A coating composition comprising a dye and a method to detect moisture in objects.

专利摘要:

公开号:NL2013295A
申请号:NL2013295
申请日:2014-08-01
公开日:2015-02-03
发明作者:Nicole Maria Matthias Meulendijks-Kiggen；Sebastiaan Joannes Franciscus Erich；Jacobus Eversdijk；Nicole Ellen Papen-Botterhuis；Johannes Wilhelmus Otto Salari
申请人:Tno；
IPC主号:

专利说明:

Title: A coating composition comprising a dye and a method to detect moisture in objects
The invention relates to the detection of moisture in coatedobjects. In particular, the invention relates to a coating compositioncomprising a dye and to a method to detect moisture in objects using asignalling layer comprising a dye. Such coatings, for example, can be usefulin detecting moisture build-up on wood or metal surfaces.
In the broad sense, the invention relates to the area of responsivecoatings. Such coatings, according to a general definition, are able to detectchanges in the environment, e.g. in the underlying surface, and make thesechanges “visible” through the signalling function. The signalling functioncan be very diverse in nature but preferably it allows to “read out” thechanges at a distance. The signalling function can for example be the changeof absorption properties of the coating (e.g., colour).
However, it is undesired for the coatings used for decorativepurposes such as paints for wood or other surfaces to change colour underthe influence of the environment. Therefore, responsive coatings shouldpreferably not absorb in the visible spectrum, i.e. have no colour. (Near)Infrared (IR) and ultraviolet (UV) dyes, that is, dyes that absorb in the(near) infrared area or ultraviolet area, respectively, meet this requirementand are particularly suitable in coatings with a signalling function. Inprinciple, the solar spectrum can be used as a light source enabling thesignalling function.
Coatings comprising microparticles with NIR dyes are forexample known from US 8,367,193. This patent describes nanocompositedispersions which are used to provide transparent coatings having enhancedbarrier properties featuring an invisible marker dye in the dispersion forimproved quality control, security, and manufacturing development. Themarker dye is a water soluble infrared (IR) or near infrared (NIR) dye. The coatings provide transparent high barrier coatings at thicknesses from 1-10microns that include an IR or an NIR dye that enables rapid measurementof coating thickness and uniformity. The described coating is howeverunsuitable to detect any changes in the environment as the describedpolymer-dye system is stable and not susceptible to a change. Thus, thedescribed coating is not a responsive coating.
One of the important functionalities of responsive coatings is thedetection of moisture build-up in the surfaces under the coatings, such aswooden surfaces, metal surfaces or other surfaces.
For wooden surfaces, existing methods to detect moisture aremainly destructive, e.g. wherein two pins are inserted in a wooden object tomeasure the moisture resistance in the wood. Non-destructive methodsbased on e.g. unilateral mobile NMR and infrared thermography are notalways sufficiently precise or applicable. Also, for other types of surfacesnon-destructive methods are not known.
Moreover, existing methods only allow a local measurement of themoisture content of the surface under the coating, and not of the wholesurface at once.
An object of the present invention is therefore to provide a coatingfor different kinds of surfaces that is suitable for detecting moisture inobjects. It is a further object of the present invention to provide a method todetect moisture in objects that is non-destructive, precise and allows toanalyse the whole object at once. It is also desired that the method is simplein use and does not require costly detection equipment.
In order to better address one or more of the foregoing desires, theinvention, in one aspect, provides a coating composition comprising a systemcomprising a dye encapsulated in a matrix of a polymer, wherein the dyeonly shows absorption in a non-visible part of the light spectrum, whereinthe encapsulated system is able to undergo a detectable change in theabsorption properties under the influence of a solvent, preferably moisture.
The invention is based on the judicious insight that a rapid, non¬destructive and simple moisture detection of large surfaces can be realisedusing a signalling layer with encapsulated systems comprising a dye and apolymer, wherein the dye does not absorb in the visible spectrum whileshowing absorption in a non-visible part of the spectrum, and wherein thecombination of the dye and the polymer is able to change absorptionproperties under influence of solvent (moisture) in the environment. It canalso be said that the dye only shows absorption (above detection limits) inthe non-visible part of the spectrum. The system can also be used to detectthe presence of other solvents than moisture.
The system comprising a dye in a matrix of a polymer ispreferably realized in the form of microparticles. In a preferred embodiment,as described below in more details, the microparticles have a core-shellstructure wherein the core comprises the dye and the shell comprises thepolymer. This has as an advantage that the encapsulated system showshigh chemical stability and is also easy to handle. In an alternativeembodiment, the system is realized in the form a (semi-)continuous matrixof the polymer wherein the dye particles are dispersed.
In such a signalling coating the absorption properties of the dyecan be changed, from absorbing to non-absorbing or vice versa, due to atrigger. The system can thus undergo a detectable change in the absorptionproperties at a particular wavelength. The change should be detectable withconventional means such as by a modified camera. Particularly, the changein absorption at a particular wavelength should be at least 10% inabsorption units (AU), preferably at least 20%, more preferably at least50%. The trigger can be thermal, mechanical or chemical such as pH,presence of moisture, corrosion, etc. The change of state of the dye can forexample be triggered by the change of polarity by solvents, redistributionover the coating or redistribution of particle sizes of the dispersed dye.
In some embodiments, the trigger can be a mechanical trigger.Examples of such triggers in various application areas are described in thefollowing references. “Interaction between microcapsules and cementitiousmatrix after cracking in a self-healing system”, Wang, X., Xing, F., Zhang,M., Han, N., Qian, Z,, ICSHM 2013: Proceedings of the 4th InternationalConference on Self-Healing Materials, Ghent, Belgium, 16-20 June 2013.“Mechanical Properties of Microcapsules Used in a Self-Healing Polymer”M.W. Keller and N.R. Sottos, Department of Theoretical and AppliedMechanics and Beckman Institute for Advanced Science and TechnologyUniversity of Illinois at Urbana-Champaign, Urbana, IL 61801, September6, 2005.
In some embodiments, the trigger can be thermal. Examples ofsuch triggers in other application areas are described in the followingreferences. “Temperature-triggered on-demand drug release enabled byhydrogen-bonded multilayers of block copolymer micelles”, Zhichen Zhu,Ning Gao, Hongjun Wang, Svetlana A. Sukhishvili, Department ofChemistry, Chemical Biology and Biomedical Engineering, Stevens Instituteof Technology, Hoboken 07030, USA, Journal of Controlled Release.“Thermo-stimulable wax-Si02 core shell particles”, Mathieu Destribats,Véronique Schmitt et Rénal Backov. Langmuir, 2 February 2010. “TriggeredRelease from Polymer Capsules”, Aaron P. Esser-Kahn, Susan A. Odom,Nancy R. Sottos, Scott R. White and Jeffrey S. Moore, Beckman Institute forAdvanced Science and Technology, Department of Chemistry, Departmentof Materials Science and Engineering, and Department of AerospaceEngineering, University of Illinois at Urbana Champaign, Urbana, Illinois61801, United States, Macromolecules.
Particularly, in one embodiment, such trigger can be pH, or theproton activity in the surface, which is in direct contact with the coatingcomprising the dye. The composition therefore in one embodiment comprisesa pH sensitive polymer. The presence of moisture in the object near the coating at certain proton activity or pH, at which the pH sensitive polymerexhibits hydrophilic properties, leads to the rupture or disintegration of thecapsules with the dye in the coating due to the swelling or hydrolysis of thepolymer. Other examples of triggers are other solvents than water. In otherembodiments, the polymer is pH degradable. Such polymer does not swellupon action of the trigger but degrades leading to the permeability of thepolymer shell.
If the encapsulated system also contains a solvent and the dye isdissolved in that solvent, the disintegration then leads to the solventdiffusing out of the capsules and a change in the state of the dye. This canfor example be the change from a solvated to a non-solvated state. Thechange can also be in the altered concentration of the dye, or a differentdispersion of the dye in the matrix, etc.
It is also possible that a solvent is encapsulated in the polymermatrix separately from the dye, and after disintegration of the capsule, thesolvent diffuses to the dye and at least partially dissolves it. In all theseembodiments, the dye changes its absorption properties, for example, it doesnot absorb in the IR or UV area anymore. The change in absorption can bedetected with a suitable camera. A preferred embodiment of the invention is a coating comprisingmicroparticles applied to a wooden surface and a pH as the trigger for aswitch in the state of an IR dye. However, this does not limit the applicationof this invention, which can be applied to other surfaces, such as metalsurfaces, and also other triggers such as change of polarity by solvents, etc.
In a preferred embodiment, microcapsules containing a dyedissolved in a solvent within the microcapsule shell, are uniformlydistributed in a coating matrix, e.g. paint. Water from the surroundingenvironment comes in contact with the wood and generates acids, such astannic acids. The resulting decrease of the pH under the coating serves as atrigger for the decomposition of the microcapsule shell. This allows the encapsulated solvent to diffuse in the coating matrix. When the dye has avery low solubility in the coating matrix it will not diffuse into the coatingmatrix and precipitate, resulting in a decrease of absorption signal.Alternatively, the dye is dispersed in its undissolved state in the coatingmatrix and the diffusion of solvent in the coating dissolves the activeingredient leading to an increase in absorption signal. The decrease (orpossible increase) in absorption is the signal for the moisture getting incontact with the wood.
The system used in the coating according to the present inventioncomprises a dye in the matrix of a polymer. Preferably, the system ispresent in the form of microparticles, which preferably comprise a core anda shell surrounding the core. It is to be understood that a microparticle canalso have multiple cores; likewise, also multiple shells are possible. Themicroparticles preferably have a particle size less than 30 pm, preferablyless than 10 pm, more preferably less than 1 pm. Also other structures ofthe microparticle are possible, e.g. solid dye particles being dispersed, orembedded, in the polymer matrix. In that case, the solid dye particlespreferably have a particle size less than 30 pm, preferably less than 10 pm,more preferably less than 1 pm. In the present context, the particle sizerefers to the largest particle diameter as measured on a representativenumber of microscope photos (such as 20).
In one embodiment, the encapsulates system further comprises asolvent. This can be a solvent in which the dye is soluble, the dye thus beingpresent in a solvated form. It can also be a non-solvent for the dye. Thesolvent can also be present in the encapsulated system (microparticle) in anencapsulated form itself, so that no interaction between the solvent and thedye takes place before the polymer matrix disintegrates under the influenceof the trigger. In this case the dye is present initially in a non-solvated formin the system and becomes solvated after the disintegration. Theencapsulated system can also comprise a plasticizer, which can also act as a solvent for the dye. A skilled person is able to choose a suitable plasticizerfor a particular system. In one embodiment, aliphatic esters are used as aplasticizer, preferably, 1,2-cyclohexane dicarboxylic acid diisononyl ester(DINCH, Hexamoll®).
Preferably, the change in the dye properties under the influenceof the trigger is the change in the absorption properties of the solvated andthe non-solvated states. For example, one of these states should exhibitabsorption in a certain (IR or UV) area, while the other state should exhibitsubstantially no absorption in the same area, or at least absorption in alesser degree. Substantially no absorption means here at least 10 timeslower absorption than in the absorbing state. In one such embodiment, thedye in a solvated form preferably absorbs in the IR area, while in the non-solvated form it does not absorb in that area. In another embodiment, thedye in a solvated form does not absorb in the IR area, while in the non-solvated form it absorbs in that area. Particularly, the dye in the solvatedform preferably absorbs light with a wavelength in the range of 700-2400nm, and in a non-solvated form it does not absorb light in that area, or viceversa.
Preferably, the dye is an IR or UV dye, which means that the dyeshows absorption in, respectively, the IR or the UV part of the lightspectrum. More preferably, the dye only shows absorption in the non-visiblepart of the light spectrum. In some embodiments, the dye is an IR dye.
It is preferred that the dye exhibits a single strong absorptionpeak in the IR or UV area. Preferably, in the most absorbing state (e.g.solvated form), the dye has an absorption peak in the wavelength region700-2400 nm or 10-400 nm, more preferably 750-1200 nm. In the other state(e.g. non-solvated form), the dye should not absorb light in the same area, orabsorb in a lesser degree. Preferably, in the less absorbing state (e.g. non-solvated) the dye should absorb less than 50%, preferably less than 30%,more preferably less than 10% than the most absorbing state (e.g. solvated), measured as the ratio of intensities at a same wavelength. The same appliesto the case when a non-solvated form absorbs the most in the non-visiblelight spectrum (IR or UV area).
The solvated state refers to the situation in which the dye canmolecularly interact with the matrix and/or a solvent present, in such amanner that it will change the absorption behaviour of the dye moleculerelative to the non-solvated state. The non-solvated state refers to thesituation in which the majority of the dye molecules do not interact with thematrix and/or a solvent.
Without wishing to be bound by particular theory, it is believedthat in order to have optical effects, the distribution of the particles in thecoating is relevant, since only the surface molecules of a finely dispersedpowder have optical effects. It is also believed that only these surfacemolecules interacting with the matrix and/or solvent provide the opticaleffects and not the bulk. Since the dyes have such molecular interaction, thebehaviour can be switched on and off by changing the compatibility with theenvironment, e.g. use of a non-solvent or solvent. This allows the dyes tochange from an absorbing to a non-absorbing state and vice-versa.
The dye used in the present invention preferably essentially doesnot absorb light in the visible region (wavelength in the range 400-700 nm)and therefore has no colour for the naked eye. The non-absorption in thevisible spectrum allows the dye to be used in decorative coatings withoutaffecting the colour of the coating (e.g. paints).
Suitable dyes can for example be organic dyes, polymeric dyes,metal complexes, plasmonic particles. Some specific examples of particularlysuitable NIR dyes are NIR1002 and NIR1047 of QCR. Examples of UV dyesinclude coumarin and its derivatives, such as 7-hydroxy-4-methylcoumarinor 7-hydroxy-3-methylcoumarin, but also benzophenones, p-aminobenzoicacid, camphor, dibenzoylmethane, homosalate, cinnamates, crylenes andderivatives thereof. In a particular embodiment, non-fluorescent dyes are used. A skilled person is able to determine which dyes do not showfluorescence. Fluorescence in the visible spectrum is even undesirable, e.g.in decorative coatings it would influence the colour of the coating (paint). A group of preferred organic dyes includes quaterrylenes,quinophthalones, anthraquinones, dioxazines, cyanines. Suitable dyes arefor example LUMOGEN® from BASF like LUMOGEN 765, a quaterrylenedye with an absorption maximum at 765 nm, NIR dyes from QCR Solutions,ADS and FEW Chemicals.
Some suitable NIR absorbing organic dyes are shown in Table 1herein-below together with their chemical formula (if known) and theabsorption maximum wavelength.
Table 1
Another group of suitable dyes is metal chelates, preferably nickelchelates. Suitable dyes from this group include ADS845MC, ADS920MC,ADS870MC (from ADS dyes), bis(dithiobenzyl)niekel, bis(4,4'-dimethoxydithiobenzyl) nickel, bis(4-dimethylaminodithiobenzyl)nickel.These dyes are shown in Table 2 below with their chemical structure andthe absorption maximum wavelength.
Table 2
In a preferred embodiment, the encapsulated system furthercomprises a solvent. The dye can be dissolved in the solvent, or it can beencapsulated separately to prevent the contact. The dye can thus be presentin a solvated form, or in a non-solvated form initially in the microparticle.Any suitable solvent wherein the dye is soluble, can be used. In someembodiment, solvents wherein the dye is not soluble are used, e.g. incombination with other solvents wherein the dye is soluble - in this way thesolubility of the dye can be influenced. A skilled person is able to find asuitable solvent for a particular dye.
In some embodiments, the solvent is preferably not water and thesolution is thus non-aqueous. Preferably, an organic solvent is used.Accordingly, in these embodiments the dye is not a water-soluble dye.Typically, organic solvents such as ketones, esters, and alcohols aresuitable. For example, for the NIR1002 and NIR1047 dyes a particularlysuitable solvent is methyl isobutyl ketone (MIBK).
The dye is preferably present in the solution in an amount of lessthan 1 wt.%, preferably less than 0,1 wt.%, more preferably at most 0.01wt.%, such as 0.00001 - 0.01 wt.%, preferably 0.0001-0.005 wt.%.
The composition according to the invention comprises further apolymer. In one embodiment, the polymer is a pH sensitive polymer andpreferably have a critical swelling pH under 7, more preferably at 2.5-6.0,yet more preferably 2.6-5.8, most preferably 3.0-5.0. This pH range isparticularly useful for wood surfaces, since it has been found by theinventors to correspond to the pH in the wood which has been subjected tomoisture. This pH is applicable to all non-chemically treated wood sorts.Preferably, the wood sorts include larch, fir, pine, Douglas fir, maple, birch,beech, ash, meranti, teak. In other applications, a basic critical swelling pH(that is, greater than 7, preferably at least 8) may be desirable.
The critical swelling pH of a polymer is a pH at which a switch inhydrophobic/hydrophilic properties takes place. Particularly, in oneembodiment, the polymer has hydrophilic properties at a pH below theswelling pH and exists in a swelled form with hydrated polymer chains. At apH above the critical swelling pH, it has hydrophobic properties and is in acollapsed form. Prefer ably, copolymers (or hydrogels) having moietiescapable of being protonated and thereby becoming cationic (cationiccopolymers) are used as pH-sensitive polymers in the present invention.Such copolymers contain cationic (positively charged) moieties on theirbackbones, that is moieties that are capable of being protonated. Thecopolymer shows either hydrophilic or hydrophobic properties depending onthe pH of the environment. At pH values higher than the pKa of the cationicmoieties, the copolymer is hydrophobic (excludes water from the system)and is in the collapsed state whereas at pH values lower than the pKa thecopolymer becomes hydrophilic and absorbs water resulting in a swollenstate. The pH of the switch in the hydrophobic-hydrophilic properties can be referred to as the critical swelling pH. At this pH, the transition betweenthe swollen and the collapsed states takes place.
Copolymers capable of being protonated can be prepared by thecopolymerisation of monomers capable of being protonated onto a polymerbackbone. Such copolymer is therefore preferably a polymer copolymerisedwith at least one monomer capable of being protonated. The monomercapable of being protonated is preferably selected from the group consistingof acrylates, methacrylates, vinylics containing at least one primary,secondary or tertiary amine or sulfide group and derivatives thereof.
Preferably, the polymer backbone contains at least one tertiaryamine group, since these protonate at a low pH. When the pH is decreasedbelow the pKa of the ionisable groups, protonation of the amine groupsoccurs resulting in the formation of positive charges along the backbonechain.
Suitable copolymers can be prepared from dimethylaminoethylmethacrylate (DMAEM) or diethylaminoethyl methacrylate (DEAEM) withmethyl methacrylate (MMA). Another example is a copolymer ofdimethylaminoethyl methacrylate, butyl methacrylate, and methylmethacrylate. A suitable polymer is for example Eudragit E PO.
In another embodiment, hydrolysable polyesters are used as a pH-sensitive polymer. Examples of these are polylactic acid (PLA), polyglycolicacid (PGA), poly(lactie-co-glyeolic acid) (PLGA), polycaprolactones. In thisembodiment, the polymer is a pH degradable polymer, which degrades at aparticular pH. Preferably, the critical point is pH under 7, more preferablyat 2.5-6.0, yet more preferably 2.6-5.8, most preferably 3.0-5.0. Particularlysuitable pH degradable polymers are acid-catalyzed hydrolysable polyesters,preferably aliphatic-aromatic polyesters such as Ecoflex® from BASF.
The encapsulated system can further contain other components,such as at least one of surfactants, dispersion aids, wetting agents,thickeners, anti-foaming agents, stabilizers.
In one embodiment, the coated surface is a wooden surface.Preferably, the wood sorts include larch, fir, pine, Douglas fir, maple, birch,beech, ash, meranti, teak.
The encapsulated system such as microparticles described abovecan be prepared by a method, comprising encapsulation of the dye in amatrix comprising the polymer. Any suitable encapsulation method knownto the skilled person can be used, for example solvent-evaporationtechnique. During encapsulation surfactants can be used to reduceagglomeration, if necessary. Suitable surfactants are known to a skilledperson. When the microparticles also comprises a solvent, in which the dyeis dissolved, the dye may be dissolved in this solvent prior to theencapsulation.
The encapsulated system used in the invention is preferably usedin the form of a dispersion of microparticles in a suitable organic orinorganic solvent, e.g. in coatings for wooden or other surfaces. The coatingcomposition can further comprise conventional components such as a liquidphase (organic solvents or aqueous), binders, etc.
The coating composition according to the invention is generallyapplied to a substrate (e.g. a wooden or metal surface) and dried to form acoating. After the coating is applied, the moisture content of the coatedsurface can be detected due to the presence, change or lack of the absorptionof the dye present in the coating.
In a further aspect, the invention provides a method to detectmoisture in objects, the method comprising the steps of: (a) providing an object with a signalling layer, said signallinglayer showing light absorption in a non-visible part of the light spectrumand a change in this light absorption under the influence of moisture, and (b) measuring the light absorption or reflectance of the coatedobject in the non-visible part of the light spectrum.
In a preferred embodiment, the signalling layer comprises anencapsulated system as described above, that is, comprising a dye in amatrix of a polymer, wherein the dye shows absorption in a non-visible partof the light spectrum and wherein the encapsulated system of the dye andthe polymer undergoes a change in its light absorption under the influenceof moisture.
In another preferred embodiment, the step of measuring the lightreflectance or absorption is carried out at least twice, the method furthercomprising the step of detecting differences in the light reflectance orabsorption of the object in the non-visible part of the light spectrum.
The differences can be determined in various ways. For example,this can be done in time, wherein at least two measurements of the lightreflectance or absorption are carried out with a time interval, such as,weeks, months, years. In this case only the non-visible part of the spectrumshould be analysed.
In another embodiment, the differences of the whole spectrum aredetected, e.g. it is possible to make measurements at the same moment(although not strictly necessary) of the whole spectrum and of the non-visible part. This can also be combined with measurements with timeintervals, e.g. to perform a double check, to monitor the differences in thevisible and non-visible part of the spectrum in time. In this embodiment alsoimage analysis can be used, for example if a visibly smooth coating has anirregular pattern in UV or IR, the presence of irregularities (spots) maypoint to the spots with moisture present. This makes it possible to alsodetermine the exact place of the moisture build-up.
The invention further relates to a software program product,preferably comprising a tangible data carrier, which software programproduct comprises instructions for carrying out the step of detecting thedifferences in absorption or reflection, optionally differences in time or of location. The data carrier can, for example, be a DVD, USB stick or anothersuitable carrier.
Preferably, in the described method the dye changes its state fromabsorbing to non-absorbing or vice versa, under the influence of a trigger,preferably thermal, mechanical or chemical such as pH, presence ofmoisture, or corrosion.
In the present invention, the moisture is detected by detecting thereflectance or absorption (both influenced by absorption properties of thematerials) of light having a wavelength in the non-visible part (IE or UVarea) of the light spectrum of the coated surface. The precise wavelengthrange where the absorption is to be detected preferably corresponds to theabsorption peak of the used dye.
In a preferred embodiment, the reflectance in the IR area cansuitably be detected using a CCD camera. Current CCD chip technologiesare used in everyday mirror-reflex photo cameras. The CCD chips used inthese cameras have a sensitive region all the way up to 1200 nm in theinfrared (IR) region. However, when taking images usually only theinformation from the visible spectrum is relevant and therefore filters for IRcut-off are placed in these cameras to filter out the information from the IRregion. However, by removing these filters and applying alternative filtersspecific signals in the infra-red can be detected.
For example, by taking two images - one of the whole spectrum(IR filter switched on, or present) and one only of the visible part (IR filterswitched off, or removed), image analysis can be used to only analyse the IRpart of the image. In this way the region in which the absorption orreflectance has changed considerably can be identified. Specially designedsoftware can be used for the image analysis, which is subsequently used for“assessing” the need for intervention such as maintenance, e.g. to preventfurther damage.
Therefore, in a preferred embodiment, the detection is carried outby making at least two images of the coated object, more preferably a firstimage using a filter and a second image without using the filter, the firstand the second image being made at substantially the same point in time orat substantially different points in time.
As an example, a coating can be used wherein a dye is dissolved ina solvent and both are encapsulated in a pH-sensitive polymer matrix. Incase the dye is used that shows absorption in a solvated state and noabsorption in a non-solvated state, the object without moisture will showabsorption (e.g. dark or black areas) in the NIR picture. If the objecthowever contains moisture, this will be visible in the NIR picture as lack ofabsorption.
In a preferred embodiment, the method is applied to a coatedsurface of an object which is a wooden or metal surface, and is preferably awooden surface. The wood sort is preferably selected from larch, fir, pine,Douglas fir, maple, birch, beech, ash, meranti, or teak.
By detecting the absorption or reflectance of the coating atdifferent points of time, the presence of moisture in the material underlyingthe coating, e.g. wood, can be monitored in time in all weather conditions.Preferably, the method is applied to objects with wooden and metal surfaces,however other applications are also possible.
For the purpose of clarity and a concise description features aredescribed herein as part of the same or separate embodiments, however, itwill be appreciated that the scope of the invention may includeembodiments having combinations of all or some of the features described.The invention will now be illustrated in the following, non-limitingexamples. Parts and percentages mentioned in the examples and throughthe description, are by weight, unless otherwise indicated.
Example 1: Solvent based triggering
The organic NIR dye NIR1002A was chosen as signalling agentbecause of its high absorption coefficient in the NIR area. The transmissionspectra of the dye in a dissolved state, 0.001wt.% in MIBK, measured in 1cm cuvette, is shown in Figure 1. Figure 1 also contains the transmissionspectrum of the solvent MIBK.
The dye is dispersed as solid particles in a polyacrylatetransparent coating prepared from polyacrylate latex dispersion, in the formof coating films with the thickness of 15 microns. Figure 2 shows theabsorption spectrum of the coating film with NIR1002A (upper curve) andwithout the dye (lower curve), in the area 400-1100 nm.
As seen in Figure 2, no substantial absorption is measured in theNIR area of the coating films, when the dye is not solvated.
The dye NIR1002A was formulated in the polyacrylate coating,applied on a glass substrate, and dried. To trigger the switch in theabsorption properties, the lower half of the surface of the coating is wettedby the solvent MIBK. This leads to a dissolved state of the dye andswitching from a non-absorbing to an absorbing state.
Figure 3 shows a picture taken in both the visible (top) and NIRregion (bottom) using a camera. For the NIR image a filter with the cut-off850 nm was used. Over a distance of circa 2 meter, the solvent-wetted areais clearly visible. In the visible light however, no colour change is visible.This also shows that only a low concentration of the dye is already sufficientto create the switch effect.
Example 2: Encapsulation of NIR dye using pH degradable polymer
The hydrophobic NIR dye, dissolved in a hydrophobic plasticizerHexamoll, was encapsulated with an acid-catalyzed hydrolysable polyester(Ecoflex®) using solvent-evaporation technique, which results in core/shellmicrocapsules. During encapsulation a surfactant TAMOL® (condensatednaphtalenesulphonic acid)/PVA has been used to reduce aggregation. Theobtained microcapsules are shown in the microscopic (SEM) images inFigure 4.
The images in Figure 4 clearly show the formation of core/shellcapsules. The inset of the SEM image showing an indented capsule indicatesthat the formed particles are hollow. The reason for the indentation is thatthe environment of the SEM is a high vacuum. Even though the plasticizerhas a high boiling point, at such low pressures the plasticizer evaporates.The evaporating core causes the polymer shell to collapse in itself.
The obtained microcapsules are then incorporated in the coating.The absorption characteristics of the coating are measured with aspectrophotometer and the resulting spectra are shown in Figure 5. Thelower curve corresponds to the coating with incorporated microcapsules, theupper curve corresponds to the aqueous dispersion of the microcapsules.
The aqueous dispersion is measured in a cuvette, while thecoating is applied on a glass microscope slide and inserted as such in thespectrophotometer. The absorption was also measured with the respect tocapsules containing no NIR dye and it was concluded that the absorption inFigure 5 is due to the presence of the NIR dye.
Figure 5 shows that the characteristic absorption of the NIR dyeis present in both the coating and the dispersion, although to a differentextent. The difference in absorption of the NIR dye in the coating and in theaqueous dispersion is explained by the thickness of the measured layer - the coating is only 75 pm thick, wMle the cuvette has an internal width of 5 mm. This is an order of magnitude difference which explains the largedifference in absorption.
Example 3: Particulate NIR dyes in coating systems
Moisture signalling can also be achieved by gradual dissolution ofthe NIR dye solid particles and redistribution of the dye within the coating.Upon dissolution and redistribution, the coating changes its opticalproperties from respectively non-absorbing to absorbing. A solvent-borne alkyd coating containing a water-soluble NIR dyeS2161 (FEW Chemicals) was prepared. In Figure 6, an optical image takenwith a camera with a NIR filter (cut-off: 652 nm) is shown. The image showstwo coatings: on the left half is the coating with the NIR dye and on theright half is the coating without the NIR dye. The figure shows that there isno difference in absorption. Both the NIR dye containing coating as well asthe reference coating show no absorption in NIR spectral region.
Figure 7 shows the optical image of a water-borne acrylate coatingcontaining the same NIR dye S2161. The dye is more finely dispersed(probably even nearly molecularly distributed in the coating), due to similarsolubility of the NIR dye and coating material. The difference in absorptionbetween the dye containing coating (left) and the reference coating (right) isclear. The molecularly distributed dye-containing coating shows a strongabsorption, which is detectable with a common digital camera.
The difference in dispersion state can be triggered by the presenceof water in the coating and possibly accelerated by acids.

权利要求:
Claims (25)
[1]
A coating composition comprising a system comprising a dye encapsulated in a polymer matrix, the dye showing absorption only in an invisible portion of the light spectrum, the encapsulated system being able to undergo an appreciable difference in absorption properties under the influence of a solvent, preferably moisture.
[2]
The coating composition of claim 1, wherein the encapsulated system is in the form of microparticles.
[3]
The coating composition of claim 2, wherein the microparticles have a core-shell structure and wherein the core comprises the dye and the shell comprises the polymer.
[4]
The coating composition according to any of the preceding claims, wherein the polymer is a pH sensitive polymer that has a critical swelling pH, which is preferably below 7 and more preferably in the range 2.5-6.
[5]
The coating composition of any one of claims 2-4, wherein the microparticle further comprises a solvent.
[6]
The coating composition of claim 5, wherein the colorant is dissolved in the solvent, whereby the colorant is present in a solvated form.
[7]
The coating composition of claim 6, wherein the colorant is present in the solution in an amount of less than 1% by weight, preferably less than 0.1% by weight.
[8]
The coating composition according to claim 6 or 7, wherein the dye in the solvated form absorbs light with a wavelength in the invisible part of the light spectrum, and in an unsolvated form does not absorb light from that part of the spectrum.
[9]
The coating composition according to claim 6 or 7, wherein the dye in the solvated form does not absorb light with the wavelength in the invisible part of the light spectrum, and in a non-solvated form absorbs light from that part of the spectrum.
[10]
The coating composition according to any one of the preceding claims, wherein the pH-sensitive polymer is a copolymer that can be protonated.
[11]
The coating composition according to claim 10, wherein the copolymer is polymerized from at least one monomer that can be protonated selected from the group consisting of acrylates, methacrylates, vinyl polymers comprising at least one primary, secondary or tertiary amine or sulfide group and derivatives thereof.
[12]
The coating composition according to any of the preceding claims, wherein the pH-sensitive polymer is a hydrolyzable polyester, preferably selected from the list consisting of polylactic acid, polyglycolic acid, poly (milk-co-glycolic acid), polycaprolactones.
[13]
The coating composition according to any of the preceding claims, wherein the dye is an IR or a UV dye, and preferably a non-fluorescent dye.
[14]
The coating composition according to claim 13, wherein the dye is an IR dye with an absorption maximum in the wavelength range 700-2400 nm, preferably 750-1200 nm.
[15]
The coating composition of claim 13, wherein the dye is a UV dye with an absorption maximum in the wavelength range 10-400 nm.
[16]
The coating composition according to any of the preceding claims, wherein the dye is selected from the list consisting of organic dyes, polymer dyes, metal complexes, and plasma particles.
[17]
The coating composition of claim 16, wherein the dye is an organic dye selected from the list consisting of coumarin, benzophenones, p-aminobenzoic acid, camphor, dibenzoylmethane, homosalate, cinnamates, crylenes, and derivatives thereof.
[18]
The coating composition according to any of the preceding claims, wherein the encapsulated system further comprises at least one of surfactants, dispersants, wetting agents, thickeners, antifoaming agents.
[19]
A method for detecting moisture in objects comprising the steps of: (a) providing an object with a signaling layer, wherein the signaling layer only exhibits adhesion in a non-visible part of the binding spectrum and shows an appreciable difference in this adhesion under the influence of moisture and (b) measuring the moisture absorption or reflection of the coated object in the non-visible portion of the bend spectrum.
[20]
The method of claim 19, wherein the signaling layer comprises an encapsulated system, which system comprises a dye in a polymer matrix, the dye exhibiting absorption in a non-visible portion of the bend spectrum and wherein the dye and polymer encapsulated system a difference in the moisture absorption undergoes under the influence of moisture.
[21]
The method of claim 19 or 20, wherein the step of measuring light reflection or absorption is performed at least twice, the method further comprising the step of detecting differences in the light reflection or absorption of the object in the staple -visible part of the bend spectrum.
[22]
The method according to any of claims 19-21, wherein the dye changes its state from absorbent to non-absorbent or vice versa, under the influence of a trigger, preferably a thermal, mechanical or chemical trigger, such as pH, presence of moisture or corrosion.
[23]
The method of any one of claims 19-22, wherein dereflection of the coated object is detected using a CCD camera, preferably by taking at least two images of the coated object, more preferably a first image using a filter and a second image without using the filter, wherein the first and the second images are taken at essentially the same time point or essentially different time points.
[24]
The method of any one of claims 19-23, wherein the coated surface of the object is a wooden or metal surface, preferably a wooden surface.
[25]
The method of claim 24, wherein the wood species is selected from larch, spruce, pine, Douglas fir, maple, birch, beech, ash, meranti or teak.

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同族专利:

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公开号 | 公开日

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CA2919336A1|2015-02-05|

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WO2015016716A1|2015-02-05|

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RU2662522C2|2018-07-26|

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NL2013295B1|2016-05-18|

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US20160178510A1|2016-06-23|

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RU2016102089A|2017-09-07|

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EP3027693A1|2016-06-08|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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EP13179121|2013-08-02|

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EP13179121|2013-08-02|

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