Water-responsive multi-phosphorescent anti-counterfeit coating, preparation method thereof and anti-counterfeit label

Abstract

The invention relates to the technical field of anti-counterfeiting coatings, in particular to a water-responsive multi-phosphorescent anti-counterfeiting coating, a preparation method thereof and an anti-counterfeiting label, and the preparation method comprises the following steps: smashing black brin and then drying to obtain black brin powder; mixing 1-5 parts by weight of the black brin powder, 5-20 parts by weight of m-phenylenediamine, 5-20 parts by weight of sodium alginate and 350-500 parts by weight of water, carrying out a hydrothermal reaction at a preset temperature, and after the reaction is completed, carrying out filtering treatment to obtain a phosphorescent carbon dot solution; and embedding the phosphorescent carbon dot solution into a polymer matrix to obtain the phosphorescent anti-counterfeiting coating. The water-responsive multi-phosphorescent anti-counterfeiting coating provided by the invention can realize fluorescent / phosphorescent dual-mode anti-counterfeiting, and the fluorescent color of the label is changed from blue to green when the label encounters water, so that the multi-anti-counterfeiting and information encryption capabilities are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-counterfeiting coatings, and in particular to a water-responsive multi-phosphorescent anti-counterfeiting coating and a preparation method thereof, and an anti-counterfeiting label. Background Art

[0002] Nowadays, the problem of counterfeiting and shoddy products is becoming increasingly serious. Common fluorescent anti-counterfeiting can no longer meet people's needs. The more complex room temperature phosphorescent (RTP) material is a material with continuous luminescence characteristics. It is widely used in many fields such as information anti-counterfeiting and optoelectronics and has attracted much attention. At present, the more traditional room temperature phosphorescent materials are mainly composed of inorganic compounds containing rare earth elements and organic metal complexes. However, these materials have some problems: high toxicity, complex preparation process, high cost, etc. In response to these problems, researchers have vigorously developed metal-free organic room temperature phosphorescent materials in recent years. However, although most of the current organic phosphorescent materials avoid the above problems, their intersystem crossing (ISC) is relatively inefficient, resulting in poor room temperature phosphorescence performance, which greatly limits its scope of application. Therefore, it is very necessary to develop a new room temperature phosphorescent material with excellent optical properties. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide a method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating, which can realize fluorescent / phosphorescent dual-mode anti-counterfeiting, and the fluorescent color of the label changes from blue to green when it comes into contact with water, thereby achieving multiple anti-counterfeiting and information encryption capabilities.

[0004] The technical problem to be solved by the present invention is also to provide a water-responsive multi-phosphorescent anti-counterfeiting coating, which can achieve fluorescent / phosphorescent dual-mode anti-counterfeiting, and the fluorescent color of the label changes from blue to green when it comes into contact with water, thereby achieving multiple anti-counterfeiting and information encryption capabilities.

[0005] In order to solve the above technical problems, the present invention provides a method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating, comprising the following steps:

[0006] The black plum is crushed and dried to obtain black plum powder;

[0007] According to weight parts, 1 to 5 parts of the black plum powder, 5 to 20 parts of m-phenylenediamine, 5 to 20 parts of sodium alginate and 350 to 500 parts of water are mixed, and a hydrothermal reaction is carried out at a preset temperature. After the reaction is completed, filtering is carried out to obtain a phosphorescent carbon dot solution;

[0008] The phosphorescent carbon dot solution is embedded in a polymer matrix to obtain a phosphorescent anti-counterfeiting coating.

[0009] In some embodiments, the step of crushing the black plums and then drying them comprises:

[0010] The black plum is crushed and dried at 130° C. to 160° C. for 4 h to 8 h, and the powder is collected and ground to obtain black plum powder.

[0011] In some embodiments, the preset temperature is 160° C. to 250° C.; and the reaction time of the hydrothermal reaction is 10 h to 15 h.

[0012] In some embodiments, the filtering process comprises:

[0013] First, filter using a 0.1 μm to 0.5 μm filter to obtain a filtrate;

[0014] Then, the filtrate is dialyzed using a dialysis bag with a molecular weight cut-off of 8000-1500.

[0015] In some embodiments, embedding the phosphorescent carbon dot solution into a polymer matrix comprises:

[0016] mixing the polymer with water to obtain a polymer matrix;

[0017] According to volume, 20 to 30 parts of the polymer matrix and 0.1 to 2 parts of the phosphorescent carbon dot solution are mixed and stirred.

[0018] In some embodiments, the polymer includes one or more of polyacrylic acid, polyvinyl alcohol and polyacrylamide; and the concentration of the polymer matrix is ​​45 wt % to 65 wt %.

[0019] In order to solve the above technical problems, the present invention also provides a water-responsive multiple phosphorescent anti-counterfeiting coating, and the water-responsive multiple phosphorescent anti-counterfeiting coating is prepared by the preparation method of the water-responsive multiple phosphorescent anti-counterfeiting coating as described above.

[0020] In some embodiments, the water-responsive multi-phosphorescent anti-counterfeiting coating exhibits no fluorescence display under sunlight, displays blue fluorescence under a 365nm ultraviolet lamp, and continues to display blue fluorescence for 3s-10s after the 365nm ultraviolet lamp is removed.

[0021] In some embodiments, the water-responsive multi-phosphorescent anti-counterfeiting coating displays green fluorescence under a 365nm ultraviolet lamp when in contact with water, and displays blue fluorescence under a 365nm ultraviolet lamp after being heated to dry the moisture.

[0022] Correspondingly, the present invention also provides a water-responsive multiple phosphorescent anti-counterfeiting label, wherein the water-responsive multiple phosphorescent anti-counterfeiting label comprises a substrate, and the substrate is coated with the water-responsive multiple phosphorescent anti-counterfeiting coating.

[0023] The implementation of the present invention has the following beneficial effects:

[0024] (1) The use of biomass as a carbon source to prepare phosphorescent carbon quantum dots has the advantages of being non-toxic, environmentally friendly, low-cost, and having a simple preparation process compared to traditional phosphorescent materials prepared from inorganic compounds of rare earth elements and organic metal complexes.

[0025] (2) Water-responsive multi-phosphorescent anti-counterfeiting coatings not only have fluorescent / phosphorescent dual-mode anti-counterfeiting properties, but also change their fluorescent color from blue to green when exposed to water, and change from green to blue again after drying. They can be reused, which plays a role in multiple anti-counterfeiting information encryption and solves the problem of insufficient anti-counterfeiting ability of traditional single fluorescent or phosphorescent anti-counterfeiting on labels, and is more in line with the anti-counterfeiting needs of current high-end products. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a test result diagram of anti-counterfeiting verification of a water-responsive multi-phosphorescent anti-counterfeiting coating provided in one embodiment of the present invention. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. In addition, it should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0028] In the description of the present invention, it is necessary to understand that the terms "length", "width", "up", "down", "left", "right", "horizontal", "top", "bottom", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0029] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0030] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, an electrical connection, or mutual communication; it can be a direct connection, or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0031] In the present invention, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may include that the first and second features are in direct contact, or may include that the first and second features are not in direct contact but are in contact through another feature between them. Moreover, a first feature being "above", "above" and "above" a second feature includes that the first feature is directly above and obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. A first feature being "below", "below" and "below" a second feature includes that the first feature is directly below and obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature.

[0032] The disclosure below provides many different embodiments or examples to realize different structures of the present invention. In order to simplify the disclosure of the present invention, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present invention. In addition, the present invention can repeat reference numbers and / or reference letters in different examples, and this repetition is for the purpose of simplification and clarity, which itself does not indicate the relationship between the various embodiments and / or settings discussed. In addition, the examples of various specific processes and materials provided by the present invention, but those of ordinary skill in the art can be aware of the application of other processes and / or the use of other materials.

[0033] In the present invention, "preferred" and "better" are only used to describe implementation methods or embodiments with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of the present invention. In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features. In the present invention, when involving numerical ranges, unless otherwise specified, the two endpoints of the numerical range are included.

[0034] In order to solve the above problems, the present invention provides a method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating, comprising the following steps:

[0035] (1) crushing the black plum and drying it to obtain black plum powder;

[0036] In some embodiments, the step of crushing the black plums and then drying them comprises:

[0037] The black plum is crushed and dried at 130° C. to 160° C. for 4 h to 8 h, and the powder is collected and ground to obtain black plum powder.

[0038] It should be noted that the black plum is a pitted black plum, including peel and pulp; it can also be a single black plum peel.

[0039] Preferably, the black plum is crushed and placed in a forced air drying oven at 140° C. to 150° C. for 4 to 8 hours, and then the powder is scraped off and ground with a mortar to obtain brown-yellow black plum powder.

[0040] (2) mixing 1 to 5 parts of the black plum powder, 5 to 20 parts of m-phenylenediamine, 5 to 20 parts of sodium alginate and 350 to 500 parts of water in parts by weight, performing a hydrothermal reaction at a preset temperature, and filtering after the reaction is completed to obtain a phosphorescent carbon dot solution;

[0041] Preferably, 1 to 4 parts of the black plum powder, 6 to 15 parts of meta-phenylenediamine, 6 to 15 parts of sodium alginate and 370 to 450 parts of water are mixed.

[0042] In some embodiments, the preset temperature is 160°C to 250°C, and the reaction time of the hydrothermal reaction is 10h to 15h. Preferably, the preset temperature is 170°C to 230°C, and the reaction time of the hydrothermal reaction is 11h to 14h.

[0043] In some embodiments, the filtration treatment includes: first filtering with a 0.1 μm to 0.5 μm filter to obtain a filtrate; then dialyzing the filtrate with a dialysis bag with a molecular weight cutoff of 8000 to 1500. Preferably, first filtering with a 0.22 μm filter to remove larger particle impurities to obtain a filtrate; then dialyzing the filtrate with a dialysis bag with a molecular weight cutoff of 1000 to remove substances with larger molecular weight, and the dialysis time is 24h to 48h.

[0044] (3) embedding the phosphorescent carbon dot solution into a polymer matrix to obtain a phosphorescent anti-counterfeiting coating.

[0045] In some embodiments, embedding the phosphorescent carbon dot solution into a polymer matrix comprises:

[0046] 3.1) mixing the polymer with water to obtain a polymer matrix;

[0047] In some embodiments, the polymer includes one or more of polyacrylic acid, polyvinyl alcohol and polyacrylamide, and the concentration of the polymer matrix is ​​45wt% to 65wt%. Preferably, the polymer is polyacrylic acid, and the concentration of the polymer matrix is ​​47wt% to 62wt%.

[0048] 3.2) According to volume, 20 to 30 parts of the polymer matrix and 0.1 to 2 parts of the phosphorescent carbon dot solution are mixed and stirred.

[0049] In some embodiments, 21 to 28 parts of the polymer matrix and 0.4 to 1.8 parts of the phosphorescent carbon dot solution are mixed and stirred for 10 to 30 minutes, and then ultrasonically treated for 8 to 15 minutes to remove foam to obtain a water-responsive multi-phosphorescent anti-counterfeiting coating.

[0050] Through the above method, a water-responsive multi-phosphorescent anti-counterfeiting coating can be prepared, which is prepared by a hydrothermal method, and is a phosphorescent ink obtained by compounding phosphorescent carbon quantum dots and hydrophilic polymers, which displays blue fluorescence under a 365nm ultraviolet lamp, and after removing the ultraviolet light source, produces blue phosphorescence and continues to emit light for 3-10s, or even longer, to achieve fluorescence / phosphorescence dual-mode anti-counterfeiting. At the same time, the ink-printed pattern containing the water-responsive multi-phosphorescent anti-counterfeiting coating prepared by the present invention has a special responsiveness to water, and phosphorescence quenching occurs after encountering water, and its fluorescent color changes from blue to green. After heating and drying the water, its fluorescent color changes from green to blue again, and it can be used repeatedly to achieve static / dynamic response anti-counterfeiting, and has a multi-mode anti-counterfeiting function with stimulus response characteristics.

[0051] Compared with traditional single-mode fluorescent anti-counterfeiting or phosphorescent anti-counterfeiting, the preparation process provided by the present invention can significantly improve the information encryption and information anti-counterfeiting capabilities of the label by preparing a water-responsive multi-phosphorescent anti-counterfeiting coating with excellent optical properties.

[0052] At the same time, the present invention also provides a water-responsive multiple phosphorescent anti-counterfeiting coating, and the water-responsive multiple phosphorescent anti-counterfeiting coating is prepared by the preparation method of the water-responsive multiple phosphorescent anti-counterfeiting coating as described above.

[0053] In some embodiments, the water-responsive multi-phosphorescent anti-counterfeiting coating exhibits no fluorescence display under sunlight, displays blue fluorescence under a 365nm ultraviolet lamp, and continues to display blue fluorescence for 3s-10s after the 365nm ultraviolet lamp is removed.

[0054] Preferably, blue fluorescence is displayed under a 365nm ultraviolet lamp, and after the 365nm ultraviolet lamp is removed, the blue fluorescence continues to be displayed for 3s-6s. Phosphorescent materials can usually continue to emit light for a period of time after the light source stops irradiating. In other words, after the 365nm ultraviolet lamp is removed, the blue fluorescence continues to be displayed, showing the phosphorescent characteristics.

[0055] In some embodiments, the water-responsive multi-phosphorescent anti-counterfeiting coating displays green fluorescence under a 365nm ultraviolet lamp when in contact with water, and displays blue fluorescence under a 365nm ultraviolet lamp after being heated to dry the moisture.

[0056] In addition, the present invention also provides a water-responsive multiple phosphorescent anti-counterfeiting label, the water-responsive multiple phosphorescent anti-counterfeiting label comprises a substrate, and the substrate is coated with the water-responsive multiple phosphorescent anti-counterfeiting coating.

[0057] In some embodiments, the water-responsive multi-phosphorescent anti-counterfeiting coating is coated on the substrate by screen printing.

[0058] In some embodiments, the substrate is non-fluorescent paper.

[0059] The water-responsive multi-phosphorescent anti-counterfeiting coating is overprinted onto non-fluorescent paper by screen printing to prepare an anti-counterfeiting label. The prepared water-responsive multi-phosphorescent anti-counterfeiting coating is applied to multiple anti-counterfeiting applications through a designed screen printing plate. Screen printing uses the principle that the mesh holes in the graphic part of the screen plate can pass through ink, while the mesh holes in the rest of the screen plate cannot pass through ink. Pour the prepared water-responsive multi-phosphorescent anti-counterfeiting coating on one side of the screen printing plate, use a scraper to apply an appropriate degree of pressure, and move toward the other side of the screen printing plate repeatedly. Since the coating has a sticky effect, the coating adheres to the non-fluorescent paper through the penetration of the mesh holes during the process of being moved by the scraper, thereby completing a screen printing process.

[0060] In some embodiments, after the water-responsive multi-phosphorescent anti-counterfeiting coating is coated on the substrate by screen printing, a varnish layer is further formed. The varnish layer can form a protective film that effectively resists friction and scratches, protects the label from being easily worn, and thus extends its service life.

[0061] The following will be further described in conjunction with embodiments:

[0062] Example 1

[0063] A method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating comprises the following steps:

[0064] The black plum was crushed and dried at 150°C for 6 hours, and the powder was collected and ground to obtain black plum powder;

[0065] According to weight parts, 3 parts of the black plum powder, 8 parts of m-phenylenediamine, 10 parts of sodium alginate and 400 parts of water were mixed, and a hydrothermal reaction was carried out at 200° C. for 12 hours. After the reaction was completed, the mixture was filtered to obtain a phosphorescent carbon dot solution;

[0066] The phosphorescent carbon dot solution is embedded in a polymer matrix. Specifically, by volume, 25 parts of a polyacrylic acid aqueous solution and 0.8 parts of the phosphorescent carbon dot solution are mixed and stirred to obtain a phosphorescent anti-counterfeiting coating.

[0067] Example 2

[0068] A method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating comprises the following steps:

[0069] The black plum was crushed and dried at 150°C for 6 hours, and the powder was collected and ground to obtain black plum powder;

[0070] According to weight parts, 2 parts of the black plum powder, 10 parts of m-phenylenediamine, 9 parts of sodium alginate and 400 parts of water were mixed, and a hydrothermal reaction was carried out at 200° C. for 12 hours. After the reaction was completed, the mixture was filtered to obtain a phosphorescent carbon dot solution;

[0071] The phosphorescent carbon dot solution is embedded in a polymer matrix. Specifically, by volume, 25 parts of a polyacrylic acid aqueous solution and 0.8 parts of the phosphorescent carbon dot solution are mixed and stirred to obtain a phosphorescent anti-counterfeiting coating.

[0072] Example 3

[0073] A method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating comprises the following steps:

[0074] The black plum was crushed and dried at 150°C for 6 hours, and the powder was collected and ground to obtain black plum powder;

[0075] According to weight parts, 3 parts of the black plum powder, 8 parts of m-phenylenediamine, 10 parts of sodium alginate and 400 parts of water were mixed, and a hydrothermal reaction was carried out at 200° C. for 12 hours. After the reaction was completed, the mixture was filtered to obtain a phosphorescent carbon dot solution;

[0076] The phosphorescent carbon dot solution is embedded in a polymer matrix. Specifically, by volume, 30 parts of a polyacrylic acid aqueous solution and 0.5 parts of the phosphorescent carbon dot solution are mixed and stirred to obtain a phosphorescent anti-counterfeiting coating.

[0077] The water-responsive multi-phosphorescent anti-counterfeiting coatings prepared in Examples 1 to 3 were screen-printed onto non-fluorescent paper to obtain water-responsive multi-phosphorescent anti-counterfeiting labels. The anti-counterfeiting labels were verified for anti-counterfeiting. The verification results were as follows: Figure 1 As shown: the water-responsive multi-phosphorescent anti-counterfeiting coating shows no fluorescence under sunlight, and shows blue fluorescence under a 365nm ultraviolet lamp. After the 365nm ultraviolet lamp is removed, it continues to show blue fluorescence for 3s, showing the phosphating property, that is, it can continue to emit light for a period of time after the light source stops irradiating. The water-responsive multi-phosphorescent anti-counterfeiting coating shows green fluorescence under a 365nm ultraviolet lamp after it comes into contact with water, and shows blue fluorescence under a 365nm ultraviolet lamp after heating to dry the water.

[0078] In the description of this specification, the description with reference to the terms "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiments or examples are included in at least one embodiment or example of the present application. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0079] The above is a preferred embodiment of the invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the invention. These improvements and modifications are also considered to be within the scope of protection of the invention.

Claims

1. A method for preparing a water-responsive multi-phosphorescent anti-counterfeiting coating, characterized in that: The following steps are involved: The black plum is crushed and dried to obtain black plum powder; According to weight parts, 1 to 5 parts of the black plum powder, 5 to 20 parts of m-phenylenediamine, 5 to 20 parts of sodium alginate and 350 to 500 parts of water are mixed, and a hydrothermal reaction is carried out at a preset temperature. After the reaction is completed, filtering is carried out to obtain a phosphorescent carbon dot solution; The phosphorescent carbon dot solution is embedded in a polymer matrix to obtain a phosphorescent anti-counterfeiting coating.

2. The method for preparing the water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 1, characterized in that: The method of crushing the black plum and drying it comprises: The black plum is crushed and dried at 130° C. to 160° C. for 4 h to 8 h, and the powder is collected and ground to obtain black plum powder.

3. The method for preparing the water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 1, characterized in that: The preset temperature is 160° C. to 250° C.; and the reaction time of the hydrothermal reaction is 10 h to 15 h.

4. The method for preparing the water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 1, characterized in that: The filtering process includes: First, filter using a 0.1 μm to 0.5 μm filter to obtain a filtrate; Then, the filtrate is dialyzed using a dialysis bag with a molecular weight cut-off of 8000-1500.

5. The method for preparing the water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 1, characterized in that: Embedding the phosphorescent carbon dot solution into a polymer matrix comprises: mixing the polymer with water to obtain a polymer matrix; According to volume, 20 to 30 parts of the polymer matrix and 0.1 to 2 parts of the phosphorescent carbon dot solution are mixed and stirred.

6. The method for preparing the water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 1, characterized in that: The polymer includes one or more of polyacrylic acid, polyvinyl alcohol and polyacrylamide; and the concentration of the polymer matrix is ​​45wt% to 65wt%.

7. A water-responsive multi-phosphorescent anti-counterfeiting coating, characterized in that: The water-responsive multi-phosphorescent anti-counterfeiting coating is prepared by the preparation method of the water-responsive multi-phosphorescent anti-counterfeiting coating according to any one of claims 1 to 6.

8. The water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 7, characterized in that: The water-responsive multi-phosphorescent anti-counterfeiting coating exhibits no fluorescence display under sunlight, displays blue fluorescence under a 365nm ultraviolet lamp, and continues to display blue fluorescence for 3s-10s after the 365nm ultraviolet lamp is removed.

9. The water-responsive multi-phosphorescent anti-counterfeiting coating according to claim 7, characterized in that: The water-responsive multi-phosphorescent anti-counterfeiting coating displays green fluorescence under a 365nm ultraviolet lamp when in contact with water, and displays blue fluorescence under a 365nm ultraviolet lamp after being heated to dry the water.

10. A water-responsive multi-phosphorescent anti-counterfeiting label, characterized in that: The water-responsive multi-phosphorescent anti-counterfeiting label comprises a substrate, and the substrate is coated with the water-responsive multi-phosphorescent anti-counterfeiting coating as claimed in any one of claims 7 to 9.

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