Microlens protective coating with floating image using material with shape memory

FIELD: physics.

SUBSTANCE: protective coating has a layer of polymer material with shape memory, having a surface made of microlenses, where each microlens is associated with one of a plurality of images on the protective coating. The layer of polymer material with shape memory is sensitive to external stimulating effect, for example to temperature, a solvent or moisture, owing to transition from a first state in which the optical property of the microlens has a first value to a second state in which the optical property of the microlens has a second value. The microlenses have refracting surfaces which transmit light to positions in the protective coating, yielding a composite image from images formed on the protective coating when the layer of polymer material with shape memory is in one of a first or second state.

EFFECT: invention provides change in optical properties of the article as a result of the external effect.

9 cl, 19 dwg

 

Reference to related applications

This application is related to jointly consider the application for U.S. patent No. 11/460685, filed July 28, 2006, entitled "Polymeric product shape memory with a microstructured surface", and together with the considered application for U.S. patent No. 11/460682, filed July 28, 2006, entitled "Methods of changing the shape of the surface of a polymeric product shape memory".

The technical field to which the invention relates.

The invention relates to a protective coating that provides one or more composite images.

The level of technology

The coating materials with a graphic image or other label is widely used, in particular as labels for authentication of an item or document. For example, one conventional protective cover with image uses light reflective protective coating openly-lens type with high gain, in which images are formed by irradiating the protective coating by laser through a mask or template. This protective coating contains a lot of transparent glass microspheres partially embedded in a binder layer, and partially open on the binder layer, and a metal reflecting layer deposited on the embedded surface of each of a multitude of microspheres. Swazey the third layer contains carbon black, which, as stated, which minimizes diffuse radiation, which affects the protective coating during the coating process images.

The laser beam energy is additionally concentrated due to the focusing action of the microlenses embedded in the binder layer. Images formed in this reflective protective coating, can be seen, if - and only if - protective coating is examined under almost the same angle at which the laser radiation was directed to a protective coating. This means, in other words, that the image is visible only in a very limited angle of consideration.

The invention

In General, this disclosure describes a protective coating formed from a polymer material with a shape memory that has the characteristics of shape memory that cause the protective coating to make the transition from the first state into the second state in response to an external stimulus. The protective coating includes a layer of microlenses on one surface of the polymer material with shape memory. Due to the characteristics of the shape memory polymer material with shape memory optical properties of the microlenses can be changed in a controlled and repeatable manner when exposed to an external stimulus. For example, images can be printed on the protective coating is AK, in order to present a composite image when viewed at a suitable angle of view. This is a composite image can visually "to appear" or "disappear" in response to an external stimulus. In this example, the effect is achieved by changing the optical properties of the microlenses, which is the result of changes in the physical form of a layer of microlenses due to the passage of polymeric material with shape memory. For example, when the protective coating is exposed to an external stimulus such as heat, solvent or moisture, a protective coating is transferred from the first physical state into a second physical state. One of the optical properties of the microlenses, such as the focal length changes from the first value to the second value in response to the physical transition experienced by the polymer material with shape memory.

Described here, the protective coating can be used in many applications. As one example, the protective coating can be used as a passive sensor, visually indicating the exposure to a certain temperature. As another example, the protective coating may function as a humidity sensor, pressure sensor, or may detect the presence of a solvent. The protective coating may also be used as the safety characteristic, which visually changes in response to external stimulus, thereby confirming the authenticity of the product, to which is attached a protective coating. As a protective sign of the protective coating can be used in many applications, such as banknotes, passports, driver's license, identification card, credit card or other protected documents.

In one embodiment, the protective coating includes a layer of polymeric material with shape memory, having a surface of microlenses, in which each of the microlenses is associated with one of multiple images in a protective coating. The layer of polymeric material with shape memory responds to an external stimulus by switching from a first state in which the optical property of the microlenses has a first value, a second state in which the optical property of the microlenses has a second value.

In another embodiment, the method comprises the steps, which form a protective coating comprising a layer of polymeric material with shape memory in a permanent form, and this layer has a surface of microlenses, and put the image on the protective coating so that the surface of the microlenses formed image in the provisions of the inside of the protective coating. This method additionally who engages in the stage, which deform the layer of polymeric material with shape memory in a temporary form.

In yet another embodiment, the product has attached to it a protective coating, and this protective coating includes a layer of polymeric material with shape memory, having a surface of microlenses, which visually gives a composite image of the one or more images formed in positions in the protective coating. The layer of polymeric material with shape memory responds to an external stimulus by switching from a first state in which the optical property of the microlenses has a first value, a second state in which the optical property of the microlenses has a second value.

The details of one or more embodiments of the invention are given in the accompanying following drawings and description. Other characteristics, objectives and advantages of the invention will become apparent from the description, drawings and claims.

Brief description of drawings

Figa-1B are enlarged views in cross section of example microlensing protective coatings formed from a material with shape memory.

Figure 2 is a block diagram of an algorithm illustrating an example of a manufacturing process of the protective coating with a layer of microlenses formed from a material with memory Faure is s.

Figure 3 is a graph illustrating the dependence of the temperature over time for example, the protective coating with a layer of microlenses formed from a material with shape memory.

4 is a flowchart of an algorithm illustrating an example of the programming process of the protective coating with a layer of microlenses formed from a material with shape memory.

Figure 5 is a graph illustrating the dependence of temperature on time for another example, the protective coating with a layer of microlenses formed from a material with shape memory.

Figa-6C are images of atomic microscopy, illustrating the example microlensing array.

Figa-7B are traces rays illustrating the results of the model ray tracing for molded lenses and flattened lenses.

Figa-8B are optical microgravity for molded lenses and flattened lenses.

Fig.9 is a graph illustrating a comparison of the surface profile measured using nuclear microscopy for molded microlenses and microlens, which was deformed, and then thermally restored.

Figa is atomic microscopic Microsystem showing an example of the embossed microlenses.

Figv is atomic microscopic Microsystem showing extruded lens after the film was ostanovleno to the original flat state in accordance with the principles of the invention.

Figa-11C are photographs of a sample of the protective coating, which caused the floating image disappear when the protective coating was crushed at high temperatures, and appear again when the protective coating was heated.

Detailed description of the invention

Figa is an enlarged view in cross section of an example of the protective cover 10. In this example, the protective cover 10 includes a PLANO-convex or aspheric sheet 11 base having first and second surfaces, the first surface includes an array of almost hemispherical or polusfericheskikh microlenses 14 and the second surface 12 is essentially flat. The sheet 11 of the base is formed from a polymeric material with shape memory, as described in more detail below. In this first embodiment, the shape of the microlenses and the thickness of the sheet 11 of the base are chosen so that collimated light incident on the array, centered approximately on the second surface 12. On the second surface of the protective cover 10 is provided by a layer of material 16. In some embodiments, the implementation of the layer of material 16 may be sensitive to radiation material. The sheet 11 can be transparent or translucent light-diffusing.

Figv is an enlarged view in cross section microlensing protect the spas cover 20, containing one layer of microlenses. In the illustrated embodiment, for Figv protective coating 20 contains a transparent PLANO-convex or aspheric protective coating having first and second surfaces, the first surface includes an array of almost hemispherical or polusfericheskikh microlenses 24 formed therein, and the second surface 22 is essentially flat. Layer 26 is formed from a polymeric material with shape memory, as described in more detail below. In this second embodiment, the shape of the microlenses 24 and the thickness of the layer 26 are selected so that collimated light incident on the array, focused on areas 28 inside layer 26. The thickness of the layer 26 depends at least in part on the optical characteristics of the microlenses 24, such as the distance at which the microlenses focus the light. For example, can be used with lenses that focus light at a distance of 60 μm from the front edge of the lens. In some embodiments, the implementation of the thickness of the layer 26 may be in the range of 20-100 μm, so that the microlenses focus the light within the layer 26.

Microlens protective coatings 10, 20 Figa-1B preferably are forming the image refracting surface in order to place the image formation; usually it is provided with a curved surface microl is NZ. When the curved surfaces of the microlenses will be preferable to have the same refractive index. Focal length/image spherical refracting surface surrounded by air, is defined by the formula:

where n is the refractive index of the material of the surface, R is a radius of curvature of the surface. The refractive index depends on the electronic properties of the atoms that make up the material, and therefore it is constant for a specific wavelength of light if the electronic configuration of atoms can not be changed. In this case, the only means to control the properties of the create image refracting surface is changing radius of curvature, i.e. forms a spherical refracting surface. The technology described in this review, provide a mechanism for controlled change of the shape of the refractive surfaces of the microlenses 14, 22, formed of a polymeric material with shape memory, under the influence of external stimulation or under the influence of environmental changes.

Sensitive to the environment of the microlenses can be used as a lens layer in the protective coatings with a "floating image"described in application for U.S. patent No. 11/399695, entitled "Protective coating is a composite image, which floats", filed on April 6, 2006, which is a partial continuation of application for U.S. patent No. 09/898580, filed July 3, 2001, which is a partial continuation of application for U.S. patent No. 09/510428, filed February 22, 2000, now U.S. patent No. 6288842, the entire contents of each of which are included here by reference. Because the optical properties of the microlenses, for example the radius of curvature, and thus the focal length may change under the influence of various external stimuli, can be manufactured protective coating that visually provides a floating image, the appearance of which changes in a predictable way based on environmental influences.

Although the surface of the microlenses are preferably spherical, aspherical surface is also acceptable. The microlenses may have any symmetry, for example, cylindrical or spherical, provided that the refractive surface form a real image or layer of material 16 (Figa), or in sections 26 through the decomposition of material ablation material changes in the composition of the material or phase transition (PI. 1B). The microlenses can be formed using the process of copying or extrusion, when the surface protective coating changes the form, giving a duplicate profile with the characteristics of the receipt from the expression.

In accordance with the principles of the invention, the microlenses are formed of a polymeric material with shape memory. Thus, in the examples Figa and 1B sheet 11 base Figa or layer 28 on Figv is formed from a polymeric material with shape memory. In General, polymeric materials with shape memory are polymers that respond to an external stimulus by physical shape changes. It is important that the polymeric materials with shape memory can be formed in a "regular" form (here referred to as the second physical "state"), deformed to a temporary shape (first physical "state") at temperatures above the transition temperature Ttransand chilled with maintaining the deformed shape. After the release of the material will retain its temporary shape up until not be subjected to temperatures above Ttransat which the material passes in the second physical state and restores its permanent form. One component of the material with shape memory, called "switching" segment defines permanent and temporary forms of the polymer. At temperatures above Ttransswitching segments these switching segments are flexible, the polymer can be deformed. Below Ttransthe switching of the switching segments segments lose souvislosti.

The desired shape can be made constant by cross-linking the polymer structure. Cross connection can be chemical or physical. For example, rubber transversely communicates to prevent fluidity by adding three or tetrafunctional reagents, electron beam cross-linking or peroxides, which decompose, forming free radicals that start the side chains that are cross linked polymer. For loop structure without distortion due to the fluidity of the preferred average molecular weight between cross-links, comparable to the total molecular weight or less.

An example of a preferred covalently cross-linked system can be based on ethylene copolymers. Suitable any comonomers that reduces the size of the crystal structure of polyethylene to minimize light scattering for a more pure imaginary image. You can use electron-beam radiation or peroxide cross-linking, followed by heating and cooling in a temporary form. When the material is heated to a temperature above the melting temperature, constant form will be restored.

Physically cross-linked polymers are the basis of thermoplastic elastomers. These rubber materials may be obtained l is the gage pressure and even cast again by re-melting, unlike covalently cross-linked rubbers. Block copolymers may be preferred. Some examples are polyurethane hard segments with polyolefin or polyester soft segments or polystyrene rigid segments with polyolefin soft segments. In order for these types of polymers useful for the present invention, the transition temperature for the switching segment must be lower than Tgor Tmsolid segment. For example, polyester switching segment can be based on polycaprolactone and melt in the region of 60°C, while the polyurethane hard segment may have a glass transition temperature of approximately 130°C. the Practical temperature range of formation of the permanent shape is from 130°C to boundary decomposition. Practical range for the formation of temporary forms ranging from 65 to 125°C with cooling in this form to a temperature below 50°C, which allows polyester switching segment to crystallize. Subsequent heating to temperatures above 60°C will melt polyester segments and will allow you to recover the permanent shape.

The external stimulus can be, thus, the temperature change. Alternatively, the material can be designed to change state when the impact of the tvii solvent, the effect of humidity, pressure change or other environmental changes. For example, the effect of the solvent can reduce the effective Ttransmaterial to a temperature below room temperature. The transition temperature of a material with shape memory may be melting temperature Tmor the glass transition temperature Tga material with shape memory. Although the transition temperature will usually be referred to in this review as the glass transition temperature Tgit is clear that instead, the transition temperature may be melting temperature Tmmaterial. Additionally, in some embodiments, the implementation of the polymeric material with shape memory can have more than one temperature transition.

As an example, polymer with shape memory, which are formed microlens may be polyurethane with poly(ε-caprolactone) switching segment; polyurethane with poly(tetrahydrofuranyl) switching segment; polynorbornene, polyethylene, ethylene copolymers, or other polymers, covalently cross-linked with ionizing radiation (heat-shrinkable polymers); oligo(ε-caprolacton)diola, functionalized with methacrylate end groups; or other polymer with shape memory. As another example, polymer with shape memory can be formed from telehealth siloxanes with different functionalities and ranges of molecular weights, together-reactive (meth)acrylate monomer at different proportions of siloxane with acrylate. For example, thelegality siloxane can be methacryloxyethyl siloxane (MAUS), acrylamidoethyl siloxane (ACMAS), methacrylamides siloxane (MACMAS) or methylstilbene siloxane (MeStUS). As an example, (meth)acrylate monomer may be isobutylacetate (IBA), cyclohexylacetate, the trimethyl cyclohexylamine, methyl methacrylate, methacrylic acid or t-butyl acrylate.

Microlenses with a uniform refractive index between about 1.35 and 3.0 at visible and infrared wavelengths can be most useful. Suitable materials of the microlenses will have minimal absorption of visible light, and in variants of implementation, in which the energy source is used to create the image sensitive to the emission layer, the materials should also exhibit minimal absorption of energy source. In the variant example of implementation, illustrated in Figa, the refractive power of the microlenses 14 preferably is such that light incident on the refracting surface is refracted and focused on the opposite side of each microlens, the light will be focused either on the rear surface 12 of the microlenses or the material 16 adjacent to the microlenses 14. Options is sushestvennee, in which the material layer 16 reacts to radiation, the microlenses 14 preferably form a reduced real image at an appropriate place on this layer. The reduction of the image is approximately from 100 to 800 times, particularly useful for the formation of images with good resolution.

One way to ensure structures of the image inside of the protective coating, for example in a layer of microlenses or on the layer of material adjacent to the microlenses, is the use of a radiation source to generate the image on the protective coating. It is assumed that the preferred device, capable of providing radiation with a wavelength between 200 nm and 11 micrometers. Examples of radiation sources with high peak power, useful for this invention are excimer flash lamp, crystal lasers passively modulated q and activated by neodymium yttrium-aluminum red (abbreviated as Nd:YAG), activated by neodymium yttrium-lilavatibai (abbreviated as Nd:YLF) and activated titanium sapphire (abbreviated Ti:sapphire lasers with modulated by the quality factor. These sources with high peak power is most useful with sensitive radiation materials, which form the image by ablation, i.e. removal of material, or in the processes of multiphoton absorption is possible. Other examples of useful radiation sources are devices that give a low peak power, such as diode lasers, ion lasers, solid state lasers are modulated without merit, metal vapor lasers, gas lasers, arc lamps and high-power incandescent lamp. These sources, in particular, is useful when the image is applied to the sensitive radiation environment non-ablative method.

To create images in the protective coating 10 on Figa or protective coating 20 on FIGU energy radiation source is directed onto the microlenses 14 or 22, respectively, and is controlled so as to give a highly divergent beam energy. Approximate image creation process in accordance with the present invention consists of directions of collimated light from the laser through the lens in the direction microlensing protective coating. To create a protective coating with a floating image, as further described below, in one embodiment, the light passes through the diffusing lens with a high numerical aperture (CHA), giving the cone much ambient light. For example, in some embodiments, the implementation can use the lens with net assets equal to or greater than 0,3.

Be the image of the object can be formed through the use of intensive source over the same either by delineating the contour of the object, or use masks. Thus, the recorded image was combined aspect, light from the object is radiated in a wide range of angles. When the light coming from the object, comes from one point of the object and is emitted in a wide range of angles, all the light rays carry information about the object, but only on this one point, although this information is information of the projection angle of the light beam. Because each individual microlens occupies a unique position relative to the optical axis, the light incident on each lens will have a unique angle of incidence with respect to the light falling on each other microlens. Thus, light will be transmitted by each microlens on a unique plot of the protective coating and to give a unique image.

More precisely, in the example of the delineation of the contour of the object one pulse light is emitted from only one of the imaging point of the protective coating, providing an image adjacent to each microlens, and a lot of light pulses are used to image many of the depicted points. For each pulse of the optical axis is located in a new position relative to the position of the optical axis when the previous pulse. Sequential changes in the position of the optical axis with respect to the microlenses result in appropriate and the change of angle of incidence for each microlens, respectively, in the position of the imaging point, created in the protective coating of this momentum. In the result, the incident light focused by the microlens, displays the selected picture in sensitive to the emission layer. Since the position of each microlens is unique with respect to each optical axis, the image formed is sensitive to the emission layer (or in the microlens for each microlens will be different from the image that is associated with any other lens.

Another method of forming a floating composite image uses an array of lenses to obtain much ambient light to create an image in the protective coating. An array of lenses consists of many small lenses with large numerical apertures, placed on a plane. When the entire array is illuminated by a light source, the array will give many cones strongly scattered light, each individual cone centered on the corresponding lens in the array. Due to the size of the array of individual cones energy generated by winsockapi, will be exhibited in the protective coating as if a separate lens was placed sequentially in all points of the array when receiving light pulses. The choice of lenses, the receiving incident light, is through the use of a reflective mask having transparent areas corresponding to the parts of the composite image, is the quiet must be exposed, and reflecting the areas in which the image should not be exhibited. With full coverage mask of the incident energy to those parts of the mask that allow energy will form a number of individual cones strongly scattered light outlining the floating image as if the image was defined by a single lens. It takes only one pulse of light for the formation of the whole composite image in microlesion protective coating.

Separate images formed in the protective coating, when viewed by an observer in the reflected or transmitted light, provide a composite image, which seems suspended or floating above, in the plane and (or) under a protective coating. Composite image formed by the above-described display technology, can be seen as the result of the summation of many images, partial and full, each of which is different projection of a real object. Many unique images formed by the array of tiny lenses, each of which "sees" the object or image with great perspective. For a miniature lenses protective coating creates a projection image, which depends on the shape and direction, which is the energy source. is, however, not all what the lens sees, is recorded in the protective coating. Only the part of the image or object visible with a lens, which is sufficient for modification of protective coatings energy will be recorded.

A composite image floating above the protective coating can be created using the technology of optical display, comprising dispersing lens, so that a number of hypothetical "ray image passing of the layer of material through each of the microlenses and back through the diffusing lens, met in position over the protective coating. In the same way, a composite image floating under the protective coating is created with the technology of optical display, comprising the use of a collecting lens, so that a number of hypothetical "ray image passing of the layer of material through each of the microlenses and back through the collecting lens, met in position under a protective coating.

Can be used other methods of forming the floating composite images that do not require the layer of material 16 (Figa) was sensitive to radiation. As examples, the individual images can be formed on the layer of material 16 with the technology of inkjet printing with high resolution photolithographic technology or nonreplica the AI desirable structures. Individual images can be full or partially full of images, and each image is associated with a single microlens, so that when viewed through the microlens formed a composite image. For example, the protective coating may use the principles of moiré magnification. See, for example, U.S. patent No. 5712731 in the name of Drinkwater et al., issued January 27, 1998, for Example, the protective coating may contain a separate image with components printed using ink and also components, depicted as described above. In some embodiments, the implementation in which the protective coating uses moire magnification, all individual images associated with the microlenses may be identical. As another example, the source can be used with high intensity for forming images by fotorazlozheniya or charring of the material layer for each microlens.

Composite image made in accordance with the principles of the present invention can be either two-dimensional (having length and width) and be either under or in the plane or over the protective coating; or a three-dimensional (having a length, width and height). Three-dimensional composite image can only occur above or below the sheeting, or, optionally, in any of the combinations of the provisions under in the plane of and above the protective coating.

The protective covering 10, 20 Figa and 1B can be used in many applications. As one example, the protective coating having a polymer material with shape memory and applied as described, the image can be used as a passive sensor to provide a visual indication on the impact of the set temperature. As another example, the protective coating can act as a moisture sensor, a pressure sensor, or may detect the presence of a solvent. The protective coating can also be used as a protective agent, visually changing in response to external stimulus, thereby confirming the authenticity of the product, to which is attached a protective coating. As a protective agent of the protective coating can be used in many applications, such as banknotes, passports, driving license, ID cards, credit cards or other protected documents.

Figure 2 is a block diagram of an algorithm illustrating an example of a method of manufacturing a protective coating with a layer of microlenses formed from a material with shape memory, which predictably changes the optical properties of the microlenses when exposed to one or more external stimuli. First protective coating, with the array containing a series of microlenses, is formed from a polymeric material with shape memory (30). For example, the protective coating having an array of microlenses may be obtained by pouring the solution on a tool having an array of recesses, and treatment solution of ultraviolet (UV) light. The resulting protective coating may be similar to a protective coating 10 or cover 20 to Figa, 1B, respectively. This configuration or the second state, called here a "regular" form a protective coating. Then, the protective coating is formed image (32). The image may be a composite image, referred to as "imaginary" or "floating" image generated by using one of the above mentioned technologies.

In the process of producing a protective coating may then be heated to a temperature above Tgpolymer with shape memory, and then physically deformed in some way (34). As one example, the protective coating can be flattened with the application, a compressing force to the protective coating. This deformation leads to a change in the optical properties of the microlenses, such as the focal length of the microlenses. For example, when the protective coating is flattened, the radius of curvature of the microlenses increases as focal length. Due to the changing optical properties of the virtual image can no longer be VI is Imam or can visually change. Then a protective coating is cooled, being kept in the deformed shape (36). This process leads to the fact that the protective cover is fixed in a temporary deformed shape, called the first state. This process of fixing the protective cover in the time the form is called "programming".

The protective coating will keep the flattened shape up until the protective coating again will not be heated to a temperature above the Tg of the polymer with shape memory (38), in which the protective coating restores its permanent shape (the second state) (40), and the virtual image appears again or returns to its original appearance. For example, while in the first state, the microlenses may have a radius of curvature of between 50 and 70 microns, in the second state, the microlenses may have a radius of curvature between 20 and 35 microns. In another example, in the first state, the microlenses may have a focal length of between 450 and 600 microns, while in the second state, the microlenses may have a focal length between 65 and 85 microns.

Figure 3 is a graph illustrating the dependence of the temperature over time for example, the protective coating with a layer of microlenses formed from a material with shape memory, in accordance with the principles of the invention. As shown in Figure 3, at time t1 the protective coating is made of polymer with shape memory in a permanent form at ambient temperature Tr. Constant form contains an array of microlenses. At time t2protective coating is formed virtual image, as described above. At time t3the protective coating is heated to a temperature above Tgpolymer with shape memory and is deformed to a temporary shape by flattening. In the virtual image is no longer present. Between t3and t4the protective coating is cooled back to room temperature Tr. Now the protective coating saves a temporary form. At time t5the protective coating is heated above Tg. Then a protective coating restores its permanent form, and the virtual image appears again. Thus, in this example, the virtual image is present with t2for t3invisible with t3for t5, and appears again after a time t5.

An alternative can be used temporary molding, other than a simple flattening of the microlenses described above. For example, can be used extrusion roller with a pattern different from that of the microlenses, or text that is larger than the microlens. In the case where the microlenses everywhere flattened, and drawing deeper, the object may look Boo the governmental message, or large icon without the floating image. After heating a large image can mostly (or completely) disappear, while you receive the floating image. If the areas between the indentations caused not affect the microlenses, it may be possible to have stamped the image and the floating image (with varying degrees of clarity depending on the proportions of unchanged microlenses), which becomes more visible floating image, and the extruded image becomes a phantom or disappears completely.

Figure 4 is a block diagram of the algorithm illustrating another example of a method of producing a protective coating with a layer of microlenses formed from a material with shape memory. First, the protective coating is formed from a polymeric material with shape memory (44). In this example, the protective coating can be formed almost flat shape. The flat form is a continuous form of protective coating. Then a protective coating is heated to a temperature above Tgpolymer with shape memory and deformed by extrusion using a template microlensing array (46). The protective coating is cooled on extruded in the form (48). In the extrusion of the protective coating keeps the temporary shape, having an array of microlenses.

Then in the protective coating creates an image, as described is use, so protective coating gives a virtual image when viewed at a suitable angle of view (50). The protective coating will retain the shape of the array of microlenses up until again will not be heated to temperatures above Tgpolymer with shape memory (52), in which the protective coating is almost restored to its permanent flat form (54), and the virtual image will disappear or will visually change. For example, when the protective coating returns to its flat form, due to changes in the optical properties of the microlenses, that is, the radius of curvature and, thus, the focal length, the virtual image may not be visible.

For example, in the first state, the microlenses may have a radius of curvature between 20 and 35 microns, in the second state, the microlenses may have a radius of curvature of more than 250 microns. In another example, in the first state, the microlenses may have a focal length of between 75 and 95 microns, while in the second state, the microlenses may have a focal length of between 750 and 950 microns.

Figure 5 is a graph illustrating the dependence of temperature on time to another example of the protective coating with a layer of microlenses formed from a material with shape memory, in accordance with the principles of the invention. As shown in Figure 5, at time t1protective coating tide which is a polymer with shape memory in a permanent form at ambient temperature T r. At time t2the protective coating is heated to a temperature above Tgpolymer with shape memory and is deformed to a temporary shape by extrusion using a template for forming an array of microlenses on the surface of the protective coating. Between t2and t3the protective coating is cooled back to room temperature Tr. Now the protective coating saves a temporary form. At time t4protective coating is formed virtual image, as described above.

In subsequent time t5the protective coating is heated above Tg. Then a protective coating is almost recovers its permanent flat shape. In the virtual image disappears. Thus, in this example, the virtual image is present with t4no t5and disappears at time t5. In some embodiments, the implementation of the protective coating may not return exactly to the initial shape after heating above Tgand can save a weak form of the array of microlenses. However, the virtual image can still almost disappear, because the residual shape of the microlenses may not be sufficiently small radius of curvature to play a visible imaginary image.

In the examples described in figure 3 and 5, the protective coating can be used for the operation of the sensors, retaining and visually indicating the fact that the protective coating has been subjected to temperatures above Tg. For example, the protective coating may be applied to the product and be used as a temperature sensor indicating that the product has been exposed to a certain temperature. As one example, the product may be a pharmaceutical product or food product that should not be exposed to high temperatures. The protective coating can be formed from a material with shape memory, with Tgclose to the temperature at which the product may be damaged. In the example in Figure 3, the protective coating can contain a virtual image with a message or a warning indicating that the product was subjected to high temperature and could be damaged or may be unfit for consumption. In this example, the virtual image is saved, even if the protective coating is later returned to a temperature below Tgbecause the virtual image is present, when the protective cover is returned to its permanent physical condition. Virtual image may contain text and / or graphics. In the example in Figure 5, the protective coating can include a virtual image containing text and / or graphics, showing the e, that the product is not exposed to undesirable conditions (e.g. high temperature). In this case, the virtual image disappears when exposed to high temperature protective coating. Virtual image does not appear again, even if the protective coating is later returned to a temperature below Tgbecause the virtual image is present, when the protective cover is returned to its permanent physical condition.

In some embodiments, the implementation of the protective coating may act as a sensor time/temperature, showing that the product was exposed to temperatures within the range of the total amounts of time. For example, polymer with shape memory may be such that the temperature that is only slightly greater Tgover a longer period of time gives the same effect as the temperatures considerably higher than Tgfor more than a short period of time. The shape memory effect will occur after total exposure to temperatures above Tg.

In other examples, the options for performing the protective coating may show the influence of the solvent. For example, when the protective coating comes into contact with the solvent, the solvent may cause compression of the microlenses that can change the diamonds the size or shape of the microlenses, causing the change or disappearance of the imaginary image. Moreover, the solvent may lower the effective Tga material with shape memory, in some cases, to a temperature below room temperature. In this example, when exposed to a solvent protective coating may behave as if it was heated above Tga material with shape memory, and experience described above, the shape memory effect. After evaporation of the solvent material with shape memory can substantially return to the previous size and / or shape. Preferably the solvent is not practically destroys and does not dissolve the material with shape memory.

Further examples of embodiments of the protective coating can specify the moisture. For example, the protective coating may be formed from a hydrophilic material, such as hydrophilic acrylate. In another example, the protective coating may be formed from a hydrophilic hydrogel material, such as polyethylene oxide or polyvinyl alcohol. As another example, the protective coating may be formed from a polymer water-based, cross-linked urethane. For example, when the protective coating comes in contact with moisture, optical property, such as refractive index n of the material may vary. In ka is este another example, the radius of curvature of the microlenses may also change when exposed to moisture.

As noted above, many materials with shape memory, with a wide range of Tgcan be used for forming a protective coating according to the present invention. Suitable material with shape memory and the corresponding Tgcan be selected depending on the particular application of the protective coating. For example, the protective coating may be formed from a material with shape memory, having a high transition temperature, for example above 80°C., in particular between 80 and 90°or between 100 and 110°C. In yet another example of the application of the principles of this consideration, when the protective coating is formed from a polymer with shape memory, with Tgslightly above room temperature, the virtual image may disappear or appear during the application of pressure and body temperature. In this case, the polymer shape memory may have a transition temperature between 25 and 35°C. This protective coating can be used as a protective means, for example as a means of validation for banknotes, identification cards, driver's licenses, credit cards, passports and other security documents.

The principles of the invention will now be illustrated using three examples of protective coatings, obtained as described here.

Example 1

Figa-6S ablauts the images of atomic microscopy (AFM), illustrating the results of the first experiment in which microlensing array was obtained in accordance with the technologies described here. Thelegality silicone with a molecular weight of 5000 (ending with methacryloxypropyl the polydimethylsiloxane) (5K MAUS) was dissolved in isoborneol the acrylate (IBA) in the ratio of 40/60 by volume, forming a solution. Then to the solution was added 0.5 wt.% photoinitiator Darocur™ 1173.

The film of this solution was cast on polyamide tool thickness of 5 mils. The instrument contained a hexagonal array of holes (step 34 microns)obtained by the process of planes excimer laser (ELMoF). The details of the process ELMoF see, for example, in U.S. patent No. 6285001 in the name of Fleming et al., issued September 4, 2001. Deepening had a diameter of 30 μm and a spherical shape with a radius of curvature 28.7 micron and conic constant -0,745. The polyamide film on the substrate was covered with a sheet of polyethylene terephthalate (PET) and treated by exposure to low-intensity ultraviolet (UV) light for 10 minutes. Figa is the image of the atomic microscopy (AWS), illustrating the resulting array of microlenses obtained in this process. The array of microlenses is a permanent form of film (protective coating).

The piece microlensing array was flattened by compression of the PET film at 110°C is then cooled to room temperature under pressure. Figv is an AFM image illustrating the deformed film with an array of microlenses. AFM analysis of the shape of the microlenses shown in Figa and 6B, implies that the radius of curvature of the molded microlenses was approximately 23 microns, while the radius of curvature flattened microlenses was approximately 60 microns. This increase of the radius of curvature 2.6 times had a distinct effect on the optical power of flattened microlenses compared to molded microlenses.

Figa-7B are traces rays illustrating the results of the model ray tracing (Zemax Optical Design Program Zemax Development Corporation, Bellevue, Washington) for (A) lens of molded microlenses and (C) flattened lenses flattened out of the microlenses. Figa-8B are optical micrographs for (A) molded microlenses and (C) flattened microlenses. The model assumes that the molded lens must focus visible light (Å=550 nm) in a spot with limited diffraction at a distance 74,4 μm from the front surface of the lens. On the contrary, as shown in Figv, the size of the focused spot flattened lens at this distance was seven times greater than for molded lenses. This is consistent with the optical microphotographs on Figa-8B, which show that image in the focal plane formed by the lenses molded lens array, were sharp bright the mi spots, while the image in the same plane for flattened lens array contained a much larger dull spots.

The flattened film is then heated in unlimited configurations to 110°C, which gave recovery of the structure shown in Figs. Fig.9 is a graph illustrating a comparison of the surface profile measured by AFM, molded microlenses and microlens, which was deformed, and then thermally recovered. Note that the 30-micron diameter, the difference in the profile of these two lenses was a maximum of approximately 200 nm, which indicates a perfect recovery of the original shape. These results showed that the material can be introduced into the optical device that can passively and pay to change their optical characteristics depending on its thermal history. In this example, the optical characteristics of the microlenses were destroyed by heat and pressure, with subsequent restoration of the focus lens by using heat.

Example 2

In the second experiment, a flat film 40/60 5K MAUS/IBA was prepared by the polymerization solution MAUS/IBA as in Example 1 between two PET films, separated by the delimiter to control the thickness. The obtained film using a pattern of the array of microlenses were made by extrusion using p is Luminoso tool described in Example 1. The extrusion procedure consisted of placing the tool on the strip, put on the steel plate. Film MAUS/IBA was placed on the instrument was covered with another PET film and another steel plate. Then this construction was placed in a precision press, was heated to 110°C., was pressed for 10 minutes, and then cooled to room temperature under pressure. Part of the film was heated in unlimited configurations to a temperature of 110°C for 10 minutes, to restore the original topology of the film.

Figa shows atomic microscopic micrograph of extruded microlenses in this experiment, as In figure 10 shows the atomic microscopy micrograph of extruded lenses after the film was "restored" in the initial flat condition. F profiles forms of lenses assume that the radius of curvature of the extruded lens was approximately 29 μm, while the radius of curvature "restored" lenses is at least ten times greater value. According to Equation 1 above, the extruded lens had a focal length of approximately 87 µm, compared with a focal length of 870 µm for lenses, "restored" in a flat condition. This example showed that by using films MAUS/IBA can squeeze functioning microl is NZ on the material with shape memory using heat and pressure, and that the microlenses have a strong change of the optical power at the subsequent action of heat.

Example 3

A protective coating was formed by applying the microlenses shape memory on the polycarbonate film of a thickness of 7 mils, containing the additive, which turns black when exposed to light of a Nd:YAG laser (wavelength =1064 nm). The film was covered with a solution containing 40% by weight of silicone resin (5K methylstilbene siloxane (MeStUS)) and 60% by weight of isobutylacetate (IBA). Darcour 1173 (0,5%) was used as photoinitiator. Part fluorinated cartonnage tool, marked up with process ELMoF containing the desired lens pattern, clung to the floor, and the floor was processed through the substrate using a 4-minute exposure to radiation from a mercury lamp in the microwave with the intensity of 31.4 mW/cm2and the peak wavelength of 371 nm. The obtained protective coating contained lens shape memory 30 μm in diameter and a focal length of 60 μm, formed from a polymer material with shape memory. Floating images were drawn in the engraving laser polycarbonate film through the microlenses using a pulsed Nd:YAG laser operating with an average output power of 1 W (pulse width of 1 nanosecond, the pulse frequency of 1 kHz). Floating images were formed, ischemic microimages, get behind each microlens.

Figa is a photograph of three sample images 52, drawn in the sample described above, a protective coating. Images are floating/diving squares and circles. A sample of the protective coating with the images shown on Figa was compressed at 280°F (137,8°C) for one minute and forty-five seconds between two polished chrome plates, measuring approximately 3"×3", with a force of 16,000 pounds. When a sample of the protective coating was removed from the press, the protective cover is maintained in a flattened configuration and contained areas, ex clean because of the flattening of the microlenses. In these net sites floating images of floating/diving circles and squares were no longer visible.

FIGU is a photograph of one of the pure plots of the compressed sample of the protective coating. Despite the fact that the floating image disappeared, the sample protective coating retained phantom two-dimensional image 54, the sending of square and circular shape. It exists at the expense of black microimages made for the microlenses in the process of recording the floating image. These two-dimensional images were placed in the forms of the floating image, giving the phantom a two-dimensional structure, but does not look like a floating/diving floating images. When the sample sasanov the coating was again heated to a temperature above the component IBA in the formula of the lens, the original form of microlenses recovered, and the floating image 52 appeared again. Figs is a photograph of a sample of the protective coating after reheating.

Described various embodiments of the invention. These and other embodiments of the are within the scope the following claims.

1. The protective coating contains:
the layer of polymeric material with shape memory containing a surface of microlenses, and a polymeric material with shape memory is polysiloxan with poly(meth)acrylate switching segment, and each of the microlenses is associated with one of multiple images in a protective coating,
when this layer of polymeric material with shape memory is characterized by the ability to respond to external stimulus through a transition from a first state in which the optical property of the microlenses has a first value, a second state in which the optical property of the microlenses has a second value.

2. Protective coating according to claim 1, wherein the microlenses are characterized by the refractive surfaces, which provide for the passage of light in the inside of the protective coating, thereby forming a composite image from the images formed within the protective coating, when the layer of polymer material with shape memory nah who is in one of the first state or the second state.

3. Protective coating according to claim 1, wherein the external stimulus is a temperature higher than the transition temperature of the polymer material with shape memory.

4. Protective coating according to claim 1, characterized in that the optical property is the focal length of the microlenses and microlens is arranged to change the radius of curvature of the microlenses in the transition layer of polymeric material with shape memory of the first physical state into a second physical state.

5. Protective coating according to claim 1, characterized in that it is combined with one of the banknotes, passports, driving license, ID card, credit card or protected document.

6. Method of forming a protective coating according to claim 1, comprising stages, which are:
form a protective coating in a permanent form;
put the image on the protective coating so that the surface of microlenses formed image in the provisions of the inside of the protective coating; and
deform the layer of polymeric material with shape memory in a temporary form.

7. The method according to claim 6, characterized in that the step of deforming the layer of polymeric material with shape memory includes the steps are:
deform the layer of polymeric material with shape memory to a temporary shape by flattening the surface microl the NC at a temperature greater than the transition temperature of the polymer material with shape memory; and
cool protective coating during deformation protective coating.

8. The method according to claim 6, wherein after cooling the protective coating protective coating is heated to a temperature above the transition temperature of the polymer material with shape memory, when this protective coating is transferred from the temporary shape to the permanent shape.

9. The protective coating contains:
the layer of polymeric material with shape memory containing a surface of microlenses, and a polymeric material with shape memory contains one polymer from the group consisting of polyurethane with poly(ε-caprolactone) switching segment; polyurethane with poly(tetrahydrofuranyl) switching segment; polynorbornene; polyethylene or ethylene copolymers covalently cross linked; and oligo(ε-caprolactone)diol functionalized with methacrylate end groups,
each of the microlenses is associated with one of multiple images in a protective coating, and a layer of polymeric material with shape memory is characterized by the ability to respond to external stimulus through a transition from a first state in which the optical property of the microlenses has a first value, a second state in which the optical with eusto of microlenses has a second value.



 

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