Preparation method of photovoltaic module solder strip, photovoltaic module solder strip and photovoltaic module
By forming a multi-layer metal structure with depressions during the preparation of photovoltaic module welding tape, the shortcomings of existing welding tapes in light reflection and connection stability are solved, and more efficient light reflection and welding stability are achieved.
Patent Information
- Application Number
- CN202411645685.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-18
- Publication Date
- 2025-02-28
Smart Images
Figure CN119545952A_ABST
Abstract
Description
Technical Field
[0001] The present application mainly relates to the field of photovoltaic technology, and in particular to a method for preparing a photovoltaic module welding ribbon, a photovoltaic module welding ribbon and a photovoltaic module. Background Art
[0002] The soldering ribbon is a key component in the battery assembly, mainly used to connect the battery cells and play a conductive role. The soldering ribbon has a significant impact on the efficiency and quality of the battery assembly. Among them, improving the reflection of the incident light by the soldering ribbon and improving the connection stability between the soldering ribbon and the grid line are hot issues in this field. Summary of the invention
[0003] The technical problem to be solved by the present application is to provide a method for preparing a photovoltaic module welding strip, a photovoltaic module welding strip and a photovoltaic module. The method for preparing a photovoltaic module welding strip, the photovoltaic module welding strip and the photovoltaic module can improve the reflection of the welding strip to incident light and improve the connection stability between the welding strip and the grid line.
[0004] To solve the above technical problems, the present application provides a method for preparing a photovoltaic module welding strip, comprising: providing a mold, the mold being insulated and having a groove; forming a first metal layer on the inner wall of the groove; arranging a plurality of spaced-apart electrode points on the first metal layer; applying voltage to the plurality of electrode points, and electroplating a second metal layer on the first metal layer, the second metal layer having a depression with an opening facing the mold opening; and separating the first metal layer and the second metal layer from the mold.
[0005] In one embodiment of the present application, the electrode point includes a wire, a conductive glue and an insulating glue. The conductive glue is used to fix the wire on the first metal layer, and the insulating glue is coated on the conductive glue.
[0006] In one embodiment of the present application, the mold includes a first side wall and a second side wall, one side of the first side wall is connected to one side of the second side wall, and the other side of the first side wall and the other side of the second side wall constitute two sides of the opening of the mold.
[0007] In one embodiment of the present application, the angle between the first side wall and the second side wall is 30° to 60°, and the width of the opening of the mold is 80 μm to 200 μm.
[0008] In one embodiment of the present application, the multiple electrode points are divided into a first row of electrode points and a second row of electrode points, the first row of electrode points are arranged on the first side wall at intervals along the extension direction of the mold, and the second row of electrode points are arranged on the second side wall at intervals along the extension direction of the mold, wherein the distance between the electrode points and the opening of the mold is equal to or greater than a preset distance.
[0009] In one embodiment of the present application, the preparation method further includes: increasing the distance between the electrode point and the opening to increase the depth of the recess, or reducing the distance between the electrode point and the opening to reduce the depth of the recess.
[0010] In one embodiment of the present application, the cross section of the recess is V-shaped.
[0011] In an embodiment of the present application, the preparation method further includes electroplating a third metal layer on the surface of the recess.
[0012] In an embodiment of the present application, the first metal layer includes silver, the second metal layer includes copper, and the third metal layer includes tin.
[0013] In one embodiment of the present application, the preparation method further includes forming a layer of release agent on the inner wall of the mold before forming the first metal layer, and forming the first metal layer on the release agent.
[0014] In one embodiment of the present application, the cross-section of the groove is V-shaped.
[0015] On the other hand, the present application also proposes a photovoltaic module welding strip, comprising: a first metal layer, the cross-section of the first metal layer is V-shaped; and a second metal layer, located on the inner wall of the first metal layer, the second metal layer has a recess with an opening facing the opening of the first metal layer.
[0016] In an embodiment of the present application, the photovoltaic module welding ribbon further includes a third metal layer, and the third metal layer is located on the surface of the recess.
[0017] In an embodiment of the present application, the first metal layer includes silver, the second metal layer includes copper, and the third metal layer includes tin.
[0018] In one embodiment of the present application, the depression is V-shaped.
[0019] In one embodiment of the present application, a cross-section of the first metal layer is V-shaped.
[0020] On the other hand, the present application further proposes a photovoltaic module, comprising: the photovoltaic module welding strip as described above.
[0021] Compared with the prior art, this application has the following advantages:
[0022] (1) The soldering strip of the present application has a depression. Compared with the traditional soldering strip, the depression can increase the contact area between the soldering strip and the gate line, thereby improving the connection stability between the soldering strip and the gate line.
[0023] (2) The first metal layer of the present application is formed on two sides of the second metal layer, and the third metal layer is formed on the other side of the second metal layer. The first metal layer can reflect more light to the active area, and the third metal layer is easier to connect with the gate line.
[0024] (3) The depth of the depression can be controlled by controlling the distance between the electrode point and the mold opening. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The accompanying drawings are included to provide a further understanding of the present application. They are included and constitute a part of the present application. The accompanying drawings illustrate embodiments of the present application and together with the present specification serve to explain the principles of the present application. In the accompanying drawings:
[0026] Figure 1 It is a schematic flow chart of a method for preparing a photovoltaic module welding ribbon in one embodiment of the present application;
[0027] Figure 2 1 is a top view and a cross-sectional view of a mold in one embodiment of the present application;
[0028] Figures 3 to 7 is a schematic diagram of a soldering ribbon and a mold in a process of preparing a soldering ribbon in one embodiment of the present application;
[0029] Figure 8 Schematic diagram of the cross section of the welding strip in one embodiment of the present application.
[0030] Figure numerals: mold 210, first side wall 211, second side wall 212, opening 213, groove 214, first metal layer 220, release agent 230, electrode point 240, conductive glue 241, wire 242, second metal layer 250, first recess 251, third metal layer 260 and second recess 270. DETAILED DESCRIPTION
[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for the description of the embodiments. Obviously, the drawings described below are only some examples or embodiments of the present application. For ordinary technicians in this field, the present application can also be applied to other similar scenarios based on these drawings without creative work. Unless it is obvious from the language environment or otherwise explained, the same reference numerals in the figures represent the same structure or operation.
[0032] As shown in this application and claims, unless the context clearly indicates an exception, the words "a", "an", "an" and / or "the" do not refer to the singular and may also include the plural. Generally speaking, the terms "include" and "comprise" only indicate the inclusion of the steps and elements that have been clearly identified, and these steps and elements do not constitute an exclusive list. The method or device may also include other steps or elements.
[0033] Unless otherwise specifically stated, the relative arrangement, numerical expressions and numerical values of the parts and steps set forth in these embodiments do not limit the scope of the present application. At the same time, it should be understood that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to the actual proportional relationship. The technology, method and equipment known to those of ordinary skill in the relevant field may not be discussed in detail, but in appropriate cases, the technology, method and equipment should be considered as a part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters represent similar items in the following drawings, so that once a certain item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.
[0034] In the description of the present application, it should be understood that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings, and are only for the convenience of describing the present application and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction, and therefore cannot be understood as limiting the scope of protection of the present application; the directional words "inside and outside" refer to the inside and outside relative to the contours of each component itself.
[0035] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.
[0036] In addition, it should be noted that the use of words such as "first" and "second" to define components is only for the convenience of distinguishing the corresponding components. If not otherwise stated, the above words have no special meaning and cannot be understood as limiting the scope of protection of this application. In addition, although the terms used in this application are selected from well-known and commonly used terms, some terms mentioned in the specification of this application may be selected by the applicant at his or her discretion, and their detailed meanings are explained in the relevant parts of the description of this article. In addition, it is required to understand this application not only by the actual terms used, but also by the meaning implied by each term.
[0037] Flowcharts are used in the present application to illustrate the operations performed by the system according to the embodiments of the present application. It should be understood that the preceding or following operations are not necessarily performed accurately in order. On the contrary, various steps may be processed in reverse order or simultaneously. At the same time, other operations may be added to these processes, or one or more operations may be removed from these processes.
[0038] Next, the preparation method of the photovoltaic module welding ribbon, the photovoltaic module welding ribbon and the photovoltaic module of the present application are described through examples.
[0039] refer to Figure 1 The schematic flow chart of a method for preparing a photovoltaic module welding strip in an embodiment is shown. The preparation method in this embodiment includes the following steps S110 to S150.
[0040] S110: providing a mold, wherein the mold is insulated and has a groove;
[0041] S120: forming a first metal layer on the inner wall of the groove;
[0042] S130: Arranging a plurality of electrode points distributed at intervals on the first metal layer;
[0043] S140: applying voltage to the plurality of electrode points, and electroplating a second metal layer on the first metal layer, wherein the second metal layer has a recess with an opening facing the mold opening;
[0044] S150: Separating the first metal layer and the second metal layer from the mold.
[0045] Next, steps S110 to S150 are described in detail.
[0046] refer to Figure 2 The top view and cross-sectional view of the mold 210 in one embodiment are shown. In step S110, a mold 210 is provided. The mold 210 is insulated. The material of the mold 210 can be polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC) or acrylic (PMMA). The mold 210 can be prepared by injection molding, welding or gluing.
[0047] like Figure 2 As shown, the mold 210 has a long groove 214. Preferably, the cross section of the groove 214 is V-shaped. The cross section of the groove 214 can also be a trapezoid. The "V-shape" in this application may not be a strict V-shape. For example, the side and bottom of the V-shape may be curved. Figure 2 In the embodiment, the mold 210 has a first side wall 211, a second side wall 212 and an opening 213, one side of the first side wall 211 is connected to one side of the second side wall 212, the other side of the first side wall 211 and the other side of the second side wall 212 respectively constitute the left and right sides of the opening 213, and the first side wall 211 and the second side wall 212 form a groove 214.
[0048] An angle α between the first side wall 211 and the second side wall 212 may be 30° to 60°, for example, the angle α is 30°, 40°, 50° or 60°, a width W1 of the opening 213 may be 80μm to 200μm, for example, the width W1 is 80μm, 100μm, 120μm, 140μm, 160μm, 180μm or 200μm, a length L1 of the mold 210 may be 220mm to 1000mm, for example, the length L1 is 220mm, 400mm, 600mm, 800mm, 1000mm, 1200mm, 1400mm, 1600mm, 1800mm or 2000mm. The thickness of the side wall of the mold 210 may be 0.1 mm to 0.5 mm, for example, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, or 0.5 mm.
[0049] In one embodiment, the roughness of the inner wall of the mold 210 is less than 0.2 μm, which facilitates subsequent demolding.
[0050] refer to Figure 2 and Figure 3 As shown, in step S120, a first metal layer 220 is formed on the inner wall of the groove 214. Figure 3 In the embodiment, the first metal layer 220 directly contacts the inner wall of the mold 210. Figure 4 As shown, in one embodiment, before forming the first metal layer 220, a layer of release agent 230 is formed on the inner wall of the mold 210, and then the first metal layer 220 is formed on the release agent 230. The release agent 230 helps in subsequent demolding. The release agent 230 can be formed on the inner wall of the mold 210 by spraying, and the release agent 230 can include a fluorine-containing resin compound.
[0051] The first metal layer 220 may include a material with high reflectivity, for example, metallic silver. A layer of metallic silver with a thickness of 0.1 μm to 0.2 μm may be prepared by vacuum evaporation equipment or physical vapor deposition equipment, and the layer of metallic silver is used as the first metal layer 220. The first metal layer 220 may increase the reflection of the solder strip to the incident light, thereby reflecting more light to the photoactive area of the solar cell.
[0052] refer to Figure 4 and Figure 5 As shown, in step S130, a plurality of electrode points 240 are arranged on the first metal layer 220. Figure 4 and Figure 5 In the embodiment, the electrode point 240 includes a conductive glue 241, a wire 242 and an insulating glue (not shown). The conductive glue 241 is used to fix the wire 242 on the first metal layer 220, and the insulating glue is coated on the conductive glue 241. The insulating glue can avoid interference caused by the plating of the conductive glue during the subsequent electroplating process, thereby improving the uniformity of the electroplating. It should be noted that the insulating glue is not required. In addition, the composition of the electrode point 240 is not limited to the above-mentioned embodiment. For example, the wire 242 can also be connected to the first metal layer 220 by welding or the like. Any structure and method that can connect multiple points of the first metal layer 220 to the power supply setting are within the protection scope of this application.
[0053] Continue to refer Figure 4 and Figure 5 As shown, in Figure 4 and Figure 5In the embodiment, the six electrode points 240 are divided into two rows: a first row of electrode points and a second row of electrode points. The first row of electrode points has three electrode points 240, and the three electrode points 240 are arranged on the first side wall 211 along the extension direction of the mold 210 at intervals. The second row of electrode points also has three electrode points 240, and the three electrode points 240 are arranged on the second side wall 212 along the extension direction of the mold 210 at intervals. The distance D1 between the electrode point 240 and the opening 213 of the mold is equal to or greater than the preset distance. For the description of the spacing D1 and the preset distance, please refer to the following text. It can be understood that the number and distribution of the electrode points 240 are not limited to Figure 4 and Figure 5 The embodiments in the embodiment can be adjusted according to actual conditions, for example, reducing or increasing the number of electrode points 240, dividing the electrode points 240 into four rows, etc.
[0054] refer to Figure 6 As shown, it is a simplified schematic diagram. Figure 6 Not drawn Figure 4 , Figure 5 In step S140, voltage is applied to the plurality of electrode points, and the mold is immersed in the electroplating solution, and the second metal layer 250 is electroplated on the first metal layer 220. The second metal layer 250 obtained by electroplating has a first recess 251, and the opening of the first recess 251 faces the opening of the mold 210, or in other words, the direction of the opening of the first recess 251 is the same as the direction of the opening of the mold 210. The reason for the formation of the first recess 251 is that the electric field strength at different positions during the electroplating process is different.
[0055] exist Figure 6 In the embodiment, the cross section of the first recess 251 is V-shaped. When laying the welding tape, the first recess 251 contacts the gate line. Compared with the traditional welding tape, the first recess 251 of the present application can increase the contact area between the welding tape and the gate line, thereby improving the connection stability between the welding tape and the gate line.
[0056] Here, the spacing D1 and the preset distance mentioned above are explained. The first recess 251 can be obtained by controlling the spacing D1 to be equal to or less than the preset distance. Further, the depth of the first recess 251 can be controlled by adjusting the spacing D1. Increasing the spacing D1 can increase the depth of the first recess 251, and reducing the spacing D1 can reduce the depth of the first recess 251. The preset distance can be set according to the required minimum depth of the first recess 251. Controlling the spacing D1 to be equal to or greater than the preset distance can ensure that the depth of the first recess 251 is equal to or greater than the required minimum depth.
[0057] In one embodiment, the second metal layer 250 includes copper. The second metal layer 250 can be electroplated by applying voltage to a plurality of electrode points and immersing the mold in an electroplating solution for 16 to 40 minutes, wherein the electroplating solution includes a main salt (e.g., copper sulfate), a conductive medium (e.g., sulfuric acid), and an additive.
[0058] refer to Figure 6 and Figure 7 As shown, in one embodiment, the preparation method of the present application also includes electroplating a third metal layer 260 on the surface of the first recess 251, the third metal layer 260 does not completely fill the first recess 251, the third metal layer 260 surrounds a second recess 270, the second recess 270 can increase the contact area between the third metal layer 260 and the gate line, and the cross-section of the second recess 270 can be V-shaped.
[0059] In one embodiment, the third metal layer 260 may include tin. The third metal layer 260 may be electroplated by the following method: immersing the mold in an electroplating solution for electroplating for 1 min to 3 min, and the electroplating solution may include stannous methanesulfonate, methanesulfonic acid, and additives.
[0060] refer to Figure 7 and Figure 8 As shown, in step S150, the first metal layer 220 and the second metal layer 250 are separated from the mold 210. Figure 7 and Figure 8 In the embodiment of the present invention, there is also a third metal layer 260, so step S150 also separates the third metal layer 260 from the mold 210. The first metal layer 220, the second metal layer 250 and the third metal layer 260 form a welding strip. Step S150 can also be called a demolding step.
[0061] refer to Figure 8 As shown, the first metal layer 220 is formed on two sides of the second metal layer 250, and the third metal layer 260 is formed on the other side of the second metal layer 250 (i.e., on the first recess 251). In the battery assembly, the first metal layer 220 faces the incident light and can reflect the incident light to the active area. Compared with the second metal layer 250 and the third metal layer 260, the first metal layer 220 has a higher reflectivity to light, so more light can be reflected to the active area. The third metal layer 260 is used to connect to the grid line. Compared with the first metal layer 220 and the second metal layer 250, the third metal layer 260 is easier to connect to the grid line. The first metal layer 220 can be metal silver, the second metal layer 250 can be metal copper, and the third metal layer 260 can be metal tin.
[0062] On the other hand, the present application also proposes a photovoltaic module welding strip, referring to Figure 8As shown, the photovoltaic module welding strip includes: a first metal layer 220, a second metal layer 250 and a third metal layer 260, the first metal layer 220 has a groove, and preferably, the cross section of the first metal layer 220 is V-shaped. The second metal layer 250 is located on the inner wall of the first metal layer 220, and the second metal layer 250 has a depression, which can be V-shaped. The third metal layer 260 is located on the surface of the depression. In some embodiments, the photovoltaic module welding strip may not include the third metal layer 260.
[0063] like Figure 8 As shown, the photovoltaic module welding strip has a second recess 270 surrounded by the third metal layer 260. The second recess 270 can increase the contact area between the third metal layer 260 and the grid line. The cross section of the second recess 270 can be V-shaped.
[0064] In one embodiment, the first metal layer 220 includes silver, the second metal layer 250 includes copper, and the third metal layer 260 includes tin.
[0065] On the other hand, the present application further provides a photovoltaic module, which includes the photovoltaic module welding ribbon as described above.
[0066] The basic concepts have been described above. Obviously, for those skilled in the art, the above application disclosure is only an example and does not constitute a limitation of the present application. Although not explicitly stated herein, those skilled in the art may make various modifications, improvements and amendments to the present application. Such modifications, improvements and amendments are suggested in the present application, so such modifications, improvements and amendments still belong to the spirit and scope of the exemplary embodiments of the present application.
[0067] At the same time, the present application uses specific words to describe the embodiments of the present application. For example, "one embodiment", "an embodiment", and / or "some embodiments" refer to a certain feature, structure or characteristic related to at least one embodiment of the present application. Therefore, it should be emphasized and noted that "one embodiment" or "an embodiment" or "an alternative embodiment" mentioned twice or more in different positions in this specification does not necessarily refer to the same embodiment. In addition, some features, structures or characteristics in one or more embodiments of the present application can be appropriately combined.
[0068] Similarly, it should be noted that in order to simplify the description of the disclosure of this application and thus help understand one or more application embodiments, in the above description of the embodiments of this application, multiple features are sometimes merged into one embodiment, figure or description thereof. However, this disclosure method does not mean that the features required by the object of this application are more than the features mentioned in the claims. In fact, the features of the embodiments are less than all the features of the single embodiment disclosed above.
[0069] In some embodiments, numbers describing the number of components and attributes are used. It should be understood that such numbers used in the description of the embodiments are modified by the modifiers "about", "approximately" or "substantially" in some examples. Unless otherwise specified, "about", "approximately" or "substantially" indicate that the numbers are allowed to vary by ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximate values, which may change according to the required features of individual embodiments. In some embodiments, the numerical parameters should take into account the specified significant digits and adopt the general method of retaining digits. Although the numerical domains and parameters used to confirm the breadth of their range in some embodiments of the present application are approximate values, in specific embodiments, the setting of such numerical values is as accurate as possible within the feasible range.
[0070] Although the present application has been described with reference to the current specific embodiments, ordinary technicians in this technical field should recognize that the above embodiments are only used to illustrate the present application, and various equivalent changes or substitutions may be made without departing from the spirit of the present application. Therefore, as long as the changes and modifications to the above embodiments are within the essential spirit of the present application, they will fall within the scope of the claims of the present application.
Claims
1. A method for preparing a photovoltaic module welding ribbon, characterized in that: include: Providing a mold, wherein the mold is insulated and has a groove; forming a first metal layer on an inner wall of the groove; Arranging a plurality of electrode points distributed at intervals on the first metal layer; applying voltage to the plurality of electrode points, and electroplating a second metal layer on the first metal layer, wherein the second metal layer has a recess with an opening facing the mold opening; as well as The first metal layer and the second metal layer are separated from the mold.
2. The preparation method according to claim 1, characterized in that The electrode point includes a wire, a conductive glue and an insulating glue. The conductive glue is used to fix the wire on the first metal layer, and the insulating glue is coated on the conductive glue.
3. The preparation method according to claim 1, characterized in that: The mold includes a first side wall and a second side wall, one side of the first side wall is connected to one side of the second side wall, and the other side of the first side wall and the other side of the second side wall constitute two sides of the opening of the mold.
4. The preparation method according to claim 3, characterized in that: The angle between the first side wall and the second side wall is 30° to 60°, and the width of the opening of the mold is 80 μm to 200 μm.
5. The preparation method according to claim 3, characterized in that: The multiple electrode points are divided into a first row of electrode points and a second row of electrode points, the first row of electrode points are arranged on the first side wall at intervals along the extension direction of the mold, and the second row of electrode points are arranged on the second side wall at intervals along the extension direction of the mold, wherein the distance between the electrode points and the opening of the mold is equal to or greater than a preset distance.
6. The preparation method according to claim 5, characterized in that: Also includes: The distance between the electrode point and the opening is increased to increase the depth of the recess, or the distance between the electrode point and the opening is decreased to decrease the depth of the recess.
7. The preparation method according to claim 1, characterized in that: The cross section of the recess is V-shaped.
8. The preparation method according to claim 1, characterized in that: The method also includes electroplating a third metal layer on the surface of the recess.
9. The preparation method according to claim 8, characterized in that: The first metal layer includes silver, the second metal layer includes copper, and the third metal layer includes tin.
10. The preparation method according to claim 1, characterized in that: The method further includes forming a layer of mold release agent on the inner wall of the mold before forming the first metal layer, and forming the first metal layer on the mold release agent.
11. The preparation method according to claim 1, characterized in that: The cross section of the groove is V-shaped.
12. A photovoltaic module welding strip, characterized in that: include: A first metal layer, wherein the first metal layer has a groove; as well as The second metal layer is located on the inner wall of the first metal layer, and the second metal layer has a recess with an opening facing the opening of the first metal layer.
13. The photovoltaic module welding strip according to claim 12, characterized in that: The invention also includes a third metal layer, wherein the third metal layer is located on the surface of the recess.
14. The photovoltaic module welding strip according to claim 13, characterized in that: The first metal layer includes silver, the second metal layer includes copper, and the third metal layer includes tin.
15. The photovoltaic module welding strip according to claim 12, characterized in that: The depression is V-shaped.
16. The photovoltaic module welding strip according to claim 12, characterized in that: The cross section of the first metal layer is V-shaped.
17. A photovoltaic module, characterized in that: include: The photovoltaic module welding strip according to any one of claims 12 to 16.