Patent Publication Number: US-11019875-B2

Title: Boot with an element in shell form

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of U.S. patent application Ser. No. 13/978,651 filed Jul. 8, 2013, now U.S. Pat. No. 9,949,528 which is the U.S. national phase of International Application No. PCT/AT2012/000003 filed Jan. 5, 2012, which claims priority from Austrian Patent Application No. A 23/2011 filed Jan. 7, 2011. The disclosures of these applications are incorporated herein in their entirety by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     The present invention relates to a ski boot, particularly an alpine or cross-country ski boot having an element in shell form which at least partially consists of a plastics compound material, and to a method for production of such element. 
     Boots having at least one element in shell form, i.e. particularly ski boots for alpine skiing and cross-country ski boots, are well known; in the context of the present invention, an “element in shell form” means any element covering at least part of the foot or lower leg. 
     The material for such relatively rigid elements of such boots, which are usually produced by injection molding, is usually thermoplastic elastomers. In the past two decades, particularly two groups of material have evolved which are preferably used particularly for boots in the field of professional sports. 
     One group is thermoplastic polyurethanes, both based on polyester polyol and on polyether polyol. Such materials comprise rigid segments, which are made of isocyanates in the case of polyurethane, and soft components, which are usually made of polyester polyol or polyether polyol. Such materials basically have good cold elastic properties and may be produced to have various degrees of stiffness or rigidity; however, they have two particular disadvantages. 
     The first disadvantage is that they have a relatively poor rigidity temperature behavior in the range of +20° C. to −20° C., i.e. the temperature range in which boots for alpine and cross-country skiing are usually used. In other words, these materials usually stiffen by about 400% in this temperature range. Consequently, the user will have boots having very different rigidity depending on the temperature. This is particularly disadvantageous because the future user will usually try on the boots at a sports outfitter&#39;s shop where the room temperature is usually about 20° C. In the shop the boots feel comfortable and soft. Later, however, when the boots are used for skiing, which is usually done at a temperature below freezing, the boots will be clearly more rigid, and the user will often feel uncomfortable. The second disadvantage is that for such boots having elements in shell form made of injection molded polyurethane a temperature of &gt;165° C. is needed to adapt the elements to the user&#39;s foot by means of thermoforming under vacuum or pressure. However, such temperatures are not acceptable for adapting the elements in shell form directly to the human foot. Moreover, such high temperatures result in oxidative molecular decomposition under the influence of air oxygen, i.e. the material properties such as rigidity and flexibility will change. 
     The second group of materials used for producing boot elements in shell form is polyamide elastomers, which are particularly known under the brand names Pebax or Vestamid. In such materials, the rigid segments are usually made of PA 11 (11-amino undecanoic acid) or PA 12 (laurin lactam or omega-amino decanoic acid). The soft segment is usually made of polyether. Compared to the thermoplastic polyurethanes mentioned above, polyamide elastomers have the advantage that their rigidity in the temperature range of +20° C. to −20° C. only changes by about 200%, compared to thermoplastic polyurethanes. 
     However, such polyamide materials have the disadvantage that they are not thermoformable in a temperature range of up to about 100° C., i.e. in a range acceptable to the human foot when using an inner boot between the foot or leg and the shell. 
     A boot partly made of a plastics compound material is e.g. described in US 2008/000109 A1. This document relates to a boot having elements in shell form made of polyurethane or polypropylene in a well-known manner with caprolactam based polymer admixtures in certain areas. In other words, this document discloses a polyurethane or polypropylene caprolactam compound material. This yields a shell being relatively rigid in some sections and having a softening temperature of &gt;170° C., while in the areas made of said plastics compound material a softening temperature of below 100° C. is supposed to be achievable. However, the disadvantage of such a boot is that its production is rather complex and costly because the boot necessarily comprises different material zones. 
     US 2004/0235586 A1 teaches cast plastics parts such as e.g. heel or toe caps for shoes or boots, which parts are made of compound material comprising a mixture of thermoplastic elastomers, thermoplastic ionomers, thermoplastic polyurethane and duroplastic, organic fiber-modified polyurethane. This is supposed to particularly improve rigidity and abrasion resistance of the cast plastics parts. 
     Similarly, US 2005/056669 A1 teaches plastics parts e.g. for heel or toe caps or soles, which parts are made of a mixture of ionomeric copolymers and organic acids or salts thereof, yielding high rigidity and high resilience. 
     Further, US 2008/0000109 A1 discloses an alpine ski boot having a rigid shell made of plastics material having a softening temperature above 170° C. In addition, caprolactam polyamide is added to at least one section of the shell base material in order to reduce the softening temperature of the shell in this particular section to below 100° C. 
     BRIEF SUMMARY OF THE INVENTION 
     The aim of the present invention is to provide a ski boot, particularly an alpine or cross-country ski boot having at least one element in shell form made of compound material having satisfying rigidity properties in a temperature range between +20° C. and −20° C. and being thermoformable at a temperature of &lt;100° C.; and to provide a process for producing such elements. 
     According to the present invention, this aim is reached in that said compound material comprises a mixture of caprolactam polyamide and ionomers, so that cations and anions of the ionomers form ion bonds, with the elastic components of the compound material forming a physical network that is disruptable between 60° C. and 100° C., so that the element in shell form of the ski boot that at least partly consists of said compound material is thermoformable below 100° C. 
     In other words, in the compound material according to the present invention, caprolactam polyamide is used as the base material or rigid segment, and ionomers are added to this base material as soft segments. 
     It is particularly advantageous for the ionomers to be copolymerisates of ethylene with carboxylic acid, particularly acrylic acid, including metal ions, particularly zinc or sodium. Cations and anions of the ionomers will form ion bonds, which has the advantage that the elastic components will form a physical network, which—depending on what ionomer is actually used—can usually be disrupted between 60° C. and 100° C. Therefore, the material will be excellently thermoformable, but after cooling, said ion bonds will form again and the original material properties will be restored. Advantageously, ionomers are highly elastic and have a rigidity temperature behavior similar in range to polyamide elastomers, i.e. their rigidity increases by about 200% in a temperature range from +20° C. to −20° C. 
     Depending on the desired rigidity of the compound material, the weight ratio of the ionomers advantageously is at least 20%, preferably between 25 and 70%. In order to improve workability of the compound material in injection molding processes, an organic and/or inorganic crystallization accelerating agent is conveniently admixed, preferably at a weight ratio of 0.1 to 1%. Such crystallization accelerating agents, also known as nucleating agents, are particularly advantageous if the element in shell form is produced having varying wall thicknesses, e.g. ranging from 2 mm to 20 mm, as is often the case with hard shells of alpine ski boots, and the boot element in shell form is removed from its forming tool while it is still hot. In this process, problems may occur if no nucleating agent is added because caprolactam polyamide and the ionomer component have different crystallization properties. It has proven particularly advantageous to admix talc and/or a low molecular polyamide as the crystallization accelerating agent; in this case, it is particularly advantageous to provide a mixture of organic and inorganic crystallization accelerating agents as the crystallization accelerating agent. 
     Consequently, for producing an element in shell form, preferably by injection molding, it is advantageous to essentially provide a mixture of 30 to 45% by weight of caprolactam polyamide, 0.1 to 1% by weight of crystallization accelerating agent, and the balance of essentially 55 to 70% by weight of ionomers. 
     In order to maintain the plastic properties of the compound material at an as constant level as possible over a wide temperature range, it has proven advantageous to admix a thermoplastic rubber, particularly ethylene propylene monomer rubber (EPM) or ethylene propylene diene monomer rubber (EPDM). In this case, it is particularly advantageous to have a weight ratio of thermoplastic rubber of essentially 10 to 30%. 
     In this case, it is particularly preferable to essentially provide a mixture of 30 to 45% by weight of caprolactam polyamide, 0.1 to 1% by weight of crystallization accelerating agent, 20 to 30% by weight of thermoplastic rubber, and the balance of essentially 25 to 35% by weight of ionomers. 
     The process of the above mentioned type is characterized in that ionomers are admixed to a caprolactam polyamide and this compound material is subsequently molded in an injection molding process. Thus, the compound material making up at least part of the element in shell form to be molded has the advantage of having relatively constant rigidity properties over the relevant temperature range and a relatively low softening temperature for thermoforming. In addition, it is particularly advantageous in that the compound material containing caprolactam polyamide and ionomers is easily workable in injection molding processes, and therefore the elements in shell form required for the production of boots are easy to produce. 
     Said mixture of caprolactam polyamide and ionomers may be produced in a single-step process, particularly by mixing caprolactam polyamide and ionomer at a mixing ratio corresponding to the desired rigidity in a compounding extruder, yielding an injection molding granulate. 
     Ionomers may also be added to caprolactam polyamide in a two-step compounding process, wherein in a first step essentially 5 to 15% by weight are added and in a second step essentially 25 to 50% by weight are added, each with respect to the finished compound material. In this case, in the first process step the ionomers will be distributed particularly finely in the caprolactam polyamide, and this distribution is upheld during the second addition step due to secondary valence bonding forces. The polyamide is first melted in a so-called compounding step, and the additive, i.e. the ionomers are added. Subsequently, solid agglomerates are usually split, then the ionomers are coated with molten polyamide, and subsequently the components of the compound material are distributed evenly. Caprolactam polyamide is usually heated to about 220° to 240° C. for melting. 
     To compensate for the very different crystallization properties of caprolactam polyamide and the ionomer additive, a crystallization accelerating agent is advantageously added in a further compounding step. This will significantly improve workability in the injection molding process. Moreover, in order to maintain the elastic properties of the compound material as consistent as possible within a wide temperature range, thermoplastic rubber is advantageously added in a further compounding step. 
     Hereinafter, the invention will be explained in greater detail with reference to preferred embodiments. 
    
    
     
       BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING 
         FIG. 1  shows is side view of a hard shell alpine ski boot, and 
         FIG. 2  shows a side view of a cross-country ski boot. 
     
    
    
     DESCRIPTION OF THE INVENTION 
       FIG. 1  shows a hard shell alpine ski boot of conventional outside appearance having two elements  2  in shell form, namely a lower shell  3  essentially accommodating the foot, to which a swivel-mounted collar  3 ′ essentially accommodating the lower leg in the shin region is attached via hinge  4 . A soft, padded inner boot  4  is provided in both elements  2  in shell form. According to the present invention, said two elements  2  in shell form are made of plastic compound material with caprolactam polyamide (also known as PA 6) as the base material. Ionomers are added to this base material at a weight ratio of 55 to 70%. In addition, a nucleating agent or crystallization accelerating agent comprised of a mixture of talc and low molecular polyamide is added to this plastic compound mixture at a weight ratio of about 0.1 to 1%. 
     Furthermore, said plastic compound may include about 20 to 30% of thermoplastic rubber to maintain the rigidity factor of elements  2  in shell form at a low level, i.e. preferably between 150 and 200%, in the temperature range of +20° C. to −20° C., which is the relevant temperature range for alpine ski boots. If thermoplastic plastics material is added to the compound plastics material, the ionomer ratio will be correspondingly lower. 
     Making elements  2  in shell form of such a plastic compound material gives the additional advantage that said elements  2  in shell form may be adapted to the user&#39;s foot and lower leg while the user&#39;s foot and leg are in the boot, because the softening temperature of the plastic compound material according to the present invention is below 100° C., preferably about 80° C. Consequently, said elements  2  in shell form may be heated up to their softening temperature while the user is wearing the boot with the inner boot  4  between the shell and the foot or leg. Thus, said elements  2  in shell form may be individually adapted to the user&#39;s foot and lower leg. 
     The same applies to essentially all elements  2  in shell form of a cross-country ski boot  1  as shown in  FIG. 2 . In this case, particularly the sole  6  may be made of the plastic compound material described above. Furthermore, advantageously a heel cap  6 ′ is also made of the material described above and may optionally be formed integrally with sole  6 . In addition, a collar  7 , which is hinged to lower shell  6 ′ via hinge  4  similar to collar  3 ′, may also be made of the plastic compound material in order to achieve individual adaptation to the user&#39;s leg in a simple manner and at the same time ensure consistent rigidity properties as far as possible in the relevant temperature range.