• 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:
    The invention relates to a shoe (1) with a shell-shaped element (2), which consists at least partially of a plastic compound material, wherein the compound material comprises a mixture of caprolactam polyamide and ionomers and a process for its preparation.
    公开号:AT510545A4
    申请号:T23/2011
    申请日:2011-01-07
    公开日:2012-05-15
    发明作者:
    申请人:Fischer Sports Gmbh；
    IPC主号:
    专利说明:

    1
    The invention relates to a shoe with a cup-shaped element, which consists at least partially of a plastic compound material, and a method for producing such an element.
    Shoes with at least one cup-shaped element, i. especially ski boots for alpine skiing and cross-country skiing, are well known; Under a bowl-shaped element is understood in connection with the subject invention, each of the foot or the lower leg at least partially covering element.
    As a material for these relatively hard elements of such shoes, which are usually produced by injection molding, usually thermoplastic elastomers are used. Here, in turn, in the last two decades, in particular two groups of materials have emerged, which are preferably used in particular for shoes for the high-sports sector.
    On the one hand, these are thermoplastic polyurethanes both based on polyesterpolyol and on polyether polyol. Such materials consist of hard segments, which in the case of polyurethane are formed from isocyanates, and soft components, which are usually formed by polyester-polyol or polyether-polyol. Such materials basically have good cold-elastic properties and can also be produced in different hardnesses or stiffnesses; However, they have in particular two disadvantages.
    First, it is particularly disadvantageous that the rigidity temperature behavior is in the range of + 20 ° C to -20 ° C, i. the temperature range in which alpine and cross-country boots are commonly used is relatively poor, i. that these materials tend to stiffen in this area by about 400%. Consequently, for the user results in a very different stiffness of the shoe depending on the particular temperature. In particular, this is disadvantageous in that the later user, who usually first tries on the shoe as a customer in a sports shop, in which 2 * · · ♦ ·· # ·· * ······ · · · · ··· It usually has room temperature of about 20 ° C; Here, the shoe feels comfortable and soft, with later use of the shoe as part of the skiing, which is usually carried out at minus temperatures, the shoe is then however much stiffer, which is often perceived by the user as unpleasant. In addition, in such shoes having injection-molded cup-shaped elements made of polyurethane, it is disadvantageous that temperatures of> 165 ° C are required to adapt the elements to the foot of the user in order to thermoform the material by means of vacuum or pressure. However, such temperatures are unacceptable to conform the bowl-shaped elements directly to the human foot. Furthermore, oxidative molecular degradation occurs at such high temperatures under the influence of atmospheric oxygen, i. The material properties such as stiffness and elasticity change.
    The second group of materials used to make shell-shaped elements of shoes are polyamide elastomers, which are known, in particular, under the brand names Pebax or Vestamid. In such materials, the hard segments usually consist of PA 11 (11-aminoundecanoic acid) or PA 12 {laurolactam or omega-aminodecanoic acid). As a soft segment usually polyether is used. The advantage of the polyamide elastomers over the thermoplastic polyurethanes described above is that the material stiffness in the temperature range of + 20 ° C to -20 ° C - compared to thermoplastic polyurethanes - changes only by about 200%.
    However, a disadvantage of these polyamide materials is that they are in a temperature range which is within a reasonable range for the human foot using an intermediate liner, i. up to approx. 100 ° C, are not thermoformable.
    A shoe which partly consists of a plastic compound material is described, for example, in US 2008/000109 A1. Here, a shoe is shown, in which shell-shaped elements in a known manner of polyurethane or polypropylene, which may be admixed in areas a caprolactam-based polymer; i.e. There are disclosed a polyurethane or poly-propylene-caprolactam compound material. In this way, a shell is achieved, which is comparatively stiff in sections and has a softening temperature of> 170 ° C, wherein in those areas in which the plastic compound material is provided, a softening temperature of less than 100 ° C is to be achieved. Such a structure of a shoe, which necessarily has different material zones, however, is disadvantageously expensive.
    The aim of the present invention is therefore to provide a shoe, in particular an alpine or cross-country ski, with at least one shell-shaped element made of a compound material which has sufficient rigidity properties in a temperature range between + 20 ° C and -20 ° C and also in Temperatures of <100 ° C is thermoformable; Furthermore, a method for producing such elements is to be created.
    According to the invention this is achieved in that the compound material comprises a mixture of caprolactam polyamide and ionomers. Accordingly, caprolactam polyamide is used as the base material or hard segment in the compound material according to the invention, and ionomers are added to this base material as a soft segment.
    In this case, it is particularly advantageous if, as ionomers, copolymers of ethylene with carboxylic acid, in particular acrylic acid, comprising metal ions, in particular zinc or sodium, are provided. Cations and anions of the ionomers then form ionic bonds, which has the advantage that the elastic components form a physical network which, depending on which ionomer is actually used, can usually be dissolved between 60 ° C. and 100 ° C., so that the Material is excellent thermoformable, but after cooling, the ionic bonds form again and thus the original material property is restored. Ionomers have the advantage of being highly elastic and having a stiffness temperature response on a similar order to polyamide elastomers, i. they stiffen in the temperature range of + 20 ° C to -20 ° C by about 200%.
    Depending on the desired stiffness of the compound material, it is advantageous if the proportion by weight of the ionomers is at least 20%, preferably between 25 and 70%.
    In order to improve the processability of the compound material by injection molding, it is advantageous if an organic and / or inorganic crystallization accelerator, preferably mixed with a weight fraction of 0.1 to 1%. Such crystallization accelerators, also called nucleating agents, are particularly advantageous when a bowl-shaped element with different wall thicknesses, e.g. in the order of 2mm to 20mm, as is often the case with hardshells of alpine ski boots, while the shell-shaped element of the shoe is forcedly demolded by a tool bar when warm. In this case, problems can occur without incorporation of a nucleating agent due to the different crystallization properties of the caprolactam polyamide compared with the ionomer fraction. As particularly advantageous has been found when talc and / or a low molecular weight polyamide is mixed as crystallization accelerating agent, in which case it is in turn particularly favorable when a mixture of organic and inorganic crystallization accelerating agent is provided as a crystallization accelerator.
    In order to produce a cup-shaped element, preferably by injection molding, it is therefore advantageous if essentially a mixture of 30 to 45% by weight of caprolactam polyamide, 0.1 to 1% by weight of crystallization accelerator and a radical of essentially 55 to 70% by weight. % Ionomers is provided.
    To obtain as far as possible constant plastic properties of the compound material over a wide temperature range, it has been shown that it is favorable when a thermoplastic rubber, in particular ethylene-propylene rubber (EPM) or ethylene-propylene-diene rubber (EPDM ) is mixed. Here, it is particularly advantageous if the proportion by weight of the thermoplastic rubber is substantially 10 to 5 &gt; ·· * * * • · »30%.
    Particularly preferred here is that essentially a mixture of 30 to 45% by weight of caprolactam polyamide, 0.1 to 1% by weight of crystallization accelerator, 20 to 30% by weight of thermoplastic rubber, and a radical of essentially 25 to 35% by weight -% ionomers is provided.
    The method of the initially mentioned kind is characterized in that a caprolactam polyamide ionomers are added and then the compound material is molded by injection molding. The compound material from which the shell-shaped element to be produced at least partially thus not only has the advantage of relatively equal rigidity properties in the relevant temperature range and a comparatively low softening temperature for the purpose of hot deformation, but in particular it is advantageous that the compound material, the caprolactam polyamide and ionomers, is easily processable by injection molding and, consequently, the cup-shaped elements required for the manufacture of shoes can be produced in a simple manner.
    The mixture of caprolactam polyamide and ionomers can be prepared in a one-step process, in particular by admixing caprolactam polyamide with the ionomer in a compounding ratio corresponding to the desired stiffness in a compounding extruder, thus producing an injection molding granulate.
    When the caprolactam polyamide is admixed with the ionomers in a two-stage compounding process, wherein essentially 5 to 15% by weight are mixed in a first step, and in a second step essentially 25 to 50% by weight, based in each case on the finished compound Material are mixed, it is achieved in particular that in the first process step, the ionomers are particularly finely divided in the caprolactam polyamide, this distribution being maintained due to Nebenvalenzbindungskräften in the second admixture. By means of so-called compounding, the polyamide is first melted and the additive, i. the ionomers, ΦΦ * * ΦΦ · Μ 6 • Φ ······································································. then solid agglomerates are usually cut, then the ionomers are wetted with polyamide melt and subsequently the components of the compound material are evenly distributed. To melt the caprolactam polyamide this is usually heated to about 220 ° to 240 ° C.
    To compensate for the very different crystallization properties of caprolactam polyamide and the ionomer additive, it is advantageous if a crystallization accelerator is added in a further compounding step. This results in a significantly improved processability in injection molding. Moreover, in order to keep the elastic properties of the compound material as stable as possible over a wide temperature range, it is furthermore favorable if thermoplastic rubber is added in a further compounding step.
    The invention will be explained in more detail with reference to preferred embodiments. In detail, in the drawings
    Fig. 1 is a side view of a hard shell alpine ski boot, and
    Fig. 2 is a side view of a cross-country boot.
    FIG. 1 shows an alpine hard-shell shoe with two shell-shaped elements 2 which is conventional in terms of its external appearance and in which a bottom shell 3 which essentially accommodates the foot is provided, on which a collar 3 'accommodating essentially the lower leg in the region of the tibia is inserted Joint 4 is pivotally mounted. In the two shell-shaped elements 2, a soft, padded liner 4 is added. The two shell-shaped elements 2 in this case according to the invention consist of a plastic compound material in which caprolactam polyamide {also called PA 6) is provided as the base material. This base material is mixed ionomers with a weight fraction of 55 to 70%. Furthermore, the plastic-compound mixture is a nucleating or crystallization accelerating agent which consists of a mixture of talc and low molecular weight polyamide mixed with a proportion by weight of about 0.1 to 1%.
    Furthermore, the compound plastic may have a proportion of thermoplastic rubber of about 20 to 30% in order to minimize the stiffening factor of the shell-shaped elements 2 in the temperature range of + 20 ° C to -20 ° C relevant for the application of the alpine ski boot. preferably between 150 and 200%. If thermoplastic material is added to the compound plastic, the proportion of ionomers decreases accordingly.
    With the help of the formation of the shell-shaped elements 2 made of such a plastic compound material can also be done advantageously an adaptation of the cup-shaped elements 2 to the foot or the lower leg of the user in the attracted state, since the softening temperature of the plastic compound material according to the invention below 100 ° C, preferably about 80 ° C, is. Accordingly, the shell-shaped elements 2 can be heated to their softening temperature, while the user wears the shoe with the interposition of the inner shoe 4 and thus an individual adaptation of the shell-shaped elements 2 to the foot or the lower leg of the user.
    The same applies essentially to all shell-shaped elements 2 of a cross-country boot 1 shown in FIG. 2, wherein in particular the sole 6 may consist of the above-described plastic compound material. Furthermore, however, is also advantageous that a heel cap 6 ', which may optionally also be formed integrally with the sole 6, may consist of the material described above. In addition, a sleeve 7, which is similar to the sleeve 3 'hinged to the lower shell 6' via a hinge 4, made of the plastic compound material in order to easily achieve an individual adaptation to the leg of the user and at the same time, however, in the relevant temperature range to ensure as constant as possible stiffness properties.
    权利要求:
    Claims (14)
    [1]
    ································································································································································································································ (1) with a shell-shaped element (2), which consists at least partially of a plastic compound material / characterized in that / the compound material comprises a mixture of caprolactam polyamide and ionomers.
    [2]
    2. Shoe according to claim 1, characterized in that / are provided as ionomers copolymers of ethylene with carboxylic acid, in particular acrylic acid, comprising metal ions, in particular zinc or sodium.
    [3]
    3. Shoe according to claim 1 or 2, characterized in that the weight fraction of the ionomers is at least 20%, preferably between 25 and 70%.
    [4]
    4. Shoe according to one of claims 1 to 3, characterized in that an organic and / or inorganic crystallization accelerating agent, preferably in a proportion by weight of 0.1 to 1%, is admixed.
    [5]
    5. Shoe according to claim 4, characterized in that as crystallization accelerating agent talc and / or a low molecular weight polyamide is mixed.
    [6]
    6. Shoe according to claim 4 or 5, characterized in that a mixture of organic and inorganic crystallization accelerating agent is provided as a crystallization accelerator.
    [7]
    7. Shoe according to one of claims 1 to 6, characterized by a mixture consisting essentially of: 30 to 45% by weight of caprolactam polyamide, 0.1 to 1% by weight of crystallization accelerator and a balance of substantially 55 to 70% by weight % Ionomers.
    [8]
    8. Shoe according to one of claims 1 to 6, characterized in that a thermoplastic rubber, in particular ethylene-propylene rubber (EPM) or ethylene-propylene-diene rubber 9 (EPDM), is admixed.
    [9]
    9. Shoe according to claim 8, characterized in that the weight proportion of the thermoplastic rubber is substantially 10 to 30%.
    [10]
    10. Shoe according to one of claims 1 to 6, 8 or 9, characterized by a mixture consisting essentially of: 30 to 45% by weight caprolactam polyamide, 0.1 to 1% by weight crystallization accelerator, 20 to 30% by weight thermoplastic rubber, and a balance of substantially 25 to 35% by weight ionomers.
    [11]
    11. A method for producing an element (2) for a shoe (1) according to any one of claims 1 to 10, characterized in that a caprolactam polyamide ionomers are added and then the compound material is injection molded.
    [12]
    12. The method according to claim 11, characterized in that the caprolactam polyamide, the ionomers are mixed in a two-stage compounding process, wherein in a first step substantially 5 to 15% by weight are mixed, and in a second step substantially 25 to 50th % By weight, based in each case on the finished compound material.
    [13]
    13. The method according to claim 11 or 12, characterized in that in a further compounding step, a crystallization accelerator is admixed.
    [14]
    14. The method according to any one of claims 11 to 13, characterized in that in a further compounding step thermoplastic rubber is mixed. / RB
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    引用文献:
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    US20040235586A1|2003-05-21|2004-11-25|Chen John Chu|Articles prepared from compositions modified with organic fiber micropulp|
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    法律状态:
    优先权:
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