Patent Grant
8303857
The invention relates to a composite with inverse thermochromic properties, the composite changing from a colourless into a coloured state with increasing temperature. The composite thereby contains a colourant, a developer and a fluxing agent and also an inorganic filler. The invention likewise relates to a composite material which contains a polymer-based matrix into which at least one composite with inverse thermochromic properties is doped. These composite materials are used in the field of sensor technology, solar technology, transport and communications technology and medical technology.
Under the influence of external parameters, such as e.g. pressure, light, electrical fields and temperature, chromogenic materials change their optical behaviour. Thermochromism includes the capacity of a material to change its colour as a function of temperature, reversibly or irreversibly. This can be effected both by changing the intensity and/or the wavelength maximum. In Seeboth et al., Chinese Journal of Polymer Science 2007 (2) 123, the interaction between structure and thermochromism is explained in detail.
Materials based on different material components with general thermochromic properties are known from the state of the art. It is common to them that they generally have a thermally induced colour or transparency change. EP 1 084 860, U.S. Pat. No. 4,028,118 and U.S. Pat. No. 4,421,560 describe the switching of the colour effect, based on a donor-acceptor colourant system, with at least two further components. The change in colour is effected within wide temperature ranges, such as between −50° C. to 120° C. or −40° to 80° C. The smallest temperature difference is indicated in EP 1,084,860 at 30° C. The entire colourant system can be introduced into the polymer matrix optionally also in the form of microcapsules with a diameter of approx. 50 μm.
The production of polymeric thermochromic materials by means of printing (laminating) a thermochromic colour is a practical solution for some requirements and wishes of the packaging industry but does not achieve the set goal. Thus according to US 2002/037421, glasses are printed with a colour system for use for sun protection or, corresponding to U.S. Pat. No. 4,121,010, polymers are coated with a thermochromic colour, induced by sulphates, sulphides, arsenic, bismuth, zinc and other metals and oxides thereof.
As a result, both the field of use is greatly restricted and due to the required additional coating (printing technology) a cost-reducing continuous technology is prevented.
The production of organic thermochromic composites is still to date being optimised further and further. Thus further materials are constantly being doped to the basic composite, comprising at least one colourant, developer and fluxing agent. With respect to microencapsulation or control of the interactions between colourant-developer-fluxing agent, surfactant structures are increasingly being doped to the composite. There are used caprylates, malonates, oxalates, succinates, palminates, stearates, behenates or n-dodecylphenols, dodecylgallates, as described in EP 0 677 564.
All previously described thermochromic effects, reversible or irreversible, are based on a colour transition with temperature increase from coloured to colourless or from a coloured state into a differently coloured state. The change between different colours takes place by the combination of a plurality of thermochromic composites or by means of colour subtraction effects with a non-thermochromic colourant.
Thermochromic composites which switch from a colourless into a coloured state with temperature increase—i.e. systems with inverse thermochromism—are less known to date.
An inverse complex of this type, also termed pigment here, is described in US 2006/01668822 and EP 1 323 540. In both publications, the complex comprises—analogously to the known standard switch—a) an organic electron donor, b) an organic electron acceptor and c) an organic reaction medium with a melting point below 50° C. A disadvantage of this solution, in addition to high hysteresis in the switching process, is above all inadequate mechanical and chemical stability so that use in i) thermoplasts by means of extrusion technology, ii) duromers or iii) temperature-dependent coatings is not possible. Documents U.S. Pat. No. 5,849,651, U.S. Pat. No. 5,879,443 and U.S. Pat. No. 5,928,988 relate to the switching process from colourless to coloured in an organic thermochromic mixture by rapid cooling of the liquid phase without interaction to form a matrix.
The object therefore underlying the invention is to produce a completely novel thermochromic composite which can switch reversibly or irreversibly with temperature increase from colourless to coloured and with a temperature reduction from coloured to colourless and can be doped into a matrix of a composite materials whilst maintaining the thermochromism.
This object is achieved by the composite and composite material having the features described herein The utility and advantageous developments of the invention are also described herein.
According to the invention, a composite with inverse thermochromic properties is provided, which comprises at least one colourant, at least one developer and also at least one fluxing agent. Furthermore, the composite contains at least one inorganic filler which influences the interactions between colourant and developer, which lead to the thermochromism, in such a manner that the colourless state is present at low temperatures so that, with increasing temperature, the composite changes from a colourless into a coloured state. With an increase in temperature, a molecular switching mechanism of the colourant is effected, as a result of which the composite changes into a coloured form. The fluxing agent can thereby likewise be involved actively in the interaction between colourant and developer.
Surprisingly, it could be established that the composite according to the invention is both mechanically stable and chemically resistant.
With respect to the inorganic fillers, compounds which interact with the colourant and/or the fluxing agent can be used. It is likewise possible that the inorganic filler is a complex which interacts with the colourant and/or fluxing agent.
The charged or polar centres of the fillers initiate degradation of the structure of a higher system consisting of colourant-filler-fluxing agent. The system can be supplemented by an organic developer, which is however not essential. This hybrid organic-inorganic complex controls the inverse thermochromic behaviour.
With respect to both previously mentioned variants, the filler surface can be modified cationically, anionically or amphiphilically.
Preferably, the inorganic filler is selected from the group consisting of metallic salts of the first and second main group of the periodic table, compounds based on SiOx and mixtures hereof.
The metallic salts are thereby selected preferably from the group consisting of lithium chloride, sodium chloride, magnesium chloride, aluminium chloride, boron chloride, tin chloride, titanium chloride, vanadium chloride, vanadium oxychloride, germanium chloride, phosphorus chloride, magnesium sulphate, barium sulphate, sodium sulphate, sodium hydrogen sulphate, sodium hydrogen phosphate, calcium carbonate, borax and mixtures hereof.
The compounds based on SiOx are preferably selected from the group consisting of silica, quartz glass, muscovite, nepheline syenite, wollastonite, xonolite and mixtures thereof.
A further preferred variant provides that the inorganic fillers are coated with organic or organosilicon compounds. There are hereby possible as organic compounds in particular alcohols, amines, naphthalene, anthracene and phenanthracene. The organosilicon compounds are preferably compounds of the general formula XnSiR4-n with R=alkyl, vinyl, alkoxy, aminoalkyl or aminoalkoxy, independently of each other, and X=Cl, OH, OCH3, OC2H5, independently of each other. Particularly preferred are aminoalkylsilanes, dimethyldimethoxysilane, hexamethyldisilazane, dimethyldichlorosilane and mixtures hereof. The alkyl or alkoxy groups are preferably selected from straight-chain or branched C1-C16 groups.
Reactions between organic filler and the organosilane or its hydrated form can lead to the formation of Lewis centres on the surface. This mechanism in the organic-inorganic thermochromic complex can be effected both before and directly in the extrusion step.
The colourant contained in the composite is preferably selected from the group consisting of pyridinium phenolate betaines, sulphophthalein structures, Reichhardt colourants, triphenylmethane colourants, pyranines, indicator colourants, azo colourants and mixtures thereof.
A preferred variant provides that the composite has an inorganic compound which serves as developer and filler. Hence developer and filler are present as a single compound.
The developer is preferably selected from the group comprising 2,2′-bis(4-hydroxyphenyl)propane, 2,2′-bis(4-hydroxyphenyl)sulphone, gallic acid dodecylester and mixtures hereof.
The fluxing agent is preferably selected from the group consisting of octadecanol, dodecanol, hydroxycarboxylic acids, 1-hexadecanol and mixtures hereof.
The composite is present as inorganic-organic hybrid. It is distinguished in particular in that it has mechanical, thermal and chemical stability which allows processing, e.g. by extrusion or annealing.
The switching behaviour of the composite can thereby be both reversible and irreversible.
According to the invention, a composite is likewise provided, which comprises a polymer-based matrix with at least one doped-in composite, as was described previously.
The matrix is thereby preferably selected from the group consisting of thermoplasts, duromers, varnish or hydrogels. For particular preference, the matrix comprises polyethylene, polypropylene, polyester, polyamide, acrylonitrile-butadiene-styrene copolymer and copolymers and blends thereof.
The composite can thereby be distributed preferably homogeneously in the matrix so that the matrix has no concentration gradient with respect to the composite. The application of a twin-screw extruder and the use of commercial dispersion aids, such as Dispex, Efka, Ruetasolv or Glascol, also contribute to the homogeneous distribution.
The previously described composite materials are used for production of components for sensor technology, solar technology, transport and communications technology and medical technology.
Materials with inverse thermochromism open up completely novel fields of use in sensory technology, solar technology, transportation technology and medical technology. The application possibilities are extended even more by combining with standard thermochromic composites or with non-thermochromic colour pigments.
The invention is intended to be explained in more detail with reference to the subsequent example and the subsequent FIGURE without wishing to restrict said invention to the special embodiments shown here.
According to the invention, an inverse thermochromic composite can be produced by using the individual components crystal violet lactone (CVL), xonotlite, tetradecanol in the mass ratio 1:3:3.4. Subsequently, the composite is extruded with 4.5% by weight into a polyolefin film at a temperature above 255° C., the thermochromic effect being maintained. With a temperature increase, the film becomes blue. The thermochromic switching process is reversible in the temperature range of 20° C. to 80° C. (see
A thermochromic composite comprises the components CVL, muscovite, titanium chloride, phosphorus chloride. The mass ratio is 1:3:2:1.4. The composite is extruded homogeneously distributed with 3.7% by weight into a polyolefin film above 260° C. The inverse thermochromic switching process is reversible between room temperature and 85° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2007 017 791 | Apr 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2008/003044 | 4/16/2008 | WO | 00 | 3/25/2010 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2008/125350 | 10/23/2008 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3915916 | Leverett | Oct 1975 | A |
| 4028118 | Nakasuji et al. | Jun 1977 | A |
| 4121010 | Lasky et al. | Oct 1978 | A |
| 4307942 | Chahroudi | Dec 1981 | A |
| 4421560 | Kito et al. | Dec 1983 | A |
| 5178990 | Satake et al. | Jan 1993 | A |
| 5300558 | Kurisu et al. | Apr 1994 | A |
| 5318939 | Laver et al. | Jun 1994 | A |
| 5527385 | Sumii et al. | Jun 1996 | A |
| 5849651 | Takayama et al. | Dec 1998 | A |
| 5879443 | Senga et al. | Mar 1999 | A |
| 5928988 | Yamane et al. | Jul 1999 | A |
| 6057466 | Starzewski et al. | May 2000 | A |
| 6440592 | Meyer et al. | Aug 2002 | B1 |
| 6489377 | Bicer et al. | Dec 2002 | B1 |
| 6670436 | Burgath et al. | Dec 2003 | B2 |
| 6706218 | Lucht et al. | Mar 2004 | B2 |
| 20020037421 | Arnaud et al. | Mar 2002 | A1 |
| 20020065401 | Feiler et al. | May 2002 | A1 |
| 20030109910 | Lachenbruch et al. | Jun 2003 | A1 |
| 20050147825 | Arnaud et al. | Jul 2005 | A1 |
| 20050227047 | Sutter et al. | Oct 2005 | A1 |
| 20060166822 | Senga et al. | Jul 2006 | A1 |
| 20060189737 | Pieslak et al. | Aug 2006 | A1 |
| 20060246292 | Seeboth et al. | Nov 2006 | A1 |
| Number | Date | Country |
|---|---|---|
| 133004 | Nov 1978 | DE |
| 35 23 661 | Jan 1987 | DE |
| 40 25 796 | Feb 1991 | DE |
| 196 42 886 | Apr 1998 | DE |
| 696 21 627 | Feb 2003 | DE |
| 103 12 464 | Sep 2004 | DE |
| 103 39 442 | Mar 2005 | DE |
| 102007017791 | Oct 2008 | DE |
| 0 477 140 | Mar 1992 | EP |
| 0 524 692 | Jan 1993 | EP |
| 0 677 564 | Oct 1995 | EP |
| 1 084 860 | Mar 2001 | EP |
| 1 084 860 | Mar 2001 | EP |
| 1 157 802 | Nov 2001 | EP |
| 1 211 300 | Jun 2002 | EP |
| 1 258 504 | Nov 2002 | EP |
| 1 323 540 | Jul 2003 | EP |
| 1 387 995 | Feb 2006 | EP |
| 9-235545 | Sep 1997 | JP |
| 10-2003-016589 | Mar 2003 | KR |
| WO 9315625 | Aug 1993 | WO |
| WO 9402257 | Feb 1994 | WO |
| WO 9711830 | Mar 1997 | WO |
| WO 9964488 | Dec 1999 | WO |
| WO 0208821 | Jan 2002 | WO |
| WO 03089227 | Oct 2003 | WO |
| WO 2005021627 | Mar 2005 | WO |
| WO 2005032838 | Apr 2005 | WO |
| WO 20051032838 | Apr 2005 | WO |
| WO 2005077665 | Aug 2005 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20100181541 A1 | Jul 2010 | US |
