Patent Application
20200232857
The invention pertains to a composite, a method of manufacturing such a composite and the use of such a composite.
In logistics, e.g. transport and storage, numerous goods demand cooling to be protected against spoiling, aging and/or decomposition. The needed temperature in the cooling is substantially depending on the transported good. Frozen food needs a temperature of −18° C. or lower, fresh meat requires at most 4° C., milk and milk products have to be stored at 4 to 8° C. and chocolate demands a temperature of about 15 to 18° C.
Also several medical goods such as vaccines, blood bags, infusions, bacterial cultures, chemical reagents, as well as pharmaceuticals demand cooling.
Therefore, in logistics a cold chain was established to guarantee that the temperature sensitive goods are kept below the required temperature during the whole logistical process.
To guarantee that the cold chain has not been broken, the temperature has to be monitored permanently.
For monitoring the temperature, a variety of electronical sensors are on the m market. These electronical sensors typically cost more than 1 €/sensor and are far too expensive for broad application, such as on packaging of food, medicine and/or chemicals.
Also analogous organic time-temperature integrators (TTIs) are on the market, but these TTIs are generally multiple layer devices making them more expensive.
WO 2010/084010 discloses battery-free optical TTIs that comprise a coating of cholesteric liquid crystalline (CLC) polymer. The helical pitch of the cholesteric liquid crystals causes these materials to reflect a band of circularly polarized light, centered at wavelength λ0, thereby exhibiting a structural color. When mechanical compression is performed on the coating of a CLC polymer network above its glass transition temperature (Tg), the cholesteric helices are compressed, thereby causing a reduction in the reflected wavelength λ1 (where λ1<λ0), and hence inducing a color change. When the polymer network is cooled during compression (below Tg), glass formation occurs thereby locking in the color in a temporary mode upon removing the compressive stress. Shape recovery occurs only when the deformed coating of CLC polymer network is heated above its Tg, which is accompanied by an irreversible optical response (λ1→λ0). When heated, the mechanically compressed coating of CLC polymer network can act as a time-temperature integrator (TTI), with the transition centered at the Tg of the CLC polymer network. The kinetics of the shape recovery are temperature dependent, and the rate of recovery increases with increasing temperature.
U.S. Pat. No. 6,671,031 discloses a method for manufacturing a polarization diffraction film comprising liquid crystal material comprising a liquid crystal polymer and a cross linkable substance. These polymers are fixed in cholesteric alignment.
In the prior art there are some difficulties to scale up the manufacturing process. In WO 2010/084010, compression was performed using a small spherical stamp (radius of curvature=25.8 mm), resulting in the deformed areas being limited in area (˜mm), and a color variation between the edge and the center of the deformed zone.
However, in order to obtain embossed areas over industrially relevant dimensions (many TTIs in parallel), an even mechanical compression is required across the width of the envisioned production line. Therefore the stamp for embossing has to be even about its whole surface, and it is further required that the coating of the CLC polymer is very even, which requires precise printing techniques.
Due to the fact that the surface of the stamp and the surface of the coating have to be as even as possible, contamination by particles, e.g. dust, complicates the manufacturing of the photonic TTI based on this mechanism.
For the embossing of CLC polymers, the required accuracy increases with decreasing layer thickness. For example, to achieve a red-green color shift, a compression of ˜15% is required, which equates to 3 μm for a 20 μm layer but only 300 nm for a 2 μm layer. Generating an even color shift using industrial embossing equipment is therefore very difficult, since gap accuracies are typically ±1 μm.
Furthermore, there are some difficulties associated with the use of planar CLC films for the production of time-temperature sensors. First, the reflected wavelength in Bragg-reflection based optics is angle dependent, which results in the appearance of a different color when viewed at a different angle. Second, the optical properties are dependent on the coating conditions, and often so-called alignment layers are needed to control the alignment of the LCs. Third, modification of the time-temperature response profile is not trivial since it requires modification of the liquid crystal formulation, where the phase behavior and optical properties are sensitive to changes.
The object of the present application is to provide a composite, which allows to overcome the drawbacks of the prior art and is able to be manufactured fast and cheap and in a commercial attractive amount.
A further object of the present application is to provide an optical sensor which comprises the composite.
The object of the present application is solved by a composite comprising an upper layer and a substrate layer, wherein the upper layer comprises a shape-memory polymeric material having a glass transition temperature Tg,SMP and being at least partially opaque for light, characterized in that the upper layer comprises a rough surface, having an arithmetic average roughness Ra of at least 0.1 μm.
Within the scope of the invention, light has to be understood as electromagnetic radiation having a wavelength in the range of 10 nm to 1 mm, where the range 10 nm to 400 nm corresponds to UV light, 400 nm to 700 nm corresponds to the VIS-range, and 700 nm to 1 mm corresponds to infrared light
The arithmetic average roughness Ra can be calculated by formula (1):
In formula (i) Ra is the arithmetic average roughness, n is the number of measurements, wherein the vertical distance y between a mean line and the surface of the upper layer is measured, according to DIN 4768/1 “Determination of Surface Roughness of Parameters Ra, Rz, and Rmax by Electrical Stylus Instruments”. The mean line is calculated from the data set of measuring a rough surface, which is known to a person skilled in the art.
The effect of a rough surface of the upper layer is that the shape-memory polymeric material of the upper layer becomes at least partially opaque for the light by scattering the light by the rough surface. Thus, the transmittance of light through the shape-memory polymeric material of the upper layer is at least partially inhibited by the scattering of the rough surface of the upper layer.
Moreover, if the composite is exposed to a temperature which approaches the Tg,SMP the shape-memory polymeric material can relax to its original form, e.g. an upper layer having a smooth and even surface, thus, scattering of light is reduced and the surface of the upper layer becomes at least partially transparent for light.
Advantageously, by transferring the rough surface of the upper layer into a smooth and even surface by exceeding the Tg,SMP the composite is able to show a significant optical effect, e.g. color change and/or change between a transparent and opaque surface, which is visible to the naked eye.
Surprisingly, due to the optical effect of the rough surface of the upper layer, the composite overcomes the aforementioned disadvantages. The optical effect can be visible to the naked eye or amenable to machine readout using an optical instrument. Further, the rough surface can be obtained without disturbances caused by particle contamination, and the deformation can be performed over arbitrarily large areas. Additionally, the upper layer can be fabricated using common materials, and the use of CLC materials is no longer required. Thus, the composite can be manufactured fast in a commercial attractive amount at low costs.
Further, it is surprising that the optical effect of the composite is only depending on the properties of the shape-memory polymeric material of the upper layer, thus, decoupled from properties of a potential chromophoric substance, such as CLC polymeric material in the prior art. Thus, the optical effect is depending solely on the Tg,SMP and is therefore more easily modifiable.
In a preferred embodiment, the arithmetic average roughness Ra is at least 0.2 μm, more preferably at least 0.4 μm. The arithmetic average roughness can also be indicated by ISO Grade Numbers, according to ISO 4287:1997, wherein the ISO Grade Number N3 corresponds to an Ra value of 0.1 μm, N4 to an Ra value of 0.2 μm and N5 to an Ra value of 0.4 μm.
Without being bound to theory, it is believed that an upper layer having a rough surface with an Ra value of less than 0.1 μm, the above described effect is diminished. Also without being bound to theory it is believed by having a Ra value which exceeds widely the preferred ranges, the shape memory effect can be destroyed or at least disturbed by losing the reversibility of the shape memory effect.
In a further preferred embodiment of the invention, the upper layer has a thickness of at most 20.0 μm, preferably of at most 10.0 μm, more preferably of at most 6.0 μm, even more preferably of at most 4.0 μm, and most preferably of at most 2.5 μm.
The above described effects are almost independent from the thickness of the upper layer, thus, a thickness of more than 20 μm of the upper layer is possible. But, to save resources, to provide a cheap composite and for good handleability of the composite, a thickness of the upper layer of at most 20 μm is preferred.
In a preferred embodiment the Tg,SMP is below 70° C., preferably below 50° C., more preferably below 30° C., and most preferably below 20° C.
The effect of a Tg,SMP less than 70° C. is that the composite can show its optical effect by approaching the Tg,SMP at temperatures, which are common in storing and logistical tasks. For further improved applications a Tg,SMP above 70° C. or rather below 10° C., even negative temperatures, are possible and are depending on the composition of the shape-memory polymeric material.
Accordingly, the composite can be tuned to show the optical effect at different temperatures by selecting a certain shape-memory polymeric material.
In another preferred embodiment the Tg,SMP can be lowered by humidity and water, irradiation, organic vapors, amines, metal ions, pH-values, and chemical gases such as ammonia, carbon dioxide, carbon monoxide nitrogen dioxide, nitrogen monoxide, and oxygen.
Due to lowering the Tg,SMP by further exposure to one or more of the above listed analytes, enables the composite to show the optical effect at the operational temperature, which is assumed constant. Accordingly, the composite can be tuned to show its optical effect by different exposure by selecting certain shape-memory polymeric materials for the upper layer, which are sensitive to one or more of the above shown exposures.
In a further preferred embodiment, the substrate layer comprises a laminate of at least two sheets.
The substrate layer may comprise any suitable material on which an upper layer can be attached, including laminates having at least two sheets.
In a preferred embodiment, at least one of the at least two sheets of the substrate layer is selected from the group comprising a glass sheet, a polymeric material sheet, a paper and/or paperboard sheet, a metal sheet, a mineral sheet, and a sheet made of ink.
The effect of different sheets in the substrate layer is that the certain sheets e.g. glass as a transparent sheet or a sheet made of ink as opaque but colored sheet, can support the optical effect of the composite. Depending on the application the optical effect can be more significant (e.g. improved contrast between two or more modes) and more visible to the naked eye, by different sheets of the substrate layer.
Within the scope of the invention, the optical effect comprises two or more modes which have, e.g. a first mode, which is an initial mode, wherein the upper layer m has a flat and even surface and a second mode, which is a deformed mode, wherein the upper layer has a rough surface having an Ra-value of 0.1 μm or more. The optical effect can be e.g. a color change so that the first mode comprises a first color and the second mode a second color, wherein the first color and the second color are different, or a change between transparency and opaqueness, or a combination of both.
In a preferred embodiment, the upper layer and/or at least one of the sheets of the substrate layer comprises a CLC polymeric material.
CLC polymeric material can be provided according to WO 2010/084010 A1 and due to its cholesteric structure, the CLC polymeric material exhibits color. As also stated in WO 2018/033595 A1, by compressing the CLC polymeric material a color change can be produced.
If the CLC polymeric material is comprised in the upper layer and/or in a sheet of the substrate layer, it has the effect that by deforming (which includes embossing/compressing the composite) the surface of the upper layer, the CLC polymeric material can undergo at least partially a color change. This could support the optical effect of the composite in terms of an improved contrast between two or more modes and an improved visibility for the naked eye. If the CLC polymeric material is located in the substrate layer, the color (i.e. light of a certain wavelength) originating from the CLC polymeric material can be transmitted through the upper layer to be visible for the naked eye. By having a rough surface, the surface scatters the transmitted color/light such as the upper layer is getting opaque and the color originating from the CLC polymer is at least partially invisible to the naked eye.
Preferably, the CLC polymeric material maybe arranged in a layer and/or a sheet comprising a polymeric material.
In an embodiment, the CLC polymeric material are CLC particles.
CLC particles are a form of CLC polymeric material and can be provided according to WO 2015/120950 A1. The CLC particles have the advantage that the color of the particles is not viewing angle dependent. Therefore, the viewing angle independency supports the optical effect of the composite in terms of an uniform color and/or uniform color change when e.g. exceeding the Tg,SMP.
In another preferred embodiment, the at least one sheet of the substrate layer can be transparent and/or can have any possible color including white and black, preferably the color is black.
The fact that a sheet of the substrate layer is transparent, and/or has any possible color supports the optical effect of the composite in terms of improved contrast and/or uniform color change.
A composite according to the invention can also be manufactured by a method comprising the following steps:
Preferably, the stamp has a flexible surface. A flexible surface means that the surface of the stamp is made of a material having a Young's modulus of at least below 5 GPa, preferably of at least below 2 GPa, more preferably of at least below 1 GPa, and most preferably of at least below 0.5 GPa according to ASTM E111.
Preferably, the surface of the stamp comprises a material selected from a group comprising rubber, plastic, or paper material. The surface of the stamp may be a patterned surface or a non-patterned surface. The stamp can have any suitable shape for different processing techniques e.g. plate-to-plate, roll-to-plate and roll-to-roll processes.
A flexible stamp or a stamp having a flexible surface are known to a person skilled in the art. Non-limiting examples are disclosed in WO 2016/128494 and WO 2016/128493.
The composite manufactured according to the method can also comprise any of the above mentioned embodiments.
The composite according to the invention can be used as an optical sensor on substrates comprising food, medicine, chemicals, and/or any other temperature sensitive perishable goods.
The following figs. and examples have to be understood as embodiments of the invention and not as limiting features of the invention.
m
The shown composite comprises transparent CLC polymeric material in the upper layer so that the composite shows a transparency in the initial mode and an opaqueness in the deformed mode. Further
The shown composite does not comprise CLC polymeric material in the upper layer so that the upper layer is transparent and the red color of the substrate layer becomes visible in the initial mode of the composite. In the deformed mode the composite exhibits an opaqueness. Further
The shown composite comprises CLC polymeric material in the upper layer so that the blue/grey color of the CLC-particles becomes visible in the initial mode m of the composite. In the deformed mode the composite exhibits an opaqueness. Further
A composite comprising an upper layer made of CLC polymeric material (red color) and a black flexible polyethylene terephthalate (PET) substrate layer, wherein the upper layer has a thickness of approx. 2.5 μm measured according to profilometry, was manufactured by depositing a CLC ink on a black flexible polyethylene terephthalate (PET) substrate layer using flexographic printing (IGT Printability Tester F1 from IGT Testing System Pte Ltd.), and subsequently cured using UV-irradiation. The glass transition temperature (Tg) of the upper layer was determined by differential scanning calorimetry (DSC) to be approx. 15-30° C., with a mid-point at 18.4° C. The layer was subsequently deformed above its Tg (35° C., 30 s, 6 bar) using a hot-embossing stamp (KBA-Metronic GmbH). In the experimental setup, the surface of the upper layer was in direct contact with a roughly structured rubber (Ra≈1 μm), and the upper layer was quickly cooled to room temperature upon removal of the stamp. Since room temperature falls within the Tg range, the upper layer will slowly revert back to its undeformed mode under ambient conditions.
The optical micrographs of
Profilometry experiments performed on the upper layer of the composite prior to and after deformation reveal the transformation of a smooth surface (Ra=0.02 μm;
Further, it is observed that the typical angle-dependent reflection for planar aligned CLC polymeric material is significantly reduced by the deformation-induced scattering (
A composite as in E1 was used except that the CLC polymeric material and the polyethylene terephthalate (PET) substrate layer are transparent.
As shown in
A composite comprising a transparent shape-memory polymeric material as an upper layer and a clean glass slide as a sheet of a substrate layer and a red-reflecting CLC polymeric material as a further sheet of the substrate layer was manufactured by coating a clean glass slide with a commercially available monoacrylate (DSM), crosslinker, and photoinitiator, and subsequently cured with UV-radiation. The Tg,SMP of the upper layer was determined to be approximately 30° C. The glass slide containing the acrylic coating was subsequently placed on top of the red-reflecting CLC polymeric material used in E1 as an upper layer.
Prior to deformation, the reflection spectrum of the transparent acrylic coating with the background of the CLC polymeric material (
A composite comprising an upper layer as in E3 and a glass substrate layer, wherein in the upper layer additionally CLC particles are comprised, was manufactured by coating a clean glass slide with the acrylic coating precursors from E3 and additionally, a small amount of a CLC particle mixture (according to WO 2015/120950 A1). The CLC particle mixture consisted of green- and blue-reflecting CLC polymer particles, with a Tg of approximately 60-70° C. After coating, the precursors were cured with UV-radiation to result in a particulate upper layer consisting of the CLC particle mixture embedded in the acrylic binder. To prevent scattering (prior to deformation), it was ensured that the refractive index of the CLC particles and acrylic binder were matching (n˜1.5). The substrate layer containing the upper layer was subsequently placed on top of a black PET background, to reveal a blue tint (
Prior to deformation, the reflection spectrum of the acrylic coating with CLC particles showed two weak reflection bands, centered at 540 nm and 420 nm, corresponding to the green- and blue-reflecting CLC particles, respectively (FIG. 6B). The particulate coating was subsequently deformed using identical conditions as E1-3, resulting in a partially opaque appearance. It is important to note that the temperature at which the deformation is performed is below the Tg of the CLC particles. In this example therefore, only the Tg,SMP of the acrylic binder in the upper layer is important for achieving optical contrast.
Colorimetry measurements revealed that the reflection bands broadened slightly, which may be an effect of increased scattering events. At the same time, the reflection band is shifted evenly upward across all wavelengths, indicative of increased surface scattering. After heating, the upper layer returned completely to a transparent non-scattering mode. The advantage of the “particulate upper layer” approach is that optical contrast can be achieved using a single layer, while the thermomechanical (binder) and optical properties (CLC particles) are decoupled. It is important to note that in principle any dye can be used to generate color within the binder.
In order to illustrate the advantage of the deformation of the surface of the upper layer of the composite, the effect of compressing the upper layer using a rigid and smooth/uniform (Ra<0.02 μm) brass surface in an otherwise identical experimental setup to E1 is also investigated. In this case, a non-uniform color shift across the composite dimensions after compression is observable (
