KR930000830B1 - Snow ski soles - Google Patents

Abstract

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Description

Sliding surface of object

The present invention relates to a ski sole that contacts the snow as a lower part of the ski and supports the ski and the skier.

The ski window according to the present invention is excellent in its ability to absorb and retain waxes.

The ski window is usually in the form of a sheet or film having a thickness in the range of 0.5 to 2 mm. The material is a polyolefin-based plastic material and is preferably based on high density polyethylene (HDPE), which may be selected from those having a high molecular weight (range of 150,000 to 450,000 number average molecular weight) measurable by gel-to-chromatography and chromatography.

This type of window is manufactured by conventional extruders. Until now, properties such as impact resistance, dye affinity, and the ability to absorb waxes (paraffinic analogous fatty substances) have far exceeded or inadequately met the requirements for the ski window.

For this reason, attempts have been made to modify the properties of polyethylene by incorporating additives or treating them with agents that enhance the porosity of HDPE to improve specific properties for skid windows.

U.S. Patent Publication No. 3,075,948 discloses the grafting of polyolefins (and especially polyethylene) with silanes.

Prior to extrusion in French Patent Publication No. 2,478,877, it has been proposed to modify the sliding surface by incorporating a substance dissolved in a non-aqueous liquid into HDPE and then converting it into a sheet or film.

Very high molecular weight HDPE (with a number average molecular weight in the range of 300,000 to 8,000,000) is also used in the manufacture of top sport ski windows. These windows are manufactured by the sintering method, which is very different from extrusion.

In Austrian Federal Patent Publication No. 332,273 a method for producing a ski window from sintered HDPE is disclosed.

The skid window of the present invention consists of a sheet or film of thermoplastic polymeric material based on a homogeneous mixture of one or more polyolefins and one or more polyetheresteramides. The properties of this type of ski window are especially:

-Excellent ability to absorb waxes and retain them in a continuous manner.

-Very light sliding due to low coefficient of friction.

-Excellent resistance to shock and abrasion

-Very suitable for glueing ski blades.

-Excellent anti-static at low temperature and dye affinity.

-Transparency or translucency (the screen can be masked by various prints such as designs, trademarks, etc.) to the extent that ski blades are clearly visible through the window.

As described above, the skid window according to the present invention consists of a thermoplastic polymer material based on one or more polyolefins and one or more polyetheresteramides thereof, and may contain various additives, fillers and the like. have.

The polyetheresteramides mean not only random polyetheresteramides (which are formed by random chaining reactions from various monomer components) but also block polyetheresteramides formed in the form of a mole of various components having a characteristic chain length. Of course.

Polyetheresteramides are the product of the condensation copolymerization reaction of the polyamide sequence which has a reactive terminal, the polyether sequence which has a reactive terminal, especially the polyamide sequence which has a dicarboxyl chain terminal, and a polyetherdiol sequence.

Examples of this kind of product are disclosed in French Patents Nos. 74 18913 and 77 26678, the contents of which are added to this specification.

The number average molecular weight of these polyamide sequences is usually in the range of 500 to 10,000 and more specifically in the range of 600 to 5,000. Polyamide sequences of polyetheresteramides are from polyamide 6, 6.6, 6.12, 11 or 12 (PA-6, PA-6.6, PA-6.12, PA-11, PA-12) or condensation copolymerization of these monomers It is preferably formed from the amide copolymer obtained from the reaction.

The number average molecular weight of the polyethers is usually in the range of 200 to 6,00 and more specifically in the range of 600 to 3,000.

The polyether sequence preferably consists of polytetramethylene glycol (PTMG), polypropylene glycol (PPG) or polyethylene glycol (PEG).

The intrinsic viscosity of these polyether ester amides is advantageously in the range of 0.8 to 2.05.

Intrinsic viscosity is measured at an initial concentration of 0.5 g per 100 g of ketcresol in 20 ° C. methacresol. The unit is represented by dlg ^-1 .

The polyetheresteramides according to the present invention comprise 5 to 85% by weight of polyether, 95 to 15% by weight of polyamide, and preferably 30 to 80% by weight of polyether and 70 to 20% by weight of polyamide. Can be formed from

The polypyreline or polyolefins used in the present invention, the ski window, consist of polypropylene (PP), polyethylene (PE), mixtures or copolymers thereof, but preferably polyethylene.

According to a preferred embodiment of the invention, the polyolefin or polyolefins have a high molecular weight.

The horizontal group molecular weight of the preferred polyolefins is in the range of 100,000 to 500,000 and preferably in the range of 150,000 to 400,000.

The mixture of thermoplastic polymeric materials forming the skiwind of the present invention may contain from 50 to 99% by weight of polyolefin or polyolefins and from 50 to 1% by weight of polyetheresteramide or polyetheresteramides and preferably from 60 to 90 weight percent polyolefin (s) and 40 to 10 weight percent polyetheresteramide (s).

This mixture can contain, for example, up to 70% organic or inorganic fillers, which can be in the form of fibers or powder.

Similar mixtures are disclosed in French Patent Publication No. 2,519,012.

Examples of fillers include silica, titanium oxide, glass fibers and carbon fibers.

The mixture may also contain various additives such as UV stabilizers, release agents, impact modifiers, waxes and the like.

Emulsifiers may be additionally incorporated to enhance compatibility between the other components of the mixture.

For example, maleated polypropylene can be selected as an emulsifier. Generally, 1-5% by weight of an emulsifier is incorporated into the mixture brush.

Emulsifiers are not necessarily present. However, it is especially recommended when the proportion of polyetheresteramide in the mixture is 20% by weight or more.

The production of ski windows according to the invention and in particular the formation of sheets or films made from the abovementioned mixtures can be carried out by any known extrusion method. It is further necessary to form a homogeneous mixture of the aforementioned window components before actually extruding the mixture.

This can be done by forming a mechanical mixture of the window components before they are introduced into the hopper of the extruder.

It is also possible to mix the raw materials forming the homogeneous mixture described above (in powder or granule form) and then to treat the mixture in a molten state in a single screw or twin screw extruder or kneading or rolling apparatus. . Using this technique makes the mixture more homogeneous.

Once the window components are homogeneously mixed, it is possible to proceed with the actual extrusion. Any type of single screw or twin screw extruder may be used.

Preferred extruders are extrusion-coating or extrusion-horizontal rolling.

This yields a sheet or film of the mixture described above having a thickness in the range from 0.5 to 2 mm and preferably in the range from 0.9 to 1.4 mm.

Another embodiment of the method for producing a ski window according to the present invention consists in incorporating the whole or part of the wax into the mixture for making the window before extruding. By doing so a window is obtained which is somewhat self-waxing, ie the waxing of the skies is no longer necessary at the time of providing the ski windows.

The self-waxing technique has the following advantages.

-The window can inhale a large amount of wax.

-Waxes incorporated into the structure of the window are permanently retained in the structure and the skies are waxed only once.

The term wax refers to both slim waxes that are more characteristic of Kosanski and grip waxes that are more specifically used for cross-country skiing.

The main function of so-called slip waxes is generally to reduce the coefficient of friction of the window to a lesser extent, thereby improving the sliding of the window on the snow.

So-called grip waxes mainly function to prevent skies from slipping back. The crystals of the snow can penetrate the surface layer of the wax and thus give the window the fixation specificity necessary to prevent the skier from settling well on the snow and sliding the skier in the other direction desired.

Gluing the window on skier blades can be performed in a conventional manner. By way of example, this can be done by hot adhesion—heating the film or sheet and pressing it onto the skinals under pressure.

The present invention is based on one or more polyetheresteramides and one or more polyolefins of the type described above as sliding surfaces of objects which function to slide on liquid or solid surfaces such as water, snow, glass, etc. The same may be applied in a manner that is advantageous for the production and use of sheets or films.

Examples of this type of product are turbo gun sleds, sail boards and surfboards.

The following examples illustrate, but do not limit the invention.

EXAMPLE

A-component

The ski window composition consists of the following components by weight.

-High density polyethylene (HDPE) 90 parts

(Ethylene-butene copolymer containing 2-3% butene, = 150,000)

10 parts of polyether esteramide

( With a PA-12 sequence of = 600 Polyether (PTMG) = 2,000

Obtained by condensation copolymerization of sequences)

B-Application

1. Perform a process to obtain a granular mechanical mixture of the components described in A. The mixture thus obtained is fed into a single screw extruder having a screw speed of 100 r · p.m. In the extruder, the entire mixture is heated to a temperature in the range of 225 to 230 ° C. A continuous sheet of thickness 1.2 mm and butterfly 105 mm was obtained from the dioriphytes (sample 1).

For comparison, only HDPE is extruded under the same conditions to obtain a continuous sheet 1.2 mm thick and 105 mm butterfly (sample 2).

In order to determine sheet properties from Samples 1 and 2, the surface free energy γs of the surfaces of Samples 1 and 2 sheets is measured together with their two components γs ^d and γs ^p .

The surface free energy of a solid surface is the sum of component γs ^d (contribution to London dispersion) and component γs ^p (non-dispersion-contribution of polar and other forces).

γs = γs ^d + γs ^p

To determine these values, the contact angle θ produced by the droplets of standard liquid deposited on the leveled surfaces of samples 1 and 2 is measured.

Contact angle measurement is described in W.D WARKINS's paper (The Physical Chemisty of Surface Films, P41. Reinhold Pub. Corp 1952).

Contact angle measurements were performed at 25 ° C. on two sides of the sample continuously. Standard liquids used were:

Diiodomethane, α-bromonaphthalene (low polar liquid), water, formamide (polar liquid)

A drop of 1-5 μl of standard liquid is deposited on the leveled sheet surface.

Thirty seconds to two minutes after the droplets are deposited on the horizontal sheet surface, the contact angle θ made by Paul and the horizontal surface on which it is settled is measured.

After measuring the contact angle, γs ^d , γs ^p and γs are calculated using the method of W.RABEL (Parve amd Lack-77 Hahrg-No. 10-997-1006-1971). The results are shown in Table 1.

The units of γs ^d and γs ^p γs are represented by mN, .m ⁻¹ . The accuracy of the measurement is up to ± ¹ mN.m ^-1 .

No significant difference was found between the two sides of Samples 1 and 2.

The physical properties of sample 1 and 2 are very different. Sample 1 (a mixture of HDPE and polyetheresteramides) has a 39% greater surface free energy value than Sample 2 (HDPE alone). The polar force contribution for Sample 1 is 6.7 mN.m ⁻¹ , while it is 0 for Sample 2.

TABLE 1

Example 2

A-component

The window composition consists of the following components by weight:

-HDPE ( Propylene homopolymer with = 300,000) 80 parts

20 parts of polyether esteramide

( With the PA-12 sequence = 850 Polyether (PTMG) = 2,000

Obtained by condensation copolymerization of sequences)

B-Application

The composition described in A is mixed in a molten state in a ZSK 30 type twin screw WERNER PFLEIDERER extruder.

The temperature of the whole composition is raised to 230 ° C., and the rotation speed of the screw is 150 r.p.m and the output of the material is 17 kg / h.

The obtained granules were extruded under the same conditions as in Example 1 to obtain a continuous sheet of 1.2 mm in thickness and 105 mm in butterfly.

For comparison, only HDPE was extruded under the same conditions (the properties are described in 2.A) to obtain a continuous HDPE sheet 1.2 mm thick and 105 mm butterfly.

Sheets made in this manner are suitable for glueing on ski blades and skies made in this manner can undergo a waxing process.

Example 3

2 to 3 parts by weight of commercially available waxes are added to the mixture of HDPE and polyetheresteramide prepared in the molten state described in Example 2. The mixed material thus obtained is extruded under the same conditions as in 2, B.

So-called "self-waxing" continuous sheets are obtained, which can be glued on ski days.

Depending on the amount of wax introduced into the structure of the window as described above, subsequent waxing may not be necessary.

Claims (1)

A sliding surface for sliding an object on a liquid or solid surface consisting of a sheet or film of thermoplastic polymer material based on a homogeneous mixture of one or more polyolefins and one or more polyaryletheresteramides.