Fluorescent articles having multiple film layers

FIELD: polymer material.

SUBSTANCE: invention relates to polymeric multilayer fluorescently stained particles widely applicable for distribution of visible information and provides sheet-shaped fluorescence-emitting articles. These have at least two film layers, each of which contains fluorescent dye in polymer matrix. Stained film of the upper layer is characterized by higher resistance to UV emission than stained sublayer film, and article itself has specified fluorescent coloration differing both from coloration of said stained fluorescent sublayer film and from coloration of said stained fluorescent upper layer. Manufacturing process for such articles is also described. Articles may optionally contain light-returning elements suitable as warning signs such as pedestrian crossing signs and signs indicating school zones, which emit fluorescent yellow color.

EFFECT: ensured resistance to weather conditions, increased color durability, and improved coloration characteristics regulated by industrial standards for particular conditions.

37 cl, 14 dwg, 3 tbl, 11 ex

 

The technical field to which the invention relates

The present invention generally relates to polymers containing fluorescent pigments. More specifically, the present invention relates to products possessing fluorescent properties and consisting of many layers, which together have important properties. Such properties provide the required brightness and chromaticity, with excellent resistance to weather conditions and/or General fastness.

Description of the prior art

Product in which fluorescent dyes are embedded in a polymeric matrix, are widely known and are used for various tasks, including the production of signs, license plates of cars, road signs, etc. where good visibility is required for a number of reasons, including safety rules, the need for dissemination of information, the need for good visibility, the need to supply the visual signals and the need for rapid discovery. In some cases, it is important to fulfill certain standards on color and/or reliability.

Often these polymer systems containing fluorescent pigments, structured in the form of sheets having the properties of light. Films of this type, containing fluorescent pigments, the OS is especially suitable for solving such problems, where the main function is giving signals. Usually they are in the form of characters, acquiring additional advantages due to its fluorescence. Known road and information signs containing sheet material, which has a fluorescent pigments that improve visibility of signs. These include different signs for different types of transport, product visual alarms, ensuring road safety reflectors, road markers, highway markers, street signs and other products, they can buy additional benefit due to improved visibility. Certain types of such signs require high wear resistance, which is a serious problem, since most fluorescent pigments quickly decompose under the influence of ultraviolet radiation. Some of these products have light reflective properties.

Over time, in the field of retroreflective articles appeared several directions. In General, there are three main types of retroreflective films used in the field of construction of roads, namely film-protected lenses, films with encapsulated lens and film with prisms. U.S. patent No. 2407680 (Palmquist) illustrates the so-called film svetovozvraschayuschey the products with protected lenses. It is known that products of this type are divided into three categories: construction, household and superstrategies and at an angle of incidence -4°and when the angle of reflection of 0.2° have a typical coefficient of svetovozvrascheniya 50-160 CD/Lux/m2for white film, depending on the particular product.

In U.S. patent No. 3190178 (McKenzie) in the General form illustrated the so-called reflective products with sealed lenses. These include film embedded in the polymer beads, which are sometimes referred to as "products of high brightness". For white films typical coefficient of svetovozvrascheniya approximately 300 CD/Lux/m2.

The third General category retroreflective film contains optical elements having the form of a microprism to provide exceptional reflectivity, usually component from 400 to 1600 CD/Lux/m2depending on the design of a particular product and the geometry of the corner reflectors. Retroreflective sheeting materials with corner reflectors are described in U.S. patent No. 3684348 (Rowland), 4588258 (Hoopman), 5605761 (Burns) and 6110566 (White). Publications such as U.S. patent No. 3810804 (Rowland) and 4601861 and 4486363 (Pricone), shows a method of manufacturing products of this type. It should be noted that this area also includes retroreflective sheet material through which thermoplastic material on the face of the stamping operation to obtain a prismatic sheet materials. The present invention finds application in products that have these basic designs, providing svetovanje.

Other sources described the application layer protection from ultraviolet (UV) radiation, which is located on top of or in front of the fluorescent layer. Such sources include patent publication Japan No. 2-16042 (application No. 63-165914) Koshiji, PCT publication No. WO99/48961 and WO00/47407 (Phillips) and U.S. patent No. 5387458 (Pavelka). In Japanese publication States that to protect the fluorescent sheet material can be used UV Ricadi. PCT publication relate to fluorescent polyvinyl chloride (PVC) tape with a layer of shielding from UV zlecenia with UV additives, which shields the radiation with a wavelength of 425 nm and below. In U.S. patent No. 5387458 mentions the use of a layer of shielding UV radiation on film selected from polymers containing the selected fluorescent dyes.

There are other ways to increase the durability of fluorescent colors using spatial difficult amine light stabilizers (HALS - hindered amine light stabilizer). Sources in this area include U.S. patent No. 5605761 (Burns) and 6110566 (White). The first one offers a combination of specific fluorescent dyes and HALS in the polycarbonate matrix. The latter offers a HALS with a low molecular weight is thioxanthene dye in solvent free PVC.

All of these patents, sources and patent publications included in the present description as a reference.

To a certain extent, all these sources is recognized that making retroreflective signs fluorescence properties can improve their visibility in most lighting conditions. Distinctive bright color and/or characteristics of the luminescence of the fluorescent material attract the eye to a luminous sign or another product. For example, products intended for outdoor signage and painted fluorescent pigments have an increased visual contrast, which makes these materials more visible than materials with non-luminous colors. If these signs are designed for outdoor use, there are two main obstacles. One of them is the durability for outdoor use, and the second is the availability of particular colors.

A common practice of increasing the durability of products that are intended for outdoor use is the application layer, the shielding of UV radiation, such as that described in the above sources, in an attempt to protect the base layer of the fluorescent polymer matrix. Traditionally, this layer shielding UV radiation, is made by dissolving the compounds that absorb UV radiation in a transparent polymer matrix. Known for the fluorescent product, consisting of a layer shielding UV radiation, applied before the fluorescent color layer. Layer, shielding UV radiation, is designed to absorb a specific range of wavelengths of ultraviolet range. Ultraviolet radiation has wavelengths of from 290 to 380 nm. Some sources propose to capture a certain area of the visible spectrum, for example up to about 400 or 410 nm and below. Often, such approaches are not considered and/or not solved the problem of the potential interaction between substance that absorbs UV radiation in the shielding layer, and a fluorescent dye in the underlying colored layer.

Most fluorescent pigments have poor stability under UV radiation. In some cases, the fading of the fluorescent sheet material under ultraviolet light reduces the useful life of items such as fluorescent traffic signs. Despite the fact that shielding of ultraviolet light is directed at solving the problems of durability of products for exterior use, you may experience a few difficulties. One of them is the possibility of gradual leaching or diffusion or migration of substances that absorb ultraviolet light of these shielding layers in the underlying fluorescent layer. This diffusion in certain cases the x can accelerate the fading of the fluorescent pigment.

In such sources as U.S. patent No. 5605761 (Burns) and 6110566 (White), available fluorescent film products, which do not necessarily contain a separate layer, shielding UV zlecenie. In these sources referred to the typical specific combinations of polymers and fluorescent dyes, often in conjunction with materials HALS, in the same film. In particular, in the first patent disclosed fluorescent products containing fluorescent dye and HALS inside the polycarbonate matrix. In the latter patent States that the combination of the fluorescent thioxanthene dye and material HALS in the matrix of solvent free PVC improves the light fastness of fluorescent colors in this system, PVC.

Acrylic polymers have advantages compared with such polymers like polycarbonate. Typical in this respect is polymethylmethacrylate (PMMA). Compared with other polymers, such as polycarbonate, such acrylates inexpensive, easier handling and less susceptible to degradation under UV zlecenia. For example, after several years of being outdoors polycarbonate can be designed to blur and/or yellow. Acrylates, however, can withstand such weather conditions much longer before you receive such defects.

Some sources indicate that acrylic polymers unsuitable for the introduction of fluorescent dyes. For example, in U.S. patent No. 5387458 (Pavelka) described fluorescent products containing fluorescent dyes, dispersed in various polymer matrices. It says that the durability of the glow of fluorescent dyes in PMMA small even when using sheet material, shielding UV radiation. In U.S. patent No. 5605761 (Burns) discloses fluorescent products containing specific fluorescent dyes and composition of HALS as polycarbonate and PMMA. This patent States that the introduction of substance HALS in polycarbonate matrix significantly increases the durability of the glow of the final products, but does not have the same effect on PMMA. In such sources, it is concluded that PMMA is not suitable for polymer matrix for fluorescent dyes, since the product on the basis of such acrylic does not have good durability glow when staying outdoors.

At the current stage of development of this technology, despite the fact that fluorescent acrylic products have some prospects, issues relating to stabilize the color and/or stabilization glow under UV radiation poses a significant problem. Ideally, if you can find a solution that does not require the use of the product of the individual layer, shielding and/or absorb the its ultraviolet light, this decision is all the more important and valuable. The solution to these problems is especially important for products that are intended for use outdoors and exposed to prolonged sunlight.

Referring now to the problem of creating products that meet the requirements of the standards, regulations or requests in relation to color, the color is a formidable challenge for suppliers of fluorescent products, especially those that should be very durable. This applies to governmental regulations relating to the colour, and to industry standards.

In this regard, here it is considered that there are three main approaches to obtaining the desired fluorescent color in the typical case, when the set of available fluorescent dyes do not provide the desired fluorescent color. One approach is to regulate the input amount of pigment. Often this decision is simply inadequate.

The second approach consists in mixing a variety of fluorescent dyes. This approach has serious compatibility issues between themselves, dyes, or between one or both dyes and polymer matrix in which they are placed. The problem remains and resistance to fading. Different dyes have different compatibility with different what Karami because of the differences between the chemical structures. The durability of this fluorescent pigment different in different polymer matrices. One pigment may have an adverse effect on the other in a polymer matrix. In addition, the same dye can have different resistance to fading in different polymer matrices.

The third possible approach is to introduce into the polymer matrix mixture afluorescent dye with a fluorescent dye. The problems that have been mentioned above for mixtures of multiple fluorescent dyes in a polymer matrix, remain relevant for this approach. These problems can become more acute due to the large chemical differences between a fluorescent dye and afluorescent dye. In addition, there is a chance that afluorescent dye may affect the luminescence of the fluorescent dye, which will sharply reduce the brightness of the sheet material. Afluorescent the dye can repay the total luminescence of the fluorescent dye.

Accordingly, the current state of this technology requires the solution to this problem of coloring. Usually the supplier of such products has not been able to solve the problem of colouring, dictating their decisions in the field of color. Usually the painting ordered by the user, and the availability of colored dyes is limited suppliers of dyes.

It is obvious that itca to solve the two main problems of resistance to fading and staining in the same product leads to increased difficulties associated with these problems. However, the solution of these problems will be especially valuable when both of these problems will be solved in the same product.

Brief description of the invention

According to the present invention offers products that have a fluorescent color, which can be manipulated to obtain a given color, and which at the same time are resistant to fading, especially under the influence of ultraviolet radiation. The invention uses the principle of layering. Take at least two layers, for example, films, one on top of another. Each contains a dye or pigment. For many applications, each of the multiple layers contains a fluorescent dye. One of the layers contains a polymer having a high resistance and durability under the influence of ultraviolet radiation, such as acrylate or polyarylate. Preferably, this layer is on top of another layer, that is, this first layer is located between the second layer and a medium or a source of ultraviolet radiation. From the point of view of environmental colour is created by the combined colored layers, provides color parameters needed to obtain a given color, dictated by the specific standard.

The present invention is the creation of products yepremyan, which have resistance to UV light and have the desired color, as well as methods of producing such products or items.

One object of the present invention are products with improved fluorescent colouring, which have the required color values with the properties of durability, which are very well allow you to use the item outdoors in different weather conditions.

Another object of the present invention is an improved product and method that include the use of multiple film layers, suitable for use as fluorescent laminate for retroreflective sheeting for various applications.

Another object of the present invention is an improved fluorescent colored retroreflective sheet material suitable for use in the manufacture of road signs.

Another object of the present invention is the ability to create permanent fluorescent yellow-green retro-reflective sheeting for signs on pedestrian crossings, and marks the intersection area schools, etc. that have the color desired for signs of this type.

Another object of the present invention is an approach for using the Oia resistant to weathering of polymers, such as an acrylic polymer matrix, a fluorescent system that is both permanent and durable enough for prolonged use in adverse environmental conditions such as those faced by the characters, intended for outdoor use.

Another object of the present invention are products which consist of many layers, each of which is not suitable, but together they are suitable for a permanent and properly painted products.

Another object of the present invention is a double layer with a fluorescent coloring, for retroreflective sheet materials having the requisite durability and color when the two sheets are connected, but not when they are used separately.

Another object of the present invention is a dual film having a fluorescent yellow-green color for retroreflective sheet material having a sufficient durability and color, when the two sheets are connected, but not when they are used separately.

Other objects, purposes and advantages of the present invention will be clear from the following description of a preferred implementation options with reference to the accompanying drawings, where:

Brief description of drawings

Figure 1 - cross section of flu is rescenter sheet material, with many color film layers, showing the top layer containing a fluorescent dye and a sublayer having a pigment and formed in this layer microprismatic retroreflective elements;

Figa is a cross section of the fluorescent sheet material with many color film layers on a transparent microprismatic retroreflective elements;

Figure 2 is a cross section of the fluorescent sheet material having multiple film layers and containing additional external protective layer;

Figure 3 - cross section of a retroreflective sheet material with attached lens of the present invention, where the fluorescent sheet material having multiple film layers placed over the nested structure of lenses;

4 is a cross-section of the reflective sheet material with sealed lenses of the present invention, where the fluorescent sheet material having multiple film layers placed over the structure sealed lenses;

5 is a curve of values of chromaticity "x" and "y" by standard colorimetric system CIE 1931 film structures in relation to the imposition of specified amounts of fluorescent yellow-green;

Fig. 6 is a curve of values of chromaticity "x" and "y" by standard colorimetric si is theme of the CIE 1931 for different types of retroreflective sheet material in relation to the imposition of specified amounts of fluorescent yellow-green color;

7 is a curve of light transmission, illustrating the effect of blocking the light component of the film of the present invention;

Fig - graph of the color shift depending on the time of accelerated or artificial tested for weather resistance, illustrating the various effects for a particular film and the same film with the imposition of the fluorescent polymer matrix;

Fig.9 is a graph of the color shift depending on the time of accelerated or artificial tested for weather resistance, illustrating the various effects for a particular film and the same film with the imposition of the fluorescent polymer matrix, while the underlying film contains an ultraviolet absorber;

Figure 10 - graph of the color shift depending on the time of accelerated or artificial aging, illustrating the various effects for a particular film and the same film with the imposition of the fluorescent polymer matrix, while the underlying film contains an ultraviolet absorber and HALS component;

11 is a graph of the color shift depending on the time of accelerated or artificial aging, illustrating the various effects for a particular film and the same film with the imposition of the fluorescent polymer matrix, while the underlying film contains the HALS component;

Fig - graph of the color shift depending on the time of accelerated or artificial aging for a single layer of yellow-green fluorescent acrylic film and sheet material containing such film as an upper layer on a polymeric matrix containing an orange dye, and

Fig - graph of the color shift depending on the time of accelerated or artificial aging for a single layer of yellow-green fluorescent acrylic film and sheet material containing such film as an upper layer on a polymeric matrix containing an orange dye that is different from the dye in Fig.

Description of the preferred options

The present invention relates to fluorescent sheet materials having multiple film layers that provide superior light-fastness and the settings fluorescent color. In the drawings shows the different variants of the present invention. In each case, the polymer of the top layer containing the fluorescent dye is combined with the sublayer in the form of a polymeric matrix having color attributes, which are combined with the upper layer to obtain the specified color and high light fastness.

Figure 1 shows a multilayer film sheet material, generally indicated by the position 21. This is earnest material embodied in reflective form. Shows the top layer 22 and the underlayer 23. Each layer contains a dye, preferably a fluorescent dye. In this embodiment himself painted the underlayer 23 is retroreflective elements.

In other embodiments, the retroreflective elements similar to those shown in this embodiment may be uncolored or transparent. For example, on figa has a reflective layer 23a made of a transparent polymer, suitable for stamping or forming of corner reflectors. With this design is the multiple layers of the colored polymer form a separate top layer 22A and the sublayer 22b, which have no reflective elements.

The underlayer 23 or layer 23a has many microprismatic retroreflective elements placed on the bottom surface of this layer. These retroreflective elements are known and described in such sources as the U.S. patents No. 4588258 (Hoopman) and No. 4775219 (Appledorn). Such prismatic structure can be produced, for example, U.S. patent No. 3810804 (Rowland) and No. 4486363 and 4601861 (Pricone). For the formation of microprismatic elements 24 on the sublayer 23 or layer 23a can be any suitable processes and equipment, or they can be implemented in this layer otherwise.

Property of svetovozvrascheniya created these microprismatic elements 24, shown by arrows n is 1 and 1A. For simplicity shows only two dimensions of this three-dimensional reflection. This simplified illustration of a light flux shows an incident beam, reflected twice the product for the creation of parallel reflected beam.

Figure 2 shows a similar reflective multilayer film. In this embodiment, added to the top or covering layer 25. It is added in cases where it is necessary to increase the resistance to scratching, graffiti protection and/or shielding of ultraviolet radiation. In General, this covering layer 25 has a conventional composition and method of application. Such upper or covering layer may be chosen so that it has the properties required for the front surface of the sign or similar products, such as resistance to fogging and/or easy printing.

Usually the layers are laminated with each other, for example, heat and/or pressure on conventional equipment. Depending on specific needs or wishes to multilayer film sheet material between the layers may be additional binder layers. Depending on the specific design or needs of the end user, you can use laminating adhesive. When using such a binder layer or layers, they should be selected so as not to disturb those properties, the achievement of which n is purposed fluorescent multilayer product of the present invention.

On the surface one or more layers may be applied in advance the necessary notation so that the finished laminate or finished multilayer structure had the necessary notation on the inner surface, as disclosed in U.S. patent No. 5213872 and 5310436. Specialists in the area of the retroreflective sheet materials is obvious and other such changes or other alternative design options that can be applied to the products of the present invention.

One other variant of the design shown in figure 3. As shown here, the present invention can be applied to retroreflective sheet material containing nested lenses. Retroreflective sheeting materials with nested lenses known in particular from U.S. patent No. 2407680 (Palmquist). This technology allows the use of lenses, such as glass microspheres embedded in the structure of the sheet material with a flat transparent cover film. In the embodiment of figure 3 glass microspheres 26 embedded in the sublayer 23. In accordance with known methods include specularly reflecting layer 27, which may be applied by sputtering aluminum in a vacuum. Reflective nature of this structure with nested lenses is illustrated a simplified two-dimensional diagram of the luminous flux indicated by the arrows, which is passes through the top layer 22, the underlayer 23, microspheres and through them, into the atmosphere 28 and through it back and forth.

You can also be laminated with each other, the upper layer 22 and a sublayer 23 and use a transparent adhesive layer (not shown) for connection of the balls 26 and the substrate. In this case, the balls are embedded in the adhesive as well as the underlayer 23 holds the tops of the balls in figure 3.

Figure 4 shows how the present invention can be used in retroreflective product with sealed lenses. Retroreflective properties and design of sheet material with sealed lenses are well known. A monolayer of lenses, such as glass microspheres partially embedded in the binding layer and the film of glue with the glue layer so that the lenses are encapsulated in sealed cells. In the shown embodiment, glass microspheres 31 embedded in the bonding layer 32. The underlayer 23 is fastened tightly to the binder layer to seal the lens. Lens 31 shown in the drawing, have their own reflective surface 33 to provide reflection in the direction of the arrows shown in figure 4.

The fluorescent product of the present invention contains a variety of polymer matrices. Fluorescent dye is present in one layer or in both layers - the top layer and the underlayer. Preferably, the fluorescent dye is rootsthe in the polymeric matrix of the upper layer 22 and the polymeric matrix substrate 23. In a typical product in each layer is different dye. This provides the important characteristic of the present invention, according to which it is obtained a multilayer film having a fluorescent color that is required for a specific task without having the physical placement of the dyes in the same matrix.

The polymer matrix may be different. Examples include polycarbonates, polyesters, polystyrenes, styrolacrylonitrile copolymers, polyurethanes, polyvinyl chloride, polymers formed from acrylic resin, polyarylate, apoliticality, their copolymers, and combinations thereof. The top layer and the underlayer may be made of different polymers. The top layer is a resistant to atmospheric conditions, the polymer comprising acrylic polymers, polyarylate, apoliticality and their copolymers, and combinations thereof.

In a preferred aspect of the invention, the polymer of the top layer is formed of acrylic resin. The sublayer does not require high resistance to weather conditions and may be related to the type requiring protection from the weather in more severe conditions. The preferred polymer substrate is polycarbonate. In addition to creating a matrix structure for the upper layer of the acrylic resin can be used to create a sublayer.

Polymers, including what I polyarylate and other types of matrices, and they contain the components described in more detail in pending application for U.S. patent No. 09/710510 and 09/710560 on the name of the author, both of which filed on 9 November 2000, These sources are included in the present description by reference.

In the upper layer and/or the underlayer may include other known components. These include components that absorb ultraviolet light and HALS components. At any given polymer matrix can include one or more species of both of these components together or separately.

The polymer matrix is an essential part of the mass layer. The polymer component is from about 90 to about 99.99 percent by weight of the composition constituting each polymeric matrix, preferably from about 95 to about 99 wt.%. Each dye is present in an amount of from about 0.01 to about 1.5 wt.% from the total mass of each matrix composition, preferably from about 0.02 to about 1.0 wt.%. If you are using an absorber of ultraviolet light, it is present in an amount of from about 0.1 to about 5 wt.%, preferably from about 0.3 to about 3 wt.% of the total weight of the composition of the polymer matrix. If you use a HALS component, it is present in an amount of from about 0.1 to about 2 wt.%, PR is doctitle from about 0.3 to about 1.5 wt.% by weight of the total composition of each matrix.

When using acrylic matrix in General, it is preferable that the acrylic resin had a composition such as to minimize the number of substances that enhance performance, such as sastifactory, internal lubricant, etc. is Also considered useful to minimize the number present acrylic monomer. Without being bound to any particular theory, it is now considered that such substances enhancing characteristics or residual monomers can adversely affect the fluorescent pigments in an acrylic matrix, thereby potentially accelerating the degradation of the fluorescence when exposed to light, primarily ultraviolet radiation. Currently, it is believed that this effect is enhanced in combination with moisture, heat cycles and ultraviolet radiation. The polymethyl methacrylate is preferably an acrylic resin. Specific acrylic resin, which meets these requirements, is produced under the trade name "ZRV-001E" company Cyro Industries. There are other applicable resins, for example, Plexiglas PSR-9 company Atofina.

Preferably, the chromaticity and the upper layer and sublayer is specified with a fluorescent dye. Such dyes include benzoxanthene, benzothiazine, perilene, tioksantena, thioindigo, naphthalimide and coumarins. The connection films with dyes, it is sponding different coloring properties, it was found useful according to the present invention for creating products fluorescent colors, which can be adapted to meet the real or anticipated needs.

It was found that the dyes benzoxanthenes type particularly well suited for insertion into a component of the upper layer according to the present invention. Particularly preferred fluorescent benzoxanthene dye is a yellow-green dye, marketed under the trade name Lumofast Yellow 3G company DayGlo Color Corporation. Can be numerous variations of this dye. When polymetylmetacrylate matrix of the upper layer according to the present invention, this dye gives excellent brightness in the daytime. It can be used in amounts of from about 0.2 to about 1.5 wt.%, preferably from about 0.3 to about 1.3 wt.% of the total weight of the matrix composition. Mass tabs fluorescent dye depends on the thickness of the sheet and the desired intensity of color for a particular application. For example, retroreflective articles usually require fluorescent dye had sufficient transparency so as not to impair significantly the retroreflective properties of the product.

Another class of dyes, which finds particular when is the change in the products of the present invention, this is benzothiazine dyes. It was found that very useful yellow-green fluorescent color and saturation are obtained in a multi-layer products using dye Huron Yellow D-417 companies DayGlo Color Corporation. The combination of the dye in the sublayer and benzoxanthene yellow-green dye in the upper layer gives such values of chromaticity and color saturation, which fully comply with industry standards for the yellow-green leafy materials.

Using different dyes, it is possible to obtain not only the yellow-green color. For example, the sublayer may have a fluorescent orange and/or red. To do this, use thioxanthene dye Marigold Orange D-315 company DayGlo Color Corporation. Other dyes include Lumogen F Orange 240, and Lumogen F Red 300, each of which is perylenebis the imide and produced by BASF. Another is Lumogen F Yellow 170 from BASF. You can use fluorescent blue and green dyes. Other dyes include perylenebis esters and thioindigo dyes.

It is believed that the inclusion of layers of an absorber of ultraviolet radiation may delay or prevent degradation of a component related to fluorescent dyes. In particular, it is believed that suitable benzotriazole, benzophenone and oxalanilide are absorbers of ultraviolet radiation, which could the t to delay fading of fluorescent dyes to increase the longevity of fluorescence.

Benzotriazole ultraviolet absorbers useful in systems fluorescent dyed polycarbonate matrices, especially in the sublayer layered products. Absorbers of ultraviolet radiation having a good compatibility with benzothiazine dyes, useful when such a dye is injected into a polymer matrix. Examples of manufactured benzotriazole absorbers of ultraviolet radiation include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-generati)phenol, marketed under the trade name "Tinuvin 234" by the company Ciba-Geigy; and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5(hexyl)oxyfuel available from the company Ciba-Geigy as Tinuvin 1577".

Examples of commercially available benzophenone absorbers of ultraviolet radiation include 2-hydroxy-4-n-acetoxybenzoic, available from Great Lakes Chemical Corporation under the trade name "Lowilite 22"; 2,2-hydroxy-4,4-dimethoxybenzophenone, marketed under the trade name "Uvinul 3049" by BASF; and 2,2',2,4'-tetrahydroxybenzophenone, marketed under the trade name "Uvinul 3050" by BASF. It was found that these ultraviolet absorbers benzophenone type particularly suitable for fluorescent dyed acrylic matrix.

Examples oxalanilide ultraviolet absorbers include 2-ethyl, 2'-ethoxy-oxalanilide manufactured under the trade name is the "Sanduvor VSU" by the company Clariant. There are other oxalanilide absorbers of ultraviolet radiation. Professionals it is clear that there are many types of absorbers of ultraviolet radiation, which can be used in the present invention.

In General, spatial employed amine light stabilizers (HALS) have been useful to delay the fading of fluorescent dyes. Oligomeric or polymeric HALS compounds with a molecular weight of approximately 1500 and more provide increased durability fluorescence. The combination of the ultraviolet absorber and HALS compounds usually helps even more to prevent fading and to improve the color durability. Particularly useful compounds HALS are related oligomeric amines company Great Lakes Chemical under the trade name "Lowilite 62" or "Tinuvin 622", manufactured by Ciba-Geigy.

The HALS compounds include polymer dimethylsuccinic with 4 hydroxy-2,2,6,6-tetramethyl-1-piperazineethanol, which is manufactured by Ciba Specialty Additives as "Tinuvin 622"; poly[[6-[1,1,3,3-TETRAMETHYLBUTYL)amino]-Deut.-the triazine-2,4-diyl][[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]], commercially available from Ciba Specialty Additives under the trade name Chimassorb 944; "Tinuvin 791", manufactured by Ciba Specialty Additives and represents a mixture of poly[[6-1,1,3 .3m-tetrame rbutil)amino]-Deut.-the triazine-2,4-diyl][[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]] bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacina; and Hostavin N30", which is issued by the company Clariant. Professionals understand that there are many other spatial employed amine light stabilizers that can be used in the present invention.

When using a covering or protective layer, it can also improve the durability of the fluorescence due to the shielding of ultraviolet radiation due to the presence of the compound or compounds that absorb ultraviolet radiation. Alternatively, a covering or protective layer may contain a polymer, which in itself is an absorber of ultraviolet radiation. For this approach polyarylate matrix.

In the absence of a covering or protective layer of the present invention allows to create long-lasting fluorescent product of the desired color. In the preferred embodiment, two color fluorescent film to form a durable product. Each film in the polymer matrix contains a fluorescent dye and UV additives. The top layer is a relatively long-lasting color fluorescent film, and the underlayer is a color fluorescent film meet the needs of any type. When connected together they give the desired fluorescent color. Each color separately does not necessarily have to provide the required flue scanty color.

When placing the respective dyes in the individual polymer matrices of any harmful interference which otherwise could occur because of a mixture of two dyes, is excluded. Another useful property is that the top layer has the property of shielding ultraviolet radiation, protecting the sublayer, which has a higher performance compared with conventional shielding ultraviolet layer, such as a covering or protective layer. The combination of the upper layer and the sublayer of the present invention allows to obtain a higher light-fastness of fluorescent products having a color that can be selected in accordance with dyes, which produce manufacturers of dyes. Each film individually cannot provide such properties.

When fluorescent yellow-green retro-reflective sheet material required for a specific task, such as visible signs of the zone schools or pedestrian crossings, the preferred option connects two layers, none of which by itself could not provide this type of characters. In this preferred structure, the upper layer is an acrylic matrix with benzoxanthene dye, and a sub-layer is a polycarbonate matrix with benzothiazinones dye. After sparkiv a single product is formed very durable and properly colored single product with the desired color.

More specifically, it was found that the acrylic matrix with benzoxanthene dye when used alone has three distinctive problems. Its yellow-green color has no saturation, in accordance with accepted industry criteria. Despite the fact that it has excellent properties of fluorescence, its color does not reach the specified value, with a shift towards green. In addition, it was found that sastifactory, usually important for acrylates, when the solution of many problems, in particular when used as signs to be installed outdoors, adversely affect the light fastness benzoxanthene dyes in acrylates. However, without such electification acrylic films are usually too brittle to be used for retroreflective sheet materials. Move during handling or installation can potentially lead to cracking or other damage to the acrylic sheet material. Moreover, even acrylates, showed good resistance to light, as it was discovered, by itself, is not suitable for long-term outdoor use.

Speaking more specifically about the shortcomings of the individual layers is preferred yellow-green option for outdoor use, with benzothiazinones dye in polycarbonate matrix arise the problems that arose, which make it unsuitable for use outside of the combinations of the present invention. This combination of polymer and dye has no fluorescence to the extent that is needed for such tasks. Although its saturation suitable for tasks such as signs school crossing zone, its brightness setting in the daytime, known to specialists as "Y%"is too low. In addition, the films of polycarbonate resins have insufficient light fastness when used for long periods without any protective sheet material, a laminate or shielding ultraviolet layer. Moreover, it was found that although benzothiazine dyes can be to some extent protected by an acrylic materials, their resistance to light in the acrylic polymer is lower than in the polycarbonate.

In the formation of a preferred combination of the upper layer and the sublayer of the present invention these problems are resolved favorably. Multilayer fluorescent sheet material has the desired fluorescent color, such as yellow-green, and the high fluorescence of benzoxanthene compensates for the reduced fluorescence benzothiazinones dye. That is, the total coefficient "Y%" color and luminescence in the daytime almost identical to the reference values. These effects reach more than simple the e average values, given respectively by the upper layer and the underlayer.

In addition, although the light fastness separate the upper layer is insufficient for long-term use as a retroreflective sheet material, exceptional lightfastness allows you to create extremely permanent multilayer film of fluorescent material. It was also found that the top layer of preferably acrylic matrix containing benzoxanthene, acts as a layer that absorbs ultraviolet radiation, protecting the sublayer from ultraviolet degradation. It is shown in Fig.7, which is described in more detail below in example 5 in the context of a yellow-green fluorescent sheet material.

Moreover, a structural problem for acrylic matrices that do not contain electification, quite satisfactorily solved by creating a sublayer. The underlayer, typically, is a polymer having a very high strength and impact strength, which supports the polymer top layer that gives the laminate, not prone to embrittlement. In particular, in the preferred embodiment, the polycarbonate matrix substrate works as a support layer for acrylic top layer. This allows you to get multiple fluorescent sheet material, which is not very fragile for use in adverse conditions, n is the sample for signs, placed outdoors, etc.

The thickness of the upper layer 22, the underlayer coating layer 23 and 25 (if present) may to some extent vary, depending on the specific products. Typically, the top layer has a thickness of from about 0.05 to about 0.5 mm, more typically from about 0,075 to approximately 0.25 mm Usually sublayer has a thickness of between about 0.05 and 0.5 mm, more typically between about of 0.075 and 0.25 mm When the covering layer of a thickness of from about 0.025 mm to about 0.25 mm, more typically from about 0.05 mm to approximately 0.125 mm

The following examples are given for purposes of illustration and explanation. The films used in these examples were made on a laboratory single screw Killion extruder with three heating zones or using a Brabender mixer. This single screw extruder a mixture of these polymer resins, colorants and other additives, such as UV light and/or HALS, extraditables in a film thickness of approximately 0.15 mm As an example, for roll film of acrylic matrix temperature of the heating zones was 490°F (245,4°C), 460°F (237,7° (C) and 440°F (226,6°). The polycarbonate film temperature zones amounted to 530°F (276,6°C), 540°F (282,2°C) and 550°F (287,7°C). The speed of the neka equal to 27 rpm When using a mixer, the equipment supplied by the firm C.W. Brabender Plasti-Corder Prep-Mixer. The material had a composition obtained by mixing in the melt polymer resins and other components and converted to a film thickness of approximately 0.150 mm on the press with a heated table. Temperature mixing ranged from 230 to 270°C, depending on the particular polymer, and the rotational speed of the mixer was 100 rpm in a period of time from about 3 to about 6 minutes. Made so the film was laminariales each other at approximately 185°using the laminator with hot rollers Hot Roll Laminator M manufacturing company Cheminstruments.

EXAMPLE 1

The film of the upper layer of polymetylmetacrylate matrix produced by mixing acrylic resin (Acrilite Plus ZK-V-001E - trading company name Cyro), 0.8 wt.% benzoxanthenes fluorescent dye (Lumofast Yellow 3G, trading company name DayGlo) together with 0.1 wt.% absorber of ultraviolet (Lowilite 22, the trading name of company Great Lakes Chemical) and 0.5 wt.% HALS (Lowilite 62, trade name company Great Lakes Chemical). This single-layer PMMA sample was designated as sample 1-1".

The film substrate of a polycarbonate matrix was made by mixing the polycarbonate resin (Calibre 303EP, trade name of the Dow Chemical company with 0.06 wt.% benzothiazinones fluorescent dye (Huron Yellow D-417, trade name of the company DayGlo). This single polycarbonate film was designated as sample 1-2-1". Sample 1-2-2 became laminate of sample 1-1 and sample 1-2-1.

Another polycarbonate film substrate was made of the same polycarbonate resin as in the sample 1-2-1 together from 0.05 wt.% fluorescent dye Huron Yellow D-417 and 1.5 wt.% the ultraviolet absorber (Tinuvin 1577, trade name of the company Ciba-Geigy). He received the designation of "sample 1-3-1". Example 1-3-2 became a multi-layer film sample 1-1, laminated onto a sample 1-3-1.

Another polycarbonate film substrate was manufactured using the same polycarbonate resin, this time in a mixture of from 0.05 wt.% fluorescent dye Huron Yellow D-417, 1 wt.% the ultraviolet absorber Tinuvin 1577 and 0.3 wt.% component HALS (Tinuvin 622, trade name of the company Ciba-Geigy). She received the designation of "sample 1-4-1". Example 1-4-2 became the PMMA film sample 1-1, laminated on the film sample 1-4-1.

Was made one polycarbonate film substrate. It consisted of a polycarbonate resin (Calibre 302, trade name of the Dow Chemical company), 0.08 wt.% Huron Yellow D-417 and 0.3 wt.% component HALS (Tinuvin 622). She received the designation of "sample 1-5-1". Sample 1-5-2 became the laminate film sample 1-1 on the film sample 1-5-1.

Each of the above five separate films and each of even the PEX two-layer laminated film was subjected to accelerated weather resistance test. Each sample was placed in the test apparatus for weather resistance Xenon Arc Weather-O-Meter, and the degree of discoloration was determined by the usual methods of color measurement on the HunterLab colorimeter LS-6000. Were used in the instrument light source D65, viewing angle 2° and geometrical configuration 0/45. All color measurement was recorded in the standard colorimetric system CIE 1931. To determine the degree of fading and color shift was determined ΔE* is the degree of color shift depending on the time of accelerated tests for weather resistance. Small color shift of the order of 2 or 3 units ΔE* virtually undetectable to the naked eye. Methodology testing on the device Xenon arc described in ASTM G26-90, section 1.3.1. Used borosilicate inner and outer filters and exposure amounted to 0.35 W/m2at a wavelength of 340 nm.

The results were recorded for the color difference in CIELAB, measuring ΔE*. For single-layer and multilayer films was determined values ΔE* three modes of accelerated tests for weather resistance, namely, 500 hours, 1000 hours and 1500 hours. The data are given in table I.

Table I
SampleThe film structureΔE* samples podworks is, for example by transferring them to the test during the specified period (h)
50010001500
1-1Single film PMMA23,0421,4521,63
1-2-1

1-2-2
Single PC film

Two layers of PMMA/PC
9,89

3,36
of 12.26

2,48
11,96

4,89
1-3-1

1-3-2
Single PC film

Two layers of PMMA/PC
8,04

4,51
a 10.74

3,90
12,64

6,89
1-4-1

1-4-2
Single PC film

Two layers of PMMA/PC
5,27

5,03
8,76

4,05
5,62

to 7.84
1-5-1

1-5-2
Single PC film

Two layers of PMMA/PC
4,54

2,77
11,48

3,00
11,47

3,99

The data in table I show that in a single film has been a significant color shift. Two-layer film showed superior durability fluorescent properties compared to single-layer films. It can be seen in Fig, which shows a plot of the values ΔE* from the time of accelerated tests for weather resistance single polycarbonate film 1-2-1 and two-layer PMMA/PC film 1-2-2. the same regardless of the type of graph shown in figure 9 for a single film PC 1-3-1 and two-layer films of PMMA/PC 1-3-2. Figure 10 shows in graphical form the data of table I for a single polycarbonate film 1-4-1 and two-layer PMMA/PC film 1-4-2. Figure 11 graphically presents data on pogodnosti for a single polycarbonate film 1-5-1 and for two-layer PMMA/PC film 1-5-2. These data demonstrate the durability of fluorescence and color, which are significantly improved when using the approach in the application of multilayer films, which confirms comparing values ΔE* for multilayer film structures with these values for single-layer films.

EXAMPLE 2

Single-layer polymetylmetacrylate film the matrix was made by combining an acrylic resin, namely Acrylite Plus ZK-V-001E (trade name of the company Cyro), and 0.8 wt.% fluorescent dye Lumofast Yellow 3G company DayGlo. This sample was designated 2-1. Single polycarbonate film matrix was produced from the pellets Calibre 303EP of the Dow Chemical company c 0.05 wt.% fluorescent dye Huron Yellow D-417 and 1.5 wt.% the ultraviolet absorber Tinuvin 1577. This sample was designated 2-2. Sample 2-3 was two-layer PMMA/PC film of sample 2-1, laminated onto a sample 2-2.

Test was performed to determine the chromaticity and Y%for the three film samples. The results are shown in table II.

Table II
SampleThe film structurexyY%
2-1Single PMMA-film0,37060,503494,15
2-2Single PC film0,42200,505082,53
2-3Two-layer PMMA/PC film0,41520,525489,62

The coordinates of the color saturation "x" and "y" for CIE use to compare these films with well-known recognized color standard. They can be compared with the same coordinates of a given fluorescent yellow-green color, which meets industry requirements for the color. These color coordinates for the fluorescent yellow-green are(0,387; 0,610), (0,460; 0,540), (0,421; 0,486) and (0,368; 0,539).

Figure 5 is a diagram of the coverage of the fluorescent yellow-green color that is required by the industry, as defined by these color coordinates "x", "y", above. The film, in which the chromaticity coordinates (x and y) are inside this specific area, are considered acceptable.

Coordinate "Y%" is located in the third dimension, which can be thought of as acting on the two dimensions of the region of coverage in figure 5. In General, a larger value of "Y%" indicates a greater degree of fluorescence and, therefore, of great utility in the context of the present description. The value "Y%" is the total reflectance. This is a standard indicator light (electromagnetic radiant energy, which is visually detectable by a normal observer-man)emitted from the surface, taking into account the weights of the ability of the eye convert light in the visual sense. It is defined as the ratio of the total brightness of the sample to the total brightness of an ideal diffuser, illuminated and observed under the same conditions.

From figure 5 it is clear that a single PMMA film misses the coordinates "x" and "y" the field of fluorescent yellow-green color, and a single polycarbonate film has a value on the boundary of this area. It was unexpectedly found that a two-layer film made from these two films, with or unacceptable marginal acceptable coordinates "x" and "y", gave values that were in the more affordable areas in the coordinates "x" and "y". Interestingly, the value of "x" is not simply the average of the two films, made from two-layer film. Even more surprisingly, the value of "y" was found to be greater than this value for each of the single films, which is critical for preserving the colors inside rebamol region during exposure to weather conditions. For example, for a single polycarbonate film, a small color shift when exposed to weather conditions will color this film beyond the required field.

As for the parameter "Y%", two-layer film has shades of fluorescent yellow-green color with favorable values. It should be noted that "Y%" two-layer film is larger than the average of the two values "Y%" separate films.

EXAMPLE 3

The film according to example 2 were converted into sheet material for retroreflective traffic sign, using the well known method of embossing to create a design, in the General form shown in figure 1. For this process of stamping directly on the rear surface of the fluorescent film was formed many microprismatic corner reflectors. Then was made ready retroreflective sheet material by combining a white film substrate with an embossed film in the form of a repeating cell pattern.

The values of the color coordinates (x, y) and reflectance ("Y%") ready retroreflective sheet material shown in table III. For comparison, the values of "x", "y" and "Y%" commercially produced yellow-green products. Of particular interest in this regard is set to "Y%" for two-layer color products PMMA/PC. Its value is "Y%" above, h is m each color film, of which it consists, and is close to the value of commercial product than to the values of individual films.

Table III
Type retroreflective sheet materialxatY%
Avery Dennison, T-7513

Fluorescent yellow-green
0,40760,564192,94
3M 3983 Fluorescent yellow-green0,40690,570495,28
Single color PMMA film0,34040,526085,95
Single color PC film0,43020,541783,9
Dual colored PMMA/PC film0,40670,543389,75

The coordinates "x" and "y" is shown in Fig.6 in Association with the same industry standard for color gamut yellow-green color in figure 5. Coordinates do not compare products figure 6 differ slightly from those shown in figure 5. This illustrates the expected color shift between the coordinates displayed by the original films, and coordinates shown films converted to retroreflective sheet material road who's characters. As can be seen from tables III and 6, the product of the two colored layers of the present invention has the chroma coefficient "Y%", close to the values of the known products which can be considered as standards for the achievement of which should aim at the creation of products of this type. None of the single-layer products are made of double-layered product, in and of itself is not suitable for fluorescent yellow-green retro-reflective sheet material with the desired color coordinates and Y%". Color retroreflective sheet materials made of any of these single fluorescent yellow-green layers of PMMA or polycarbonate, not correspond to existing products that are standard for such products.

EXAMPLE 4

Made two single-layer film with the same fluorescent dye, namely, 0.06 wt.% Huron Yellow D-417. One of the polymer matrix is made of polycarbonate Calibre 303-EP, and the second was an acrylic matrix, made of Acrylite Plus ZK-V-001E. Polymethylmethacrylate has shown a strong fading after only 200 hours of accelerated tests for weather resistance, where a value of ΔE* $ 36,70, which indicates a very weak light fastness of a fluorescent dye in the host acrylic matrix. In contrast, the same benzothiazinone the dye showed significantly better resistance to light in a polycarbonate resin, testifying about the suitability of the polymer for the placement of a fluorescent dye. After 200 hours of accelerated aging index ΔE* amounted to 2.55. After 500 hours it was $ 9,89 and after 1000 hours ΔE* equal of 12.26 for polycarbonate film.

EXAMPLE 5

Was made polymetylmetacrylate film thickness 0,150 mm It contained 0.8 wt.% dye Lumofast Yellow 3G, 1.0 wt.% UV absorber Lowilite 22 and 0.5 wt.% component HALS Lowilite 62. Registered information transmission. It is shown in Fig.7. in the shape of the curve of light transmission. It is noted that almost all the light with wavelengths below 460 nm was blocked by the film due to the presence of the colorant and the ultraviolet absorber. This example shows that the fluorescent yellow-green PMMA film is a powerful screen for other fluorescent colour films, illustrating its effectiveness as an upper layer in accordance with the present invention.

EXAMPLE 6

Was made of fluorescent yellow-green film of the upper layer of the same composition as sample 1-1 in example 1. This polymetylmetacrylate film was designated as sample 4-1". Was made of fluorescent orange PMMA film substrate by mixing acrylic granules (Atohaas VO-45, trading company name Atohaas) with orange fluorescently thioxanthenes Kras is Telem, namely, 0.25 wt.% Marigold Orange D-315 (trade name of the company DayGlo), 1 wt.% UV absorber Tinuvun 234 and 0.5 wt.% UV absorber Tinuvin T-144. This sample was designated as the "4-2-1". It was made a two-ply product by laminating the film of sample 4-1 on the film sample 4-2-1. The resulting product is marked "sample 4-2-2".

In PMMA matrix produced another orange film sublayer. As acrylic Plexiglas was used PSR-9 (trade name of the company Atofina) perylenediimide fluorescent dyes BASF, namely 0.2 wt.% Lumogen F Orange 240 and 0.025 wt.% Lumogen F Red 300. This sample was designated 4-3-1. Was made a two-layer film by laminating the top layer of sample 4-1 on the sublayer of the sample 4-3-1. The obtained product was designated as "4-3-2".

Each of the three single-layer films and both a double-layered product was subjected to accelerated aging in General accordance with example 1. The results are shown in table IV.

Table IV
SampleThe film structureΔE* samples subjected to the test within the specified time (h)
50010001500
4-1About Inanna PMMA film (FIS) 23,0421,4521,63
4-2-1

4-2-2
Single film VO-45 (FD)

PMMA FIS/VO-45 FO double layer
25,4

10,06
31,32

22,33
36,94

24,38
4-3-1

4-3-2
Single film PSR-9 FO

PMMA FIS/PSR-9 FO double layer
5,79

3,23
11,82

of 2.51
25,75

of 6.71

Values ΔE*obtained an accelerated weather resistance test on the device Xenon Arc for a single layer of PMMA-film fluorescent yellow-green color (FIS)gave essentially constant bad results. Single-layer sample 4-2-1 showed persistently poor results, and the single-layer sample 4-3-1 could not withstand prolonged exposure to atmospheric conditions. However, both two-layer product showed the best results. Sample 4-3-2 proved to be particularly effective. On Fig presents the results of table IV in the form of a graph for the two samples containing fluorescent orange (FO) film VO-45. On Fig in the form of the graph shows these results for products containing fluorescent orange (FO) film PSR-9.

EXAMPLE 7

Two different two-layer film structure was subjected to accelerated weather resistance test with the use of the device for the accelerated weather resistance test QUV. QUV-a device for accelerated testing for weather resistance, where the polymer samples irradiated with ultraviolet light. The UV lamp used in the test, radiated at a wavelength of 340 nm. Conditions of the test based on ASTM G 53-89.

One of the film structures was a two-ply product PMMA/PC, namely the sample 1-3-2 example 1. Another was the sample 4-3-2 example 6, a two-ply product PMMA FIS/PSR-9 FO. The results of the weather resistance test was very good. Sample 1-3-2 gave a value of ΔE*equal 0,83 at 200 hours of accelerated aging, ΔE*=1,63 at 1500 hours and ΔE*=3,23 at 3000 hours. For products on sample 4-3-2 value ΔE* at 200 hours were 1.27. At 1500 hours ΔE* was 3.8, and at 3000 hours ΔF* $ 3,56. All these results indicate the excellent lightfastness.

EXAMPLE 8

Was made of fluorescent yellow sheeting having multiple film layers. The upper layer was acrylic matrix, made of Acrylite Plus ZK-V-001E company Cyro, with 0.8 wt.% Lumofast Yellow 3G company DayGlo, 1 wt.% the ultraviolet absorber and 0.5 wt.% component HALS. Sublayer was acrylic matrix of Acrylite Plus Exp-140 company Cyro with 0.3 wt.% Lumogen F Orange 240 (perylenebis dye BASF). Optionally added absorbers of ultraviolet radiation, selected from the group consisting of Lowilite 22, Tinuvin 234 and Tinuvin P. If necessary, may be added HALS component, selected from the group Lowilite 62 and Tinuvin 770.

EXAMPLE 9

Was made another fluorescent yellow sheet material having multiple film layers. The top layer is an acrylic matrix of Acrylite Plus EXP-140 company Cyro and 0.16 wt.% Lumogen F Orange 240 from BASF. Sublayer - acrylic matrix of Acrylite Plus EXP-140 and 0.3 wt.% Lumogen F Yellow from BASF. Optionally added absorbers of ultraviolet radiation, selected from the group consisting of Tinuvin 234, Tinuvin P, Uvinil 3049 and Lowilite 22. If necessary, can be added HALS component, typically Lowilite 22, Tinuvin 770 and Tinuvin 622.

EXAMPLE 10

Was made of fluorescent yellow-green sheeting having multiple film layers. The top layer is a matrix of a mixture of polymers containing polyarylate made of U-Polymer U-6000 company Unitika, Japan, and 0.8 wt.% Lumofast Yellow 3G company DayGlo. Additives that protect from ultraviolet radiation, are not required. Sublayer - polycarbonate matrix from 0.05% Huron Yellow D-417. Additives that protect from ultraviolet radiation, are not required.

EXAMPLE 11

Was made of fluorescent yellow-green sheeting having multiple film layers. The upper layer of the polymer matrix containing soporifically Sollx, GE with 0.8 wt.% Lumofast Yellow 3G company Day-Glo. Additives that protect from ultraviolet radiation, are not required. Sublayer - polycarbonate matrix from 0.05% Huron Yellow D-417. Additives that protect from ultraviolet radiation, are not required.

It should be understood that the written variants of the present invention are illustrated some applications of the principles of the present invention. Specialists can make various modifications without going beyond the true nature and scope of the present invention.

1. The product containing colored fluorescent film substrate having a first fluorescent dye in a polymeric matrix substrate, which has a polymeric structure, colored fluorescent film of the upper layer with the second dye in the polymer matrix of the upper layer of the specified polymer matrix of the upper layer has the structure of a polymer selected from the group consisting of acrylic resin, polyarylate resin, apoliticality resin, and combinations and copolymers, with dyed polymer film of the upper layer has a greater resistance to ultraviolet radiation than the specified colored film sublayer, while the product contains the specified colored fluorescent film of the upper layer, located on top of specified colored film sublayer, and the specified item is selected fluorescent coloration that is different from the specified color colored fluorescent film substrate and the color specified colored fluorescent film of the upper layer.

2. The product according to claim 1, where the first and second dyes are different from each other.

3. The product according to claim 1 or 2 where the specified polymeric matrix substrate has the structure of a polymer, wybran the th group, consisting of acrylic resin, polycarbonate, complex polyester, polyarylate, complex stopoliticalunacy, polystyrene, styrene-Acrylonitrile, polyurethane, polyvinyl chloride, combinations thereof and copolymers.

4. The product according to claim 1 or 2 where the specified polymer matrix of the upper layer has the structure of a polymer, which is an acrylic resin.

5. The product according to claim 1, where the fluorescent coloring products selected from the group consisting of fluorescent yellow-green, fluorescent yellow, fluorescent orange, fluorescent red, fluorescent blue and fluorescent green, created by the dyes selected from the group consisting of benzoxanthenes, benzothiazinone, Pereladova, prelinking, Pereladova esters, thioxanthenes and thioindigo.

6. The product according to claim 1, where the specified selected fluorescent coloration is fluorescent yellow-green, with chromaticity coordinates x and y, which are limited to the following chromaticity coordinates x and y: (x=0,387; y=0,610), (x=0,460; y=0,540), (x=0,421; y=0,486) and (x=0,368; y=0,539).

7. The product according to claim 1, where the specified colored fluorescent film of the upper layer has an increased ability to screen ultraviolet radiation compared to the polymer substrate.

8. The product according to claim 1, where the specified second fluorescent dye has over you is Oki coefficient "Y%" brightness in the daytime, than said first dye.

9. The product according to claim 1, where the specified colored fluorescent film of the upper layer has a higher light-absorbing ability than the specified colored fluorescent film sublayer, whereby the durability of color and protect products against degradation by ultraviolet radiation is enhanced in comparison with durable color and protection from the ultraviolet radiation of each individual film outer layer or sublayer.

10. The product according to claim 1, where said first dye is more permanent in this film sublayer than in this film of the upper layer.

11. The product according to claim 1, where the specified film substrate is polycarbonate and the specified film of the upper layer is a polyacrylate, resulting in this film sublayer is less fragile than the specified film of the upper layer.

12. The product according to claim 1, where the product contains retroreflective elements, which are preferably prismatic elements.

13. The product is indicated in paragraph 12, where the specified sublayer is between the specified upper layer and these retroreflective elements so that incident light passes through the specified upper layer, and then passes to the specified sublayer, then gets on these retroreflective elements and reflected back to the specified okra is a war film substrate and passes through the specified colored film of the upper layer and out of the product.

14. The product is indicated in paragraph 12, where these retroreflective elements are made in the specified sublayer.

15. The product is indicated in paragraph 12, where these retroreflective elements are arranged so as to provide a sealed design of the lens, preferably the design is protected lenses.

16. The product according to claim 1, where the specified product is a sign suitable for outdoor use for at least three years.

17. The product according to claim 1, where the specified fluorescent dye the top layer is benzoxanthene dye.

18. The product according to claim 1, where the specified fluorescent dye sublayer is benzothiazinones dye.

19. The product according to claim 1, where the specified polymer matrix substrate is polycarbonate, a fluorescent dye specified film sublayer is benzothiazinones dye specified polymer matrix of the upper layer is an acrylic resin and a specified fluorescent dye the top layer is benzoxanthene dye.

20. The product according to claim 1, where the specified polymer matrix substrate is an acrylic resin, a fluorescent dye specified film sublayer is selected from the group consisting of thioxanthene dye and perimenopause dye specified polymer matrix of the upper layer is an acrylic resin and a specified fluorescent dye is eating the top layer is benzoxanthene dye.

21. The product according to claim 1, where the specified polymer matrix substrate is an acrylic resin, a fluorescent dye specified film sublayer is perylenebis dye specified polymer matrix of the upper layer is an acrylic resin and a specified fluorescent dye the top layer is benzoxanthene dye.

22. The product according to claim 4, where the fluorescent dye of the upper layer is perylenebis dye and the top layer is an acrylic resin.

23. The product according to claim 1, where the specified polymer matrix sublayer is a polyacrylate resin, a fluorescent dye film sublayer is thioxanthones, thioindigo, thioxanthenes, peritomy, coumarin or leckonby.

24. The product according to claim 1, where the specified polymer matrix sublayer is apoliticality resin, a fluorescent dye specified film sublayer is thioxanthones, thioindigo, thioxanthenes, peritomy, coumarin or leckonby.

25. The product according to claim 1, where the specified polymer matrix of the upper layer is polyarylate resin, a fluorescent dye specified film of the upper layer is thioxanthones, thioindigo, thioxanthenes, peritomy, coumarin or leckonby.

26. The product according to claim 1, where the specified polymer matrix of the upper layer is politicalparty resin, fluorescent dye specified film of the upper layer is thioxanthones, thioindigo, thioxanthenes, peritomy, coumarin or leckonby.

27. The product according to claim 1, additionally containing polymer film coating layer located on top of the specified colored fluorescent film of the upper layer, with the specified covering layer has properties selected from the group consisting of abrasion resistance, resistance to graffiti, resistance to fogging, and combinations thereof.

28. The product according to claim 1, additionally containing polymetylmetacrylate film matrix covering layer, with the specified covering layer provides shielding properties of ultraviolet radiation and the specified upper layer is located between the specified sublayer and the specified covering layer.

29. The product according to claim 1, where the specified film of the upper layer absorbs a considerable amount of light in the main part of the spectrum from about 250 to about 450 nm.

30. The product according to claim 1, where the product is set to ΔE* after prolonged exposure to conditions existing outside the premises, which is substantially less than the value at the specified film substrate or the film of the upper layer.

31. The product according to claim 1, where the specified product is a yellow-green fluorescent product, with full color polymer is tsei substrate is polycarbonate, the first fluorescent dye is benzothiazinones dye Huron Yellow D417 specified polymer matrix of the upper layer is polymetylmetacrylate matrix, and the second fluorescent dye is benzoxanthene dye Lumofast Yellow 3G.

32. The product according to claim 1, additionally containing a light selected from the group consisting of an absorber of ultraviolet radiation, a component of spatial difficult amine light stabilizers HALS and their combinations, while light is either in either or both of these sub-layer and the top layer.

33. The product according to claim 1, where the specified colored fluorescent film sublayer and stained with a fluorescent film of the upper layer, each individually, are not able to meet the requirements of CIE 1931 Standard Colorimetric System on standards on color fluorescent yellow-green in color, whereas the product meets these standards.

34. The product according to claim 1, where the specified film sublayer and the specified film of the upper layer are laminated to each other.

35. A method of manufacturing a product according to claims 1 to 34, which connect the first polymeric resin and the first dye in the composition of the sublayer, the second polymeric resin and a second dye in the composition of the top layer, to form the composition of the sublayer in the painted plank the sublayer, form the composition of the top layer in the colored film of the upper layer, with the specified colored film of the upper layer has a higher resistance to UV radiation than the specified colored film substrate, with at least one of these colored films is fluorescent colored foil, and place specified colored film of the upper layer to the specified colored film sublayer to create fluorescent multilayer sheet material having a selected fluorescent coloration.

36. The method according to p, additionally comprising adding retroreflective elements so that the colored film sublayer is located between the colored film of the upper layer and the retroreflective elements.

37. The method according to p or 36, further comprising applying to the specified colored film of the specified upper-layer polymer coating layer so that the colored film of the upper layer is located between the said covering layer and the colored film sublayer.



 

Same patents:

FIELD: capillary luminescent flaw detection, possible use in aviation, automobile, shipbuilding and other branches of mechanical engineering, and also power engineering, chemical and nuclear industries for detection of surface defects, cracks, pores, foliating, abscesses, inter-crystallite corrosion and other defects of material discontinuity flaw type, primarily with small dimensions, in case of especially precise control of products.

SUBSTANCE: penetration agent includes organic phosphor, non-ionic surfactant and solvent, while as organic phosphor a mixture of phosphors from the class of coumarin colorants is used - mixture of donor-coumarin and acceptor-coumarin, as nonionic surfactant a specially defined substance is used, and as solvent a mixture of dibutyl phthalate and propylene carbonate is used with mass ratio ranging from 1:1,5 to 1:0,8. As donor-coumarin, 4-methyl-7-dethyl amine coumarin (K-47) may be used, and as coumarin-acceptor, at least one coumarin of yellow-green luminescence, with mass ratio ranging from 1,1:1 to 1,8:1.

EFFECT: increased sensitivity and reliability of flaw detection, while simultaneously reducing fire hazard and toxicity of used composition.

1 ex, 1 tbl

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel compounds, namely zinc bis-[2-(tosylamino)benzylidene-N-alkyl(aryl, hetaryl)aminates] of the general formula (I): wherein Ts means tosyl; R means (C1-C6)-alkyl with exception isopropyl, (C1-C6)-alkyl-substituted phenyl, (C1-C6)-alkoxy-substituted phenyl with exception para- and ortho-methoxyphenyl, pyridyl, (C1-C6)-alkylpyridyl, or R + R form in common disulfidodialkyl group -(CH2)n-S-S-(CH2)n- wherein n = 1-3, but preferably to zinc bis-[2-(tosylamino)benzylidene-N-alkylidenemercaptoaminates] of the general formula (Ia): Compounds can be used for synthesis of light-radiating organic diode of white and visible light. Fluorescence can be observed in blue region of spectrum with fluorescence bands maximum at 428-496 nm. Quantum yields are 0.2-0.25.

EFFECT: valuable physical properties of compounds.

5 cl, 8 ex

FIELD: organic chemistry, luminophores.

SUBSTANCE: invention relates to colorless at daylight organic luminophores, in particular, to novel, water-soluble, colorless luminophores A of the formula:

wherein X means oxygen (O) or sulfur (S) atom; Q means compounds of the formulas and wherein R1 and R2 taken separately or in common mean compounds of the formulas: -NHCH2COOM, -N(CH2COOM)2, Cl wherein M means Na, K, NH4. As comparing with the known colorless organic luminophores - optical whitening agents possessing with blue-sky blue fluorescence only, novel luminophores show fluorescence in the range from blue to yellow-orange color and can be used as components of fluorescent, colorless at daylight, inks for jet printers or stamp dyes.

EFFECT: improved and valuable properties of luminophores.

14 ex

FIELD: polymer materials.

SUBSTANCE: invention provides luminescent material showing semiconductor properties and being product of complex polymerization in glow discharge, which is formed as a supported polymer layer located either between electrodes or on any of electrodes. Starting pyrromethene complex is difluoroborate complex of 1,3,5,7,8-pentamethyl-2,6-diethylpyrromethene (Pyrromethene 567). Method of preparing luminescent semiconductor polymer material comprises glow-discharge polymerization for 2 to 120 min of Pyrromethene 567 vapors at temperature preferably 250-350°C, pressure 10-1 to 10-2 Pa, and discharge power 0.5-3 W. Resulting luminescent polymer is characterized by thickness preferably 0.001-10 μm, conductivity 1·10-10 to 5·10-10 Ohm-1cm-1 (20°C), luminescence emission maximum in the region of 540-585 nm at band halfwidth 55-75 nm. Polymer is obtained with quantum yield 0.6-0.8 and is designed for creation of film light-emitting devices.

EFFECT: improved performance characteristics of material.

13 cl, 3 ex

FIELD: capillary defectoscopy; compositions of the color penetrants.

SUBSTANCE: the invention is pertaining to the color capillary defectoscopy, in particular, to the compositions of the color penetrants applied to the color control over the items of the high-duty. The penetrant contains the mixture of the following composition: xanthene dyes of the yellow-orange fluoresceine and red-dark blue rhodamine of 3-6 %, the surfactant of 10-40 %, the rest - the dissolvent. The ratio of the mixture of the yellow-orange and the dark blue - red dyes compounds 1:2, as the surfactant use neonol or syntanol. The technical result of the invention is creation of the color penetrant of the lowered volatility, the reduced flammability, the extra-high sensitivity ensuring detection of the minimal flaw with the opening width of 0.5-1 microns and the improved reliability and stability of the monitoring of the items in conditions of repairs and operation.

EFFECT: the invention ensures detection of the minimal flaw with the opening width of about 1 micron, improved reliability and stability of the monitoring of the items in conditions of repairs and operation.

1 tbl

FIELD: organic chemistry.

SUBSTANCE: invention relates to new individual compounds of benzoxazine class and to a method for their preparing. Invention describes 2-aroylmethylene-2,4-dihydro-1H-3,1-benzoxazine-4-ones of the formula (I): wherein R means hydrogen atom (H) (a), -CH3 (b), -OCH3 (c), -OC2H5 (d), chlorine atom (Cl) (e) eliciting fluorescent properties and stable in UV-light. Also, invention a method for preparing abovementioned compounds. Proposed compounds elicit fluorescent properties and can be used as the parent substances for synthesis of new heterocyclic systems.

EFFECT: improved preparing method, valuable properties of compounds.

4 cl, 6 ex

FIELD: luminescent materials.

SUBSTANCE: invention provides novel electroluminescent material comprised of injecting layer, metal chelate complex-based active luminescent layer, hole-transition layer and hole-injecting layer. Luminescent substance is selected from oxyquinolate metallocomplexes of zinc 8-hydroxy-2-methoxyquinolate and zinc 8-hydroxy-2-methylquinolate. Electroluminescent material shows emission in green spectrum region.

EFFECT: increased heat resistance and widened choice of stable green-emitting materials.

2 cl, 3 ex

FIELD: organic synthesis.

SUBSTANCE: invention provides novel compound: 1-[2-(4,6-dichloro-[1,3,5]triazine-2-ylamino)phenyl]-benzo[d][1,3]oxazine-4-one, characterized by yellow luminescence. Preparation of this compound comprises preliminarily preparing 2-(2-aminophenyl)-benzo[d][1,3]oxazine-4-one by reaction of anthralic acid with thionyl chloride followed by reaction of thus prepared compound with cyanuric acid chloride. Compound is characterized by fluorescence maximum at 560 nm and spare solubility in most organic solvents. The latter enables use of the compound in polygraphic inks as fluorescent pigment.

EFFECT: enlarged assortment of luminophors.

2 cl, 1 dwg

The invention relates to a method for ensuring the authenticity of the subject by applying to a photochromic ink

The invention relates to liquid penetrant inspection, and in particular to compositions of colored penetrants used for color control products responsible destination

FIELD: manufacture of gas-permeable materials containing layer of low-stretchable fabric and microporous coat for use in construction engineering.

SUBSTANCE: microporous coat contains composition of crystalline polymer and filler. Method of manufacture of gas-permeable material includes extrusion of coat on layer of low-stretchable material. Coat is made from composition of crystalline polymer and filler. Tension of non-woven material layer is increased.

EFFECT: enhanced strength or stiffness of non-woven material layers; facilitated procedure of process.

29 cl, 2 ex

FIELD: food industry; packing.

SUBSTANCE: proposed packing material contains main layer of fibrous material, at least one gastight polymeric barrier layer protecting packed product and at least one polymeric thermosealing layer as surface layer of material. Thermosealing layer includes light-absorbing black pigment protecting product from visible light and white pigment. White and black pigments are mixed with thermosealing polymer thus forming thermosealing layer to impart gray color to layer. Invention contains description of pack for food product formed from said packing material and method of food packing.

EFFECT: provision of packing material of improved barrier layer impermeable to light and resembling aluminum foil.

18 cl, 1 tbl, 7 dwg

FIELD: packing laminated plastic, and also folding roller, including the means for applying patterns of bending lines onto packing laminated plastic, and also to layer for usage in packing laminated plastic.

SUBSTANCE: packing laminated plastic contains one of layers, composition of which includes metallic magnetizable particles, acting as information carriers. Roller contains means for application of pattern of bending lines onto packing laminated plastic, and also additionally contains means for application of magnetic fields. Device for performing technological operation over laminated plastic additionally contains device for applying magnetic field for magnetization of magnetizable particles in laminated plastic.

EFFECT: creation of layer in packing laminated plastic, by means of which it is possible to apply decorative patterns to whole surface of package without necessity to keep free spaces for guiding marks; decreased risk of damage to said marks caused by mechanical influences; it is possible to use whole surface of package as information carrier.

5 cl, 7 dwg, 6 ex

FIELD: manufacturing multi-layered films.

SUBSTANCE: film comprises base made of bi-axially oriented polypropylene film and polyolefin film. Before laminating, the polyolefin film is colored. The multi-layered film is oriented in transverse direction or longitudinal direction and transverse direction after laminating. The thickness of the multi-layered film ranges from 8 μm to 26 μm. The method of producing the multi-layered film is also presented.

EFFECT: expanded functional capabilities.

9 cl, 3 ex

FIELD: laminated material for manufacture of packaging containers by folding and thermal sealing and packaging containers for liquid food products manufactured from said material.

SUBSTANCE: packaging material 10 has central layer 11 of paper or cardboard and layer 12 of polyolefin with mineral filler on one side of central layer. Layer 12 with mineral filler has thickness of from 30 micron to 100 micron and has mineral particles in an amount of from 40% to 70% by weight of layer 12 with mineral filler. Both sides of central layer are provided with water-impermeable coating of polyolefin.

EFFECT: increased rigidity and provision for manufacture of containers with improved capturing properties.

8 cl, 4 dwg

The invention relates to a multilayer composite material

The invention relates to a two-layer material with a plastic base and a thermoplastic adhesive layer and can be used for isolation of underground pipelines

Composite material // 2214921
The invention relates to thermoplastic composite materials, in particular materials having a layer of acrylic resin

The invention relates to a layered material consisting of at least two different polymeric materials that are directly connected to each other, where (A) is a thermoplastic polymer or thermoplastic polymer mixture containing at least one polar compound, at least one of the metals 1-5th main groups or 1-8-th side groups of the periodic system in the form of an extremely fine powder, and (B) is a polyurethane

FIELD: laminated material for manufacture of packaging containers by folding and thermal sealing and packaging containers for liquid food products manufactured from said material.

SUBSTANCE: packaging material 10 has central layer 11 of paper or cardboard and layer 12 of polyolefin with mineral filler on one side of central layer. Layer 12 with mineral filler has thickness of from 30 micron to 100 micron and has mineral particles in an amount of from 40% to 70% by weight of layer 12 with mineral filler. Both sides of central layer are provided with water-impermeable coating of polyolefin.

EFFECT: increased rigidity and provision for manufacture of containers with improved capturing properties.

8 cl, 4 dwg

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