is ensured.
    • c) anionic structures from the group consisting of: sulfonate, carboxylate, phosphate in the form of their alkali metal and / or ammonium salts.
  • When Mono- and polyols and / or mono- and polyamines (iv) with nonionic Groups are particularly suitable polyethylene glycol monoalkyl ethers, which is advantageous in the preparation of the polyurethane and above be used for dispersing and act as chain terminators.
  • Especially Polyethylene glycol monomethyl ethers are preferred.
  • When Mono- and polyols and / or mono- and polyamines (iv) with potential cationic groups characterized by protonation with acids and / or cationize quaternization by means of alkylating agents especially N, N-bishydroxyalkylalkylamines, N-alkyldialconolamines, trishydroxyalkylamines, N, N-dialkylalkylamines, N, N-Dialkylalkohole; the alkyl radicals comprise one to four Carbon atoms.
  • Especially preferred are N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, Dimethylethanolamine, diethylethanolamine, triethanolamine.
  • When Mono- and polyols and / or mono- and polyamines (iv) with potential anionic groups resulting from salt formation with ammonia or Anionise alkali hydroxides, carbonates and / or bicarbonates especially mono- and dihydroxycarboxylic acids, Mono- and diaminocarboxylic acids, mono- and diaminosulphonic acids, Mono- and Dihydroxysulfonsäuren.
  • Especially preferred are lactic acid, dimethylolpropionic acid, Glycine, taurine, 2- (2-aminoethyl) ethanesulfonic acid.
  • The dispersions are prepared, for example, according to the rules of the prior art ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 1, pages 1659 to 1681 ) either in the acetone process or in the melt dispersion process.
  • The Hydroxyl functional components (iv) may be advantageous be incorporated into the polyurethane before dispersing, the amino-functional Components (iv) are expediently the Dispersing water added during preparation of the dispersion.
  • The Dispersing water is contained in potentially cationic groups Components (iv) corresponding to the content of the polyurethane component (iv) acidified in potentially anionic components (iv) is added to the dispersing water according to the content of the polyurethane to component (iv) added to alkali.
  • The optionally used in the microcapsules dispersants preferably for better distribution of the water-insoluble in itself or sparingly soluble visible on UV irradiation Light-emitting substance in the core material.
  • For this are in principle all water-soluble polymeric dispersing aids suitable.
  • Examples include polyvinyl ethers and esters and the partial or complete saponification products of the polyvinyl esters ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, pages 1195 to 1226 ), Starch esters ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2151 to 2161 ) and ethers ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2138 to 2147 ) and starch ether esters ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, page 2151 ), Cellulose ethers ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, page 2086 to 2089 ) and -esters ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2093 to 2123 ) as well as cellulose ether esters ( Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, page 2092 ).
  • Prefers are biodegradable, water-soluble, polymeric dispersants.
  • Especially preferred is polyvinyl alcohol.
  • The Core material of the microcapsules according to the invention may continue to contain auxiliaries and additives.
  • auxiliary and additives may include, for example, flow control agents, Plasticizers, pigments, defoamers, deaerators, Dyes, fillers, matting agents, thickeners, emulsifiers and leveling agent.
  • The Production of the microcapsules may vary depending on the selected Covering material and the shell structure as well as the Core structure done in a conventional manner. It can the Encapsulation for example by reactive and non-reactive methods respectively. Examples of such processes are interfacial polycondensation, Interfacial polyaddition, solvent evaporation, Spray drying, phase separation and dropping methods. For the encapsulation of aqueous systems is z. B. the Double emulsion method.
  • The The nature of the microcapsules may vary with respect to their sensitivity against acting forces in per se known Be adapted to the desired purpose. For example, if you want only the penetration of security areas with heavy vehicles, but the intrusion of harmless Disregard objects such as smaller animals would to choose a stronger wrapping material, as for example for the detection of surface changes through personal access.
  • From The invention further comprises an agent containing the invention Microcapsules.
  • In a further embodiment of the invention the agent both the microcapsules of the invention as well as at least one free visible in UV irradiation light emitting substance. The term "free" means in this regard, that the visible in UV irradiation light emitting substance outside the microcapsules, d. H. uncapsulated.
  • The in UV irradiation visible light emitting substances of the Microcapsules and the free light visible under UV irradiation each emitting substance can be different or be identical. For the free, with UV irradiation visible light emitting substances are the same areas and preferred ranges as they are for the microcapsules above already defined.
  • The Agent containing the microcapsules according to the invention may also contain free binder. The term "free" means in this context that the binder outside the microcapsules, d. H. uncapsulated. The binders of Microcapsules and the free binders can each be different or be identical. Apply to the free binders the same areas and preferred areas as they are for the microcapsules have already been defined above.
  • In a preferred embodiment contains the agents according to the invention the microcapsules according to the invention, at least one free, visible in UV irradiation visible light Substance and free binder.
  • By the combination of free and microencapsulated material will be the Detection of surface changes and the Identifying the cause even further simplified. By the faster Leaching or the faster mechanical abrasion of the unencapsulated Material compared to the encapsulated material is in the Release of the core material by a force action also Qualitative conclusion on the time of release possible.
  • Of the Advantage of the present invention is the fact that in addition the determination of the surface change as such also the trigger can be identified. Farther Microencapsulated material is better at leaching and natural Influences protected as unencapsulated material and can thus be better used for long-term use become.
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.
  • Cited patent literature
    • - DE 10257812 [0002]
    • US 6476385 [0003]
  • Cited non-patent literature
    • - "Preparation and Application of Polynuclear Aromatics and Heteroaromatics", Nov. 28, 1991 in Bochum, on pages 95 to 118 [0041]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, page 1178-1191 [0046]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, pages 1150 to 1155 [0047]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, page 985 [0048]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 1, pages 1659 to 1681 [0049]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 1, pages 1659 to 1681 [0080]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 2, pages 1195 to 1226 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2151 to 2161 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2138 to 2147 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, page 2151 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2086 to 2089 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, pages 2093 to 2123 [0085]
    • - Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E 20, Part 3, page 2092 [0085]

Claims (11)

  1. Method for detecting surface changes or their cause, characterized in that a) a surface is treated with an agent and b) the surface treated in this way and / or the untreated surfaces adjoining thereto and / or the sources of a force acting on the surface thus treated UV light irradiated and the deviation b1) the light intensity of the emitted light of a partial surface to the mean light intensity of the emitted light of the total surface and / or b2) the light intensity of the emitted light of a portion of the adjacent, untreated surface to the mean light intensity of the emitted light of the adjacent untreated Surfaces and / or b3) the light intensity of the emitted light of the surface after the treatment with the means with the light intensity of the emitted light at a later time and / or b4) the light intensity of the emitted light of the adjacent unbeh after the treatment of the surface with the means having the light intensity of the emitted light of the adjacent, untreated surface at a later time and / or b5) the light intensity of the emitted light of the source of a force after the treatment of the surface with the means of zero value or an earlier comparative value, the agent containing microcapsules containing at least one visible upon UV irradiation light.
  2. Method according to claim 1, characterized that the irradiation with UV light is carried out by a UV laser.
  3. Method according to claim 1, characterized in that that the determination of a deviation according to step b) using a camera and using image processing software he follows.
  4. Microcapsules containing at least one upon UV irradiation includes visible light emitting substance.
  5. Microcapsules according to claim 4, characterized in that that they emit as UV radiation visible light emitting substances Polystyrylstilbene, flavonic acid derivatives, coumarins or Contain pyrazolines.
  6. Microcapsules according to one of claims 4 and 5, characterized in that they visible in UV irradiation Contain light-emitting substances in the core material.
  7. Microcapsules according to claim 6, characterized that the core material further contains at least one binder.
  8. Composition containing microcapsules according to one of the claims 4 to 7.
  9. Means according to claim 8, characterized in that it is at least an unencapsulated, visible under UV irradiation Contains light-emitting substance.
  10. Agent according to one of claims 8 and 9, characterized in that it is at least one non-encapsulated binder contains.
  11. Use of funds according to a of claims 8 to 10 or of microcapsules according to any one of Claims 4 to 7 for the detection of surface changes or their cause.
DE200710048070 2007-10-05 2007-10-05 Method for detecting surface changes Withdrawn DE102007048070A1 (en)

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Citations (2)

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US6476385B1 (en) 1999-03-22 2002-11-05 Peter M. Albert Cleaning management kit and method of use
DE10257812A1 (en) 2002-12-10 2004-07-08 Bayer Ag Detecting changes in an area, comprises treating the area with a fluorescent dispersion and determining any change in fluorescence intensity

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JPS62280082A (en) * 1986-05-30 1987-12-04 Canon Inc Optical information recording medium
JPS63266357A (en) * 1987-04-24 1988-11-02 Hitachi Ltd Acceleration sensor
FR2669735B2 (en) * 1990-06-06 1993-02-19 Hutchinson Method and highlighting device of one or shock (s) received (s) by a substrate.
JP2009502841A (en) * 2005-07-26 2009-01-29 グラクソ グループ リミテッドGlaxo Group Limited Encapsulation of lipid-based formulations in enteric polymers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6476385B1 (en) 1999-03-22 2002-11-05 Peter M. Albert Cleaning management kit and method of use
DE10257812A1 (en) 2002-12-10 2004-07-08 Bayer Ag Detecting changes in an area, comprises treating the area with a fluorescent dispersion and determining any change in fluorescence intensity

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Title
"Herstellung und Anwendung mehrkerniger Aromaten und Heteroaromaten", 28. Nov. 1991 in Bochum, auf den Seiten 95 bis 118
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 1, Seite 1659 bis 1681
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 2 Seite 1150 bis 1155
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 2 Seite 1178-1191
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 2, Seite 1195 bis 1226
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 2, Seite 985
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2086 bis 2089
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2092
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2093 bis 2123
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2138 bis 2147
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2151
Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band E 20, Teil 3, Seite 2151 bis 2161

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