• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PROCESS OF OBTAINING A SUBSTRATE COATED ON AT LEAST A PART OF ITS SURFACE AT LEAST ONE METAL AND SUBSTRATE OXIDE LAYER. The invention has as its object a process of obtaining a substrate coated on at least part of its surface of at least one oxide layer of a metal M whose physical thickness is less than or equal to 30 nm, said oxide layer not being comprised of a stack of layers comprising at least one silver layer, said process comprising the following steps: at least one intermediate layer of a material chosen from the metal M, a nitride of the emtal M, a carbide is deposited by catholic spraying of the emtal M, or a sub-stoichiometric oxide in oxygen of the metal M, said intermediate layer not being deposited above or below a layer based on titanium oxide, the physical thickness of said intermediate layer being less than or equal to 30 nmm , at least part of the surface of said intermediate layer is oxidized with the help of a heat treatment, during which said intermediate layer is in direct contact with an atmosphere oxidant, notably (...).
    公开号:BR112012006869B1
    申请号:R112012006869-5
    申请日:2010-09-09
    公开日:2020-07-07
    发明作者:Olivier Muhlhoff；Jean-Claude Desvignes
    申请人:Compagnie Generale Des Etablissements Michelin；Michelin Recherche Et Technique S. A.；
    IPC主号:
    专利说明:

    [0001] The invention relates to the technical domain of vehicle vehicle tires, comprising high-contrast markings, as well as a process for making molds intended for the molding and vulcanization of said vehicle tires.
    [0002] More particularly, the invention is an improvement on publication W02007 / 045425 which describes particular types of high contrast markings.
    [0003] The surface of vehicle tires supports a large number of markings designed on the one hand to provide legal technical information on the quality of the vehicle tire and, on the other hand, to allow the consumer to distinguish the brand and the origin of the product.
    [0004] These markings are, as a general rule, obtained by embossed patterns arranged on the surface of the vehicle tire and corresponding to patterns in cracks made on the molding surface. Generally, vulcanization molds are made of metal with a very good surface finish appearance. But the outer surface of the vehicle tire that results therefrom, smooth and black, has the effect of returning the light.
    [0005] The contrast effect described in the publication cited above is obtained by arranging a plurality of filaments divided over the entire pattern, each filament having a medium section whose diameter is between 0.03 mm and 0.5 mm, of which the height is at least 0.1 mm, and divided over the pattern surface with a density of at least 5 filaments per mm2, and preferably greater than 15 filaments per mm2
    [0006] It is observed that the same contrast effect is obtained when, instead of filaments, parallel blades having an average width between 0.03 mm and 0.5 mm are available over the entire surface of the pattern. height is at least 0.1 mm and arranged over a maximum pitch of 0.5 mm.
    [0007] The effect of these filaments, or these blades, is to trap the incident light on the surface of the pattern and, by absorbing the light, to give a black and matte-matte appearance to the pattern being sought.
    [0008] The object of the present invention is to propose a particular form of surface state of the filaments or blades above allowing to improve the contrast effect of the patterns comprising these filaments or these blades, as well as a process allowing to make the molds intended to form the impression of vehicle tires carrying such patterns during the vulcanization stage.
    [0009] The invention therefore relates to a vehicle tire having a visible surface comprising patterns contrasting with respect to said surface, said pattern comprising over its entire surface a plurality of filaments with a density at least equal at five filaments per mm2 or a plurality of sheets parallel to each other and arranged over a pitch of another 0.5 mm, each filament having a medium section whose diameter (d) is between 0.03 mm and 0.5 mm , or each blade having an average width (d) between 0.03 mm and 0.5 mm.
    [0010] According to the invention, it is advisable that the filaments or blades have, on at least a quarter of their surface, an average roughness Rz comprised between 5 pm and 30 pm.
    [0011] Indeed, it was pointed out that the incident light is trapped to a certain extent by multiple reflections on the surface of the filaments, or the blades, when the said surface contains susceptible roughnesses, due to the multiplicity of incidence angles that they offer in relation to the middle surface, to reflect light along random directions. This results in a more matte visual impression, and in the case of patterns made on vehicle tires, a more intense black color and forming a better contrast with the rest of the tire surface.
    [0012] The contrast is all the greater when the pattern's surface is tiled with shiny surfaces.
    [0013] The contrast effect begins to be sensitive, in relation to the filaments whose surface would be less rough, when at least the quarter of the filament or blade surface has this roughness.
    [0014] Likewise, as will be seen later, it is possible to vary the intensity of the contrast by increasing the proportion of the surface having this minimum roughness or by positioning the roughest surface towards the top or bottom of the filament or the blade.
    [0015] The invention also relates to a process of making a metal mold for the molding and vulcanization of a vehicle tire according to the invention and comprising patterns forming a higher contrast with the surface.
    [0016] In accordance with this process, it is carried out, with the help of a laser, generating a luminous brush of sufficient energy to sublimate the metal constituting the mold, patterns comprising on the whole of its surface cavities having a medium section whose diameter (d) is between 0.03 mm and 0.5 mm with a density at least equal to 5 cavities per mm2, or parallel grooves with an average width (d) between 0.03 mm and 0.5 mm and at a distance of less than 0.5 mm, said cavities or grooves having a depth of at least 0.1 mm, applying the luminous brush emanating from the laser source on the surface of the mold in one or more passes successive, each of the passages having the effect of corroding the metal on a given surface and depth. This process is characterized by the fact that, during a passage, the melting and sublimation of the metal by the luminous ray have the effect of projecting the liquid metal and condensing the metal vapors on the walls of the cavity obtained during the previous passages. .
    [0017] The almost instantaneous rise in the temperature of the metal by the energy from the laser source causes the melting, but also the sublimation of the metal in the form of violent degassing, with the effect of projecting nodules of material on the walls of the cavity or the grooves made during previous passages. Upon solidifying, these nodules create surface irregularities whose characteristics correspond precisely to the roughness sought to ensure the molding of the filaments or blades making the object of the invention.
    [0018] The gases from the sublimation of the metal condense on the cavity walls and increase the irregularities.
    [0019] It is, therefore, important that the fusion and sublimation of the metal be operated in a very short time to generate this “explosive” phenomenon.
    [0020] On the other hand, it is advisable to proceed with successive passages in order to allow liquid projections and vapors to solidify or to reconnect between each pass over said walls, which are colder.
    [0021] Preferably, the passages are arranged so that the section of the corroded surface during one pass is greater than the corroded section during the previous pass.
    [0022] In a variant, the passages are arranged so that the section of the corroded surface during a passage is smaller than the corroded section during the previous passage.
    [0023] As a variant, a part of the passages is ordered so that the section of the corroded surface during one pass is greater than the section corroded during the previous pass and another part of the passages is ordered so that the section of the corroded surface during one pass is less than the corroded section during the previous pass.
    [0024] Preferably, with the aid of an adapted suction medium, the metal vapor given off by the application of the light brush on the metal surface is aspirated.
    [0025] The description that follows is based on figures 1 to 9 in which: - figure 1 represents a schematic view of the surface of a pattern comprising filaments, - figure 2 represents a schematic view of the surface of a pattern comprising blades, - figure 3 shows how to calculate the average roughness of a surface, - figure 4 represents a photograph taken with the help of an electron microscope of a pattern comprising filaments, - figure 5 represents a photograph taken with the help of a electron microscope of the top of a cavity made with the aid of a process according to the invention, - figure 6 represents a photograph taken with the help of an electron microscope of the bottom of a cavity made with the help of a process according to the invention, - figures 7, 8 and 9 represent schematic illustrations of the way of ordering the passages with respect to each other to obtain more contrast effects or less intense.
    [0026] Figure 1 represents a portion of vehicle tire 1 whose visible surface of 11 comprises a pattern 2. This pattern consists of a multiplicity of filaments 21 of a height h, and whose middle section has a diameter d. To obtain a noticeable contrast effect, as explained in publication WO 2006/009980, the diameter d of the middle section of a filament must be between 0.03 mm and 0.5 mm, and the density of filaments must be greater than five filaments per mm2 and preferably greater than fifteen filaments per mm2.
    [0027] The height h is preferably greater than 0.1 mm. The height of the filament is measured between the base of the filament, in contact with the surface 11 of the tire, and the top of the filament. It is observed, however, that when the h / d ratio between the height of the filament and the diameter of the middle section is very low, the upper part of the filaments tends to bend, which has the consequence of reducing the contrast effect wanted. Therefore, an h / d ratio between 1.2 and 6 and preferably between 2 and 4 is chosen.
    [0028] The general shape of the filaments generally tapered, the section of said filaments decreases when moving from the base to the top. Therefore, the mean section means the average of the sections measured at regular intervals from the base to the top of the filament.
    [0029] The pattern 2 represented in figure 2 comprises in it a plurality of blades 22, of height h and of medium width d. In a similar way to what was exposed above, the sought contrast effects are obtained with corresponding dimensions namely, a value of the average width d at least equal to 0.1 mm and a density, here described by a step of value p that must be less than 0.5 mm and preferably less than 0.2 mm.
    [0030] For the same reasons as for filaments, it is arranged so that the h / d ratio is between 1.2 and 6, and preferably between 2 and 4.
    [0031] According to the invention, it is advisable that at least a quarter of the outer surface of the filament or the blade, namely, the surface between the base and the top of the filament 21 or the blade 22, has a surface state whose surface average roughness Rz is between 5 pm and 30 pm.
    [0032] To calculate the average roughness Rz of a surface, cut out a given length of the surface to evaluate said evaluation length Ln, in n lengths of bases Lz of identical lengths, as illustrated in figure 3. On each of the base lengths, an individual profile height Rz is determined, which is the sum of the largest of the projecting heights and the largest of the depths of the surface profile within the base length Lz. The average height Rz is the arithmetic mean of the individual values Rz, over the set of the considered base lengths (DIN 4768; 1990), and is expressed by the following formula:

    [0033] The limits of 5 pm and 30 pm are limits established experimentally. The lower value being the value below which the surface of the filament or the blade is considered to become "smooth" and will therefore reflect the incident light which is then no longer trapped in the network formed by the filaments.
    [0034] The upper limit is given as an indication and corresponds, considering the dimensions of the filament, to the acceptable limit to avoid extractions of the filament when demoulding. This higher value, which corresponds to a maximum efficiency of the light capture phenomenon, can be obtained in a favorable way when the average section of the filaments or the width of the blades is increased, observing that the increase of this value has the consequence of decrease in the density of filaments per unit area and, therefore, a decrease in the contrast effect.
    [0035] Figure 4 is a photograph obtained with the help of an electron microscope of the surface of a vehicle tire comprising a pattern comprising filaments 21. It is observed that the base of filament 210 has a large roughness, while the upper part 220 it's smoother.
    [0036] Note also about this view of the filaments whose top is curved due to an h / d ratio close to the recommended upper limit.
    [0037] The obtaining of patterns comprising a plurality of filaments is done by molding, having, for this purpose, a baking mold on which patterns appear which seek to increase the contrast.
    [0038] The process according to the invention provides for the use of a laser light source whose power is sufficient to liquefy and sublimate the metal constituting the mold. As an example, an IPG brand laser with a power of 50W, of the recording laser type, with pulses, allowed to obtain successfully the experimental results presented in figures 4, 5 and 6 of the present description. The pulse frequency, in the order of 100 kHz, as well as the power, can be adapted to modulate the amount of energy transmitted to the mold surface in each pulse.
    [0039] As mentioned above, the luminous brush emanating from the laser source is applied to the surface of the mold in successive passes, each pass having the effect of corroding the metal on a given surface and depth.
    [0040] During a passage, it is available to communicate to the metal a thermal energy per unit of surface in a sufficiently short time, so that the melting and sublimation of the metal by the luminous ray has the effect of projecting the liquid metal and condensate the metal vapors on the cavity walls obtained during the previous passages.
    [0041] For this, the width of the luminous brush and the scanning speed are adapted.
    [0042] Thus, for a 50 W laser, the width of the luminous brush is around 70 pm. It should be noted, however, that more than 70% of the energy is concentrated in the central part of the beam, and that this value can be optimized according to the regulation of the sending optics used to guide the laser beam towards the chosen impact point on the mold surface. It follows that the useful surface of the light beam is approximately between 0.001 mm2 and 0.01 mm2
    [0043] The frequency of impacts is 100 kHz, that is, an impulse in all 10 ps. The duration of the pulse itself can be even shorter depending on the type of pulse laser like lasers currently used in the laser engraving or cutting industry.
    [0044] The increase in depth of the cavity obtained after each pass, and corresponding to the amount of metal removed, is relatively low, and remains between 0.1 mm and 0.20 mm, since the evacuation of the material is done essentially by evacuating the vapors produced.
    [0045] It is therefore necessary to provide a means of aspiration of gases in order to avoid pollution of the working environment.
    [0046] However, it is advisable not to regulate the suction power as much as possible in this type of installation, so as not to extract by forced ventilation the totality of the produced vapors, which would have the effect of reducing the amplitude of the phenomenon sought for re-condensation of metallic vapor on the cavity walls. Although they do not meet the imposed hygiene and safety standards in industrial environments, tests carried out without forced local ventilation placed in the immediate vicinity of the point of impact nevertheless presented satisfactory results.
    [0047] Figures 5 and 6 are photographs taken with the help of an electron microscope of a cavity 3, intended to mold a filament 21. It can be seen in figure 5 that the wall 310 of the cavity located in the vicinity of the opening part of the said cavity (designed to mold the base 210 of filament 21) has a high roughness. Figure 6 and the magnification arranged in a medallion shape represent a view of the bottom 320 of the cavity 3 intended to mold the top 220 of the filament. In this area, the surface of the cavity wall is much smoother. This is explained by the fact that the parts of the cavity made last are less subject to the projection of nodules and to the condensation of the vapors produced during the previous successive passages, and therefore do not have the necessary roughness.
    [0048] It is then possible to remove part of this phenomenon in order to modulate the distribution of the zones presenting the desired roughness on the surface of the filament or the blade by modulating the section of the corroded surface in each passage as shown schematically in figures 7, 8 and 9 .
    [0049] Figure 7 illustrates the case in which, during the first pass (A), the surface of the pattern corrodes over its largest section, corresponding to the section of the base of the filament, which is represented by a cut ( light colored). The next passage (B) makes it possible to excavate the cavity over a smaller section (light gray color), and so in sequence considering that the last passage (E) is made over the smaller section corresponding roughly to the part of the cavity intended to shape the top of the filament.
    [0050] Figure 8 corresponds to the inverse case in which the first passage (A) is made over the smaller section, the second passage (B) refers to an upper section, so that in each passage the section of the cavity over the whole of its depth.
    [0051] Figure 9 represents the situation in which the two preceding operating modes are combined, starting with a first passage (A) of medium section. The second (B) and third (C) pass are made by expanding the section of the previous passages, and the last two passages (D and E) are made by removing the material over successively smaller sections.
    [0052] The effect of these different operating modes is to vary the preferential zones with surfaces whose roughness is within the values sought on the one hand, and to vary the size of said roughnesses, on the other hand.
    [0053] In the case illustrated in figure 7, large roughnesses are obtained in the base area. Preferably, it was observed that this configuration corresponds to the maximum light capture and, therefore, to the maximum black density. Also, preferably, it is arranged so that the surface of the lower quarter of the filament height has the claimed roughness.
    [0054] In the case illustrated in figure 8, an average or even low roughness divided over the whole filament surface will be obtained. Finally, in the case illustrated in figure 9, a roughness will be obtained divided over the entire filament surface, but more marked on the side of the base.
    [0055] This operational mode is applicable mutatis mutandis, and with the same effects, for the realization of the blades.
    [0056] Although the process in several passages seems preferable to obtain the sought effects, it is not unreasonable to think, given the increase in the power of lasers accessible at industrially reasonable prices, and the concentration of light beams linked to the progress of industrial optics, that is possible in the near future to carry out the cavities in a single pass of the laser beam. The teachings of the present description would then be applicable in the same way.
    [0057] Finally, and to conclude, it was highlighted that the presence of a high roughness at the base of the filament or the blade, has a favorable effect for the evacuation of the occluded air in the cavity when molding the filaments.
    权利要求:
    Claims (8)
    [0001]
    1. Vehicle tire (1) having a visible surface (11) comprising patterns (2) contrasting with said surface (11), said pattern (2) comprising, over the entire surface, a plurality of filaments ( 21) with a density of at least five filaments per mm2 or a plurality of blades (22) that are parallel to each other and arranged with a pitch (p) of less than 0.5 mm, each filament having a cross section having a diameter (d) between 0.03 mm and 0.5 mm or each blade having a width (d) between 0.03 mm and 0.5 mm, characterized by the fact that the walls of the filaments (21) or the blades (22 ) have, on at least a quarter of its surface, a roughness Rz between 5 pm and 30 pm.
    [0002]
    2. Vehicle tire according to claim 1, characterized by the fact that the filament wall having said roughness is located in the lower quarter of the filament height.
    [0003]
    Vehicle tire according to claim 1, characterized in that said filaments (21) or said blades (22) have a height of at least 0.1 mm.
    [0004]
    4. Vehicle tire according to claim 1, characterized by the fact that said filaments (21) or said blades (22) have a cross section that decreases from the base of the filament or the blade towards the end of the filament or of the blade.
    [0005]
    5. Vehicle tire according to claim 1, characterized by the fact that the relationship between the height (h) of the filament (21) or the blade (22) to the diameter (d) of a cross section of the filament (21 ) or the width (d) of the blade (22) is between 1.2 and 6.
    [0006]
    6. Vehicle tire according to claim 1, characterized by the fact that the relationship between the height (h) of the filament (21) or the blade (22) to the diameter (d) of a cross section of the filament (21 ) or the width (d) of the blade (22) is between 2 and 4.
    [0007]
    7. Vehicle tire according to claim 1, characterized by the fact that the density of the filaments is less than fifteen filaments per mm2.
    [0008]
    8. Vehicle tire according to claim 1, characterized by the fact that the tread (p) of the blades is less than 0.2 mm.
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    法律状态:
    2018-02-06| B25A| Requested transfer of rights approved|Owner name: MICHELIN RECHERCHE ET TECHNIQUE S.A. (FR) , COMPAG |
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-12-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-05-19| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-07-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/09/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0956675|2009-09-28|
    FR0956675A|FR2950566B1|2009-09-28|2009-09-28|HIGH CONTRAST PNEUMATIC PATTERN AND METHOD OF OBTAINING|
    PCT/EP2010/063212|WO2011036061A1|2009-09-28|2010-09-09|High-contrast tire pattern and method for producing same|
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