JP2013117016A5 - - Google Patents

Description

Eventually, with the development of synthetic resin technology, a sliding surface material made of polyethylene was created around 60 years ago. Polyethylene sliding surfaces have many advantages in terms of wear resistance, low friction, and long life compared to plastic sliding surfaces that have been attempted so far, and they are still considered to be the best material for sliding surfaces and are still used worldwide. However, the water repellency was not so high although it was highly waterproof. In addition, when sliding on a hard snow ice surface at high speed, the surface is scraped and worn to reduce the smoothness, and the frictional resistance also increases.

Next, with respect to a sliding movement tool used on ice such as skates, the sliding property on ice greatly depends on the smooth state of the edge portion on the bottom surface of the blade. However, metal blades are prone to rust. In addition, the bottom surface of the blade is easily worn by this frictional force because it slides on a hard ice surface in a state where the overall weight of the glider is concentrated on the blade. Since these rusts and wear affect the sliding performance of the skate, oil is applied to the blades after removing the water and anticipating a rust-preventing effect, and when the blades are worn, they are lost by polishing. The smoothness is restored.

3. The root of the pseudo liquid theory dates back 160 years. However, the theory that “the surface of the ice has a fine water film” was not accepted at that time, and for the next 100 years, it was not noticed in the shadow of the explanation of frictional heat fusion. However, an experiment by the late Professor Ukichiro Nakatani of the Institute of Low Temperature Science of Hokkaido University 60 years ago showed that a liquid layer really exists on the ice surface. Eventually, when surface analysis at the molecular level becomes possible, the trend of the pseudo liquid layer depending on the temperature on the ice surface will be observed in detail, and this pseudo liquid layer will reduce friction on snow and ice to reduce lubricant. It was confirmed that he played the role of Currently, 160 years after its proposal, research on various phenomena involving this pseudo liquid layer is underway.

This pseudo-liquid layer is said to exist even at temperatures as low as 100 ° C below freezing point, and in this, 2 .
It became possible to explain the fact that dog sledding can move even at low speed. However, it is well known that when the amount of water on the snow and ice surface, which is the basis of these fluid lubrication theories, exceeds a certain amount, the resistance to sliding movement on the snow and ice is reversed by the tension.

As described above, the popularity of skiing in Japan peaked around 1991-1993, but at that time, a technique for dramatically improving the sliding performance by dispersing a fluororesin as an additive in ski wax was established. It was. This is because the molecular surface of the fluororesin is covered with fluorine groups that have no affinity for water, and the microscopic interaction between the ski running surface and the snow / ice surface is hindered, resulting in complete water repellency. To be interpreted.

In addition to the fluororesin, many additives for ski wax have been tried. The main examples taken up to now are as follows. A: Fluororesin, PTFE, etc. (for example, Patent Document 1) B: Layered structure, MoS2, BN, etc. (for example, Patent Document 2) C: Soft metal, Ga, In, etc. (for example, Patent Document 3). ) D: photocatalyst, TiO2, etc. (for example, Patent Document 4) E: spherical particles, microsilica (for example, Patent Document 5) F: nanocarbon , C60, etc. (for example, Patent Document 6).

Japan Productivity Division, “Leisure White Paper 2010”, 165 pages, 2010.7. Productivity publishers [Ministry of the Environment, Press Release] Internet <URL: http://www.env.go.jp/press/press.php?serial=11117> [METI / Chemical Substance Management Policy] Internet <URL: http://www.meti.go.jp/policy/chemical_management/law/prtr/2.html> “Structure and properties of single-digit nanodiamond particles”, Eiji Osawa, Surface Science, 2009, 30, 258-266 “Chemistry of Single-Nano Diamond Particles,” Oosawa, E., in Wudl, F .; Nagase, S .; Akasaka, K. (Ed.), 'Chemistry of Nanocarbons,' Chapt. 17, pp. 413-432, John Wiley & Sons, Oxford, 2010. “Consequences of strong and diverse electrostatic potential field on the surface of detonation nanodiamond particles,” Oosawa, E .; Ho, D .; Huang, H .; Korobov, MV; Rozhkova, NNDiam. Rel. Mater. 2009, 18, 904- 909. “Cytotoxicity andgenotoxity of carbon nanomaterials”, Schrand, AM; Johnson, J .; Dai, L .; Hussain, SM; Schlager, JJ; Zhu, L .; Hong, Y .; Oosawa, E. in Safety of Nanoparticles: From to Medical Applications, Webster, TJ (Ed.), SpringerScience + Business Media, New York, 2008, Chapter 8, p. 159-188. Bowden, F. P.; Tabor, D. The friction and lubrication of solids. Oxford University Press, Oxford, 366. First edition published in 1950. “Number effects in nanoparticles,” Liu, WK et al., In Ho, D. (Ed.) 'Nanodiamonds: Applications in Biology and Nanoscale Medicine,' Chapter 12, pp. 253-255, SpringerScience + Business Media, Inc. , Norwell, MA., 2010 [ExxonMobil / SpectraSyn Plus] Internet <URL: http://www.exxonmobilchemical.com/Chem-English/brands/spectrasyn-plus-advanced-pao.aspx?ln=productsservices> [Kashiwax / KWX] Internet <URL: http://www.kashiwax.com/kwx/>

Japan Productivity Division, “Leisure White Paper 2010”, 165 pages, 2010.7. Productivity publishers [Ministry of the Environment, Press Release] Internet <URL: http://www.env.go.jp/press/press.php?serial=11117> [METI / Chemical Substance Management Policy] Internet <URL: http://www.meti.go.jp/policy/chemical_management/law/prtr/2.html> “Structure and properties of single-digit nanodiamond particles”, Eiji Osawa, Surface Science, 2009, 30, 258-266 “Chemistry of Single-Nano Diamond Particles,” Oosawa, E., in Wudl, F .; Nagase, S .; Akasaka, K. (Ed.), 'Chemistry of Nanocarbons,' Chapt. 17, pp. 413-432, John Wiley & Sons, Oxford, 2010. “Consequences of strong and diverse electrostatic potential field on the surface of detonation nanodiamond particles,” Oosawa, E .; Ho, D .; Huang, H .; Korobov, MV; Rozhkova, NNDiam. Rel. Mater. 2009, 18, 904- 909. “Cytotoxicity andgenotoxity of carbon nanomaterials”, Schrand, AM; Johnson, J .; Dai, L .; Hussain, SM; Schlager, JJ; Zhu, L .; Hong, Y .; Oosawa, E. in Safety of Nanoparticles: From to Medical Applications, Webster, TJ (Ed.), SpringerScience + Business Media, New York, 2008, Chapter 8, p. 159-188. Bowden, F. P.; Tabor, D. The friction and lubrication of solids. Oxford University Press, Oxford, 366. First edition published in 1950. “Number effects in nanoparticles,” Liu, WK et al., In Ho, D. (Ed.) 'Nanodiamonds: Applications in Biology and Nanoscale Medicine,' Chapter 12, pp. 253-255, SpringerScience + Business Media, Inc. , Norwell, MA., 2010 [ExxonMobil / SpectraSyn Plus] Internet <URL: http://www.exxonmobilchemical.com/Chem-English/brands/spectrasyn-plus-advanced-pao.aspx?ln=productsservices> [Kashiwax / KWX] Internet <URL: http://www.kashiwax.com/kwx/> [SWIX / catalog, P2-4] Internet <URL: http://www.swix.co.jp/pdf_catalog/12-13swix_pdf_catalog.htm> [TOKO / catalog] Internet <URL: http://www.tokowax.co.jp/index/index/category/wax> [GALLIUMWEB catalog, P3-7] Internet <URL: http://www.galliumwax.co.jp/catalog/2012snowboard/index.html>

However, in the ski wax products in the goods market, the content of fluororesin is now HF (high fluorine = meaning that high concentration of fluororesin), LF (low fluorine = meaning that low concentration is added) and NF (non-fluorine = same value) Since it is even a standard that represents the commercial value of ski wax, such as 100% hydrocarbon, the product that does not contain fluororesin is positioned as a low-cost, low-performance product called "NF". There is. Actually, the “NF” product did not replace the “NF” product in terms of sliding performance (see, for example, Non-Patent Document 12 and Non-Patent Document 13) .

For this reason, in the current goods market, commercial reasons are given priority over environmental issues and biohazards, and anyway, fluororesin is added to ski wax and the message “This product slips well because it contains fluorine” is displayed. The act of advertising to buyers is usually done. Especially in alpine competitions such as skiing and snowboarding, the use of “HF” products and fluororesin itself is regarded as a regular use for victory, which is a typical “necessary evil” (for example , non-patent literature). 14.)

Therefore, attempts have been made to mix additives in the sliding surface material in the same manner as the ski wax in order to obtain sufficient sliding properties without the wax being removed. And Key examples that are taken up to now, the above-described C: soft metal, Ga, In, etc., D: a photocatalyst, such as TiO2, E: spherical particles, Miku Roshirika, F: nanocarbon, such as C60, is ( (See paragraph 0026) . However, as these sliding surface additives, only graphite, which is a low-priced layered structure, currently penetrates the market, and there are no other successful attempts from the viewpoint of market penetration. .

Looking at the commercially available C (soft metal) mixed sliding surface material , the Ga (gallium) particles are unevenly distributed and are scattered three-dimensionally in the hard polyethylene sheet. Is only visible. In this case, only a part of the additive exposed on the surface layer can actually come into contact with the snow and ice surface, and a sufficient lubrication effect to replace waxing cannot be expected. Further, many of the blended additives remain buried under the surface layer of the sheet and are not used until the end of the tool life, so that there is a lot of waste in terms of production efficiency and cost.

Why graphite is penetrated into only the market is the raw material of the main planing surface material ultra-high molecular weight polyethylene (UHMWPE) is a thermoplastic resin also has an extremely high kinematic viscosity at its melting, standard screw The reason is that it is difficult to uniformly disperse the additive in the sliding surface material in any of the injection type and high pressure / high temperature molding type production methods . In view of this, since the raw material cost is low for graphite, this problem can be solved in a large amount by dealing with it .

The second issue, which seems to be an important issue unique to Japan, is to eliminate the unpleasant phenomenon that skiers and snowboarders and other leisure activities cannot handle, leading to the extension of the actual operating period for cableway and related operators. This new additive eliminates the “gripping snow” phenomenon in spring, and it is strongly demanded that the sliding effect can be continuously exerted even on snow and ice covered with yellow sand.

The third issue is essentially an inevitable issue as a tool used on snow and ice, but it is necessary to respond to unstable and suddenly changing weather, which is also a feature of snowy mountains, and to follow climate change from winter to spring. In addition, the new additive is not required to be based on the limited lubrication mechanism that depends on the current theory of snow and ice lubrication , but is also required to have a friction reduction mechanism based on the new snow and ice lubrication theory. It is done.

In order to satisfy these “four conditions”, it is necessary to use “twelve specific means” described below. These twelve specific means correspond to the problem solving means of the present invention.

Hereinafter, the characteristics of the configuration will be described for each claim. First, the basic composition of the lubricant composition according to claims 1 and 2 and the additive composed of nanodiamond particles as the center thereof are the most important features in the present invention, and as means for solving the problems of the present invention. The first of the above four conditions for the nano-sized "roller" action necessary to make nanodiamond particles function as "rollers" of water-soluble, high-hardness nanoparticles and to develop a new lubrication theory on snow and ice. This is the only method that can satisfy the two conditions of shape and number.

This new nanodiamond primary single crystal grains, the size dynamic light scattering method The volume average particle diameter as measured by (Dynamic light scattering = DLS method) (hereinafter to referred to as the average particle diameter), 3.7 ± 0.6 At nm, the shape is a pseudo-sphere close to a sphere.

The core of this new nanodiamond particle is Mohs hardness 10 and Young's modulus 1050 GPa, which is the hardest and most resistant diamond single crystal on earth. It is hard and does not wear even with yellow sand. This unique property makes it an ideal material for rolling under high pressure at the micro level true contact surface as a nano-sized “roller”. On the other hand, the shell is a thin graphene layer , but it is much more flexible than the core part, so it easily slips between the layers and becomes a good buffer zone between the core part and the sliding and snow / ice surfaces . It was considered to induce rolling of the “roller” action (see, for example, Non-Patent Document 5).

Therefore, when this new nanodiamond particle, which has a hard core / soft shell double structure and is expected to have a rolling effect due to a slight stress due to its pseudo-spherical shape, is dispersed in a hydrophobic ski wax substrate in advance, As the wax substrate, which is much softer due to friction with the snow and ice surface, is peeled off, the nanodiamond particles spill directly under the sliding device on the snow and ice, and dissolve in the melt layer on the snow and ice surface. It was thought that it became a size “roller” particle, and its rolling action reduced friction to develop a new lubricating effect on snow and ice .

However, in order to develop a new theory of on-snow / ice lubrication through this mechanism for suppressing the generation of frictional forces on snow / ice, as a prerequisite , a large number of nano-sized “rollers” must always be sufficiently supplied to the real contact area of the interface. Don't be. The time and place where this true contact surface occurs is unpredictable, so in the end, it has a very large number of nano-sized "rollers" in the base material of the lubricating composition of the sliding tool on snow and ice. There must be particles. This is the reason why the number condition is necessary for the nano-sized “roller” action.

Here, using a general ski as a model, the upper and lower curved parts are excluded from the dimensions, the width is 100 mm, the length is 1500 mm, and the apparent sliding surface area is 1.5 × 10.
The power is 5 mm2. In another experiment, there was a result of calculating the total area of the initial true contact point using two soft iron plates. According to this result, the initial true contact area is 0.001% of the apparent contact area (for example, non-patent literature) 8).

As for the estimation from the above calculation, it is actually the most reliable verification to try skiing on snow and ice with skis etc. using ski wax in which nano diamond particles with a very slight concentration are dispersed, This estimation was verified as shown in the examples.

In order to distinguish the nanodiamond primary single crystal particles of the present invention from the nanodiamond agglomerate secondary particles described above, these nanodiamond agglomerate secondary particles are hereinafter referred to as “CD / UDD”. To do. Further, hereinafter, “nanodiamond particles” basically refers to the nanodiamond primary single crystal particles (dispersion) of the present invention.

The various substrates according to claims 3 and 7 are also an important configuration essential in the present invention, and a new additive comprising nanodiamond particles used as a means for solving the problems of the present invention is actually applied to snow and ice. Four of the nano-sized “roller” action required to store an infinite number of this additive and continue to supply a sufficient number to feed the above-mentioned true contact surfaces that occur unpredictably in sliding movement . Satisfy the ubiquitous condition among the conditions.

The manufacturing method according to claims 8 to 11 is the manufacturing method indispensable for the present invention, and as means for solving the problems of the present invention, an additive comprising nanodiamond particles is added to the nano-sized “roller” described above. It is the only method for dispersing the lubricant composition on the base material while adapting to the shape condition, the number condition, and the ubiquitous condition among the four conditions of action.

Next, how the manufacturing method according to claims 8 to 11 is indispensable for the present invention will be described in detail in comparison with the prior art.

Therefore, many people came up with the idea of lubrication using nanoparticles, even when the famous soccer ball type molecule C60 fullerene or fumed silica was discovered, and they were eagerly applied in anticipation of nano bearing applications. . However, the nanoparticles having a simple uniform structure close to the limit of the nano size are too high in agglomeration property, and the smallest particles are actually higher-order aggregates having nanopores. Therefore, even if any known surfactant is used for dispersion, it is difficult to make primary particle dispersion in a solvent, and C60 fullerene or the like cannot achieve high lubricity as in the present invention.

Specifically, it is a feature common to the production methods according to claims 8 to 11, and first, nanodiamond particles are stabilized as a dispersion medium in a colloidal state suitable for the polarity of each dispersion destination substrate. By passing through the colloidal state, the nanodiamond particles have a characteristic shell layer that interacts with the solvent, loses cohesion, and becomes stable, which is essential in the production method of the present invention.

Center of technical idea of the present invention is a nano-sized "When" effect four conditions, and C60 added ski wax produced in consists Further prior art without considering this, nano-sized "This filtrate" action according to the invention The difference in technical idea from the nano-diamond-dispersed ski wax, which was constructed for the purpose of expressing the four conditions , is obvious when sliding on snow and ice where yellow sand actually falls.

For example, hard paraffin which is still widely used, if polyethylene running surface material snowboard or the like provided it is advantageous from the prevalence, hot vaccinia Thing to applied the solid paraffin is also dissolved by heating with an iron ski In the case of cold waxing (raw coating), which is directly rubbed as it is, suitable substrates are different. The edges at the ends of the running surface, skating blades in the al is made of metal so hard paraffin is not established, it is necessary to form changing, such as with an excellent liquid fixing the metallic material. In addition, a material that meets the above-mentioned “safety conditions” should be used for the base material.

Hydrocarbon synthetic waxes have the above-mentioned advantages, but have a disadvantage that their melting point is higher than that of petroleum-derived artificial paraffin . For example, in hot waxing, work at a high ski iron temperature setting is required, so there is a concern about damage to the sliding surface material when a work mistake occurs. In this respect, the FT wax is advantageous in that it has a lower melting point and higher fluidity at the time of heating and melting, and is therefore more workable. On the other hand, low molecular weight polyolefin is more advantageous in terms of wear resistance after successful construction. Therefore, an appropriate type may be selected or used in combination depending on the worker's skill in waxing. In order to reduce the difficulty of handling low molecular weight polyolefin, low melting point solid paraffin or the like can be mixed.

In addition, a form in which nanodiamond particles are added to a raw material (ultra high molecular weight polyethylene, UHMWPE) of a sliding surface material that is a ski material as a base material is also considered. However, since UHMWPE does not flow at all even when heated to the melting point, it should first be taken into account that all past examples of attempts to disperse additives in a general mixing operation have failed to achieve their purpose (0036). See paragraph -0038). Further, in order to disperse the additive in the sliding surface material, the amount of the additive used reaches several tens of times that in the form of ski wax, so that corresponding production facilities and costs are required. Therefore, these points should be fully considered in the implementation of this embodiment.

Since nanodiamond particles generally exhibit water solubility, they are not dispersed in a hydrocarbon-based synthetic oil medium such as PAO as it is. For this reason, surfactant molecules such as nonionic glycerin monooleate and polyoxyethylene stearyl ether phosphate can be used as a dispersant in the medium. Of course, the medium dispersant that can be used to achieve the purpose of the dispersion is not limited thereto. In this embodiment, it was possible to obtain a stable hydrocarbon-based synthetic oil colloid having a concentration of about 0.1 w / v%. However, in the case of a high concentration colloid having a concentration of 1 w / v%, an abnormality was observed in the colloid in about 1.5 months. Therefore, there is a certain upper limit of concentration. Storage of the hydrocarbon-based synthetic oil colloid requires storage in a cool and dark place by sealing an inert gas such as argon gas in a sealed container.

Next, when the base material is a silicone product, a polar medium such as ethylene glycol, propylene glycol, 2-methoxyethanol or lower alcohol such as ethanol and methanol can be used. Propylene glycol is advantageous because its saturation solubility in nanodiamond particles is as high as 3%. Therefore, it can be developed into various silicone products using modified silicone as a base material through polymers such as polyethylene glycol (PEG) and polypropylene glycol as intermediate substances. Of course, colloidal media and intermediate materials that can be used to achieve the purpose of this development are not limited to these. In the present embodiment, a hard gel obtained by partially evaporating the colloid solvent instead of the colloid can be obtained, which is advantageous in terms of storage.

“Dispersion medium with hydrocarbon-based synthetic oil” In order to disperse the nanodiamond particles “ND” shown in Example 1 on a substrate such as paraffinic hydrocarbon and olefinic hydrocarbon by direct operation, it is nonpolar. As a solvent, a modified polyalphaolefin (PAO) SpectraSyn Plus 6 manufactured by Exxon-Mobil was used from among hydrocarbon synthetic oils. Since PourPoint is below 50 ° C below freezing, it can also be used for snow and ice sliding equipment used under low-temperature weather conditions. The movement of the corresponding low, when heated to melt the paraffin wax base which will be described later in this kinematic viscosity value than the dynamic viscosity of the PAO materials that kinematic viscosity which is generally commercially available in 6cSt and domestic (50-127 mm2 / s) The dispersibility is extremely excellent because it is almost the same as the viscosity value (about 6 mm2 / s), and it is optimal as a dispersion medium of this embodiment (for example, see Non-Patent Document 10).

The preparation of a specific dispersion medium will be described. In 1L Erlenmeyer flask, 1L of the above-mentioned PAO modified SpectraSyn Plus6 as a hydrocarbon-based synthetic oil, 1.0g (0.1w / v%) of nanodiamond particles “ND”, and additives are dispersed in engine oil as a medium dispersant. As a non-ionic glycerin monooleate that is often used, Kao Co., Ltd., 10.0 g of Rhedol MO-60, and as weakly acidic polyoxyethylene stearyl ether phosphate, Toho Chemical Industries Co., Ltd., LB400, Phosphor 10.0 g of diol, that is, 1.0 w / v% of both medium dispersants were added in this order, and magnetic stirring was continued for 2 days using a magnetic stirring apparatus in a nitrogen atmosphere as an inert gas at room temperature. The dissolution of “ND” started after half a day, and solids disappeared almost completely after one day, and a light blackish transparent solution with a light indigo color was obtained after two days. The dispersion medium obtained by this operation is referred to as “ND-PAO” in the following examples.

"Dispersion medium with lower alcohol" In order to disperse "ND" shown in Example 1 on a silicone product substrate by an indirect operation, ethylene glycol was used from lower alcohols as a polar solvent. In this example, PEG polymerized with ethylene glycol was used as an intermediate substance. These are easily available from test reagent handling companies such as Wako Pure Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd. This time, Wako Pure Chemical Industries, Ltd., polyethylene glycol 4000 (PEG4000) average molecular weight 3000, mp50-60 ° C. was prepared as an intermediate substance .

For ND, the same ethylene glycol colloid was obtained by direct solvent displacement from a nanoamand aqueous colloid made by Nanocarbon Laboratory, which is a dispersion . When the particle size distribution of this colloid was measured by the DLS method, the particle size was 4.1 ± 0.6 nm (100.00 vol%), which satisfied the conditions of the problem solving means of the present invention. The colloid concentration was 2.00 w / v% and the zeta potential was +47.6 m. This nanoamand ethylene glycol colloid is hereinafter abbreviated as “ND-EG”.

The preparation of a specific dispersion medium will be described. First, 57 g of the intermediate substance PEG4000 was weighed, placed in a beaker, and heated and stirred with the top covered with a wrap. After confirming that the solution was melted at a liquid temperature of 62.4 ° C. and became completely transparent, 2.5 ml of the ND-EG (ND = 0.05 g) was added dropwise, and the stirring was continued with a magnetic stirrer for about 30 minutes. In order not to oxidize atmospheric oxygen by vortex during heating and stirring and oxidize the surface structure peculiar to nanodiamond particles, high-purity N2 gas for experiment was introduced through a glass tube penetrating a lap on a beaker and dripping stirring was performed. went.

The preparation of a specific dispersion medium will be described. First, as a preliminary preparation of equipment, a magnetic stirrer , arms, and cooling water piping are installed in the draft chamber. A silicone oil bath is placed on the heating plate of the magnetic stirrer and heated to 80 ° C. A 300 ml three-necked flask equipped with a reflux condenser and a magnetic rotor was attached.

The ND concentration of the liquid mixture obtained by this operation is 0.2 w / v %, and the water content is about 0.4%. This mixed solution is abbreviated as “ND-H 2 O-tBu” in the following examples.

Specific preparation of the substrate will be described. First, main components and subcomponents of solid paraffin serving as a base material are determined and mixed and adjusted in advance. In this operation, the entire amount of ParaffinWax-140 (hereinafter abbreviated as P140) was used. Next, about 130 g of P140 was placed in a beaker and completely heated and dissolved with an electric heater. After filtering the impurities through a filter paper, 100 g was weighed and transferred to a 300 ml beaker. The beaker was placed on a magnetic stirrer , covered with a paper lid, heated to 84 ° C., and kept warm. High-purity N2 gas for experiment was continuously introduced through a heat resistant tube made of silicone from a break in the paper lid on the beaker, 1 g of “ND-PAO” of Example 2 was weighed and dropped with a whole pipette, and magnetic stirring was performed for 17 minutes. Finally, after confirming that scattering due to the Tyndall phenomenon occurred uniformly in the beaker, the contents of the beaker were immediately transferred to a silicone container for cooling molding and cooled in a cold water bath.

Specific preparation of the substrate will be described. First, a hydrocarbon-based synthetic wax as a base material is prepared and added and adjusted in advance as necessary. In this operation, the entire amount of Mitsui High Wax 400P (hereinafter abbreviated as PE400) was used as it was. Then PE 400 200 g purse was completely dissolved by heating the beaker, after heating the beaker to 0.99 ° C. covered with a resin lid was placed on a magnetic stirrer, it was the total amount dissolved magnetically攪 拌. 10 g of “ND-PAO” of Example 2 was weighed and dropped into a beaker under magnetic stirring from a hole pipette in a state where high purity N 2 gas for experiment was introduced from a beaker top lid through a silicone heat-resistant tube. Due to the high operating temperature, the ND dispersion state in the substrate during stirring was constantly observed with scattered light due to the Tyndall phenomenon while confirming uniform dispersion while applying a laser pointer from multiple directions. After stirring for 24 minutes, the operation was terminated, and the contents of the beaker were transferred to a silicone container for cooling molding, and immersed in a cold water tank for rapid cooling.

In particular, the kinematic viscosity is 6 mm2 / s at 100 ° C, which is the same as the ND-PAO (SpectraSyn Plus6) kinematic viscosity (@ 100 ° C 6cst ). . If the melting point is 73.5 ° C and the waxing operation temperature is 80 ° C, the kinematic viscosity is 9mm2 / S and low viscosity. The difficulty is that the penetrating and fixing properties of sliding surfaces (UHMWPE / HDPE, etc.) are poor, so the best mode is to use the entire amount as a wax for sliding by the hot waxing technique. The prior art corresponds to a sliding wax that is waxed from above the base wax, specializing in sliding performance.

Specific preparation of the substrate will be described. First, the main component and subcomponent of the FT method wax as the base material are determined and added and adjusted in advance. In this operation, the entire amount of the above FT-0165 was used, but of course, it may be adjusted by mixing with other FT waxes. Next, FT-0165 was put into a beaker A and completely heated and dissolved with an electric heater, and transferred to a 900 ml heat-resistant glass container B so that the total amount was 400 g. Place this container B on a magnetic stirrer , cover it with a resin lid, heat it at a temperature setting of 130 ° C so that the subsequent dispersion operation is optimal, and use a non-contact type thermometer to FT-0165 in container B The solution temperature was adjusted to be kept at 100 ° C. Next, the subsequent operations were carried out in a state where the high purity N2 gas for experiment was continuously blown out from the top. A plurality of laser pointers were placed on the container B so that the dispersion of ND on the substrate could be easily confirmed. In this state, when 4 g of “ND-PAO” of Example 2 was weighed and poured from the upper part of the container B , the Tyndall phenomenon was immediately confirmed from a plurality of directions. After the magnetic stirring was continued for 7 minutes, the contents of Container B were transferred to a silicone container for cooling molding and immersed in a cold water tank to be cooled and solidified.

“Substrate by wax produced by FT method 2” As described above, since “ND-PAO-FT” is used for hot waxing, adjustment for cold waxing will be described next. First, the main component and subcomponent of the FT method wax as the base material are determined and added and adjusted in advance. In this operation, the entire amount of the above FT-0165 was used, but of course, it may be adjusted by mixing with other FT waxes. Next, the operation of Example 4 was performed, and a mixed solution “ND-H 2 O having an ND concentration of 0.2 w / v% using 240 ml of nanoamand 5% aqueous colloid as ND and 59.5 g of t-BuOh as an intermediate substance was used. -tBu "was adjusted. Third, 4.7 g of this ND-H2O-tBu (5.998 ml as a specific gravity of 0.78581) was taken and poured into a liquid in which 31.5 g of FT-0165 was heated and melted in a three-necked flask, and magnetically stirred in an argon atmosphere. Went. The ND dispersion state in the base material was inspected by the Tyndall phenomenon by applying a laser pointer from multiple directions, and after about 30 minutes when it was confirmed that the scattering occurred uniformly, this operation was stopped, and the three-necked flask composite composition was The product was transferred to a PP container, and the PP container was rotated while applying a strong water flow to be rapidly cooled to obtain a solidified product in the PP container.

In the composite composition cooled and solidified, 0.028 wt% of ND is dispersed. Finally, in the fourth operation, 5.1 g of this ND-dispersed composite composition was weighed, and 10.2 g of the above FT-0165 was weighed and dissolved, and magnetically stirred to obtain a final substrate. In the final substrate, 0.009 wt% of ND is dispersed. This final substrate obtained by the above operation is referred to as “ND-tBu-FT” in the following examples.

Specific preparation of the substrate will be described. First, the base material was selected, but in this example, as described above, the entire amount of ELCRYSTA CPAO grade XF4100 (hereinafter abbreviated as CPAO) was used. Next, 50 g of CPAO was weighed into a 100 ml Erlenmeyer flask and completely heated and dissolved on an electric heating board. After heating the Erlenmeyer flask to 95 ° C. on a magnetic stirrer, it was kept. Weighed 5g of "ND-PAO" of Example 2 while continuing to flow into the Erlenmeyer flask from the Erlenmeyer flask via the glass tapered tube, and dropped with a whole pipette, followed by 37 minutes of electromagnetic stirring. Went. The Tyndall phenomenon at this point was examined (see FIG. 7, A), and then the contents of the Erlenmeyer flask were transferred to a resin petri dish container for cooling molding (see FIG. 7, B), and air-cooled as it was. This solid obtained by the above operation is referred to as “ND-PAO-CPAO” in the following examples.

“Substrate with Polymer Having Siloxane Bonding, Part 1” A polyoxyethylene-modified water-dispersible low-melting-point silicone wax was used as a base material of a lubricating composition for incorporating ND therein via a dispersion medium. This is a hydrophilic soft wax which is used in skin care applications is a cosmetic material, a DOWCORNING 2501COSMETICWAX manufactured by Dow Corning Toray Co., Ltd.. In this example, this was used as it is for the edge or blade and side wall as a soft wax-like base material for cold waxing.

Specific preparation of the substrate will be described. First, a substrate was selected, but in this example, as described above, DOWCORNING 2501COSMETICWAX (hereinafter abbreviated as 2501) was used in its entirety. 18.5g of 2501 was weighed in a heat-resistant glass cup and dissolved by heating on an electric heating board. The cup was placed on a magnetic stirrer and heated to 76 ° C. and then kept at this temperature. In this, 0.37 g of “ND-EG-PEG” of Example 3 was weighed and added, and magnetic stirring was performed for about 17 minutes. The ND was inspected by scattering due to the Tyndall phenomenon, and the contents of the back cup were transferred to a PP resin container for cooling molding and air-cooled as it was.

“Substrate with polymer having siloxane bond skeleton, part 2” High fatty acid ester-modified silicone oil was used as the base material of the lubricating composition for incorporating ND therein via a dispersion medium. This is a kind of modified silicone excellent in lubricity and is commercially available as TSF411 (hereinafter abbreviated as 411) manufactured by Momentive Performance Materials Japan as a lubricant additive. Since the pour point is 0 ° C., in this embodiment, it is mixed with the same TSF431 ( methylphenyl silicone oil, hereinafter abbreviated as 431) in the specified environment and used as a liquid base material for edge or blade and side wall. Using.

Specific preparation of the substrate will be described. First, a base material is selected. In this example, 411 was mixed with 431 as described above. Placed sterile resin cup 411 by 80.3g weighed cups leave placed in magnetic攪 拌 device on, the "ND-PAO" in Example 2 was added dropwise to 2.4g weighed into this, its 42 minutes Magnetic stirring was continued. Next, this mixed solution was weighed to 16 g, 84 g of 431 was added, and magnetic stirring was further continued for 40 minutes. The ND ubiquity in the substrate was simply inspected by scattering due to the Tyndall phenomenon, and the mixed solution in the back cup was filtered with a filter paper.

In the liquid base material obtained by the above operation, ND of 0.0006 w / v% is dispersed. The liquid substrate obtained by the above operation is referred to as “ND-PAO-411 + 431” in the following examples.

Specific preparation of the substrate will be described. 75 g of the above-mentioned KWX-3 was weighed into a beaker and dissolved by heating to around 85 degrees on an electric heating board. This KWX-3 melt was poured into a silicon cup and kept warm, and the subsequent operations were performed while blowing high-purity N2 gas for experiment from above. Next, 0.87 g of “ND-PAO” of Example 2 was weighed and added, and magnetic stirring was performed for about 17 minutes. Simplified inspection of ND ubiquity in the base material by scattering due to Tyndall phenomenon, whether the ND ubiquity condition in the base material is satisfied, by directing the laser pointer from multiple directions, and simple inspection by scattering by Tyndall effect, silicon The cup was air-cooled as it was.

Since ND-PAO-P140 is inferior in sliding performance as a single unit, it is used as a base (fixing or base) wax in the prior art for pretreatment of “ND-PAO-FT”, which is weakly fixed on the sliding surface. Is desirable. Since ND-PAO-PE400 is difficult to construct by itself, it is desirable to use ND-PAO-PE400 as a hard base wax referred to in the prior art by mixing it with an FT method wax having a lower melting point and lower viscosity. Since ND-PAO-KWX3 is a product group of Kashiwax, it is used in the usage and procedure recommended by Kashiwax.

Finally, “ND-PAO-411 + 431”, which is classified as cold waxing, is applied in the same way as conventional liquid ski wax. That is, the liquid is dropped on the sliding surface as it is and spread with a cloth or the like, or is dropped on a sponge or the like and applied to a narrow portion such as an edge or a side wall. When used for skate blades, it can be applied to the bottom side of the blade as well as the bottom surface of the blade that comes into contact with snow and ice, so that it can be replenished to the bottom side . Those that take this embodiment are given “/ Liquid” in the following examples, and are called “ND-PAO-411 + 431 / Liquid” to distinguish them from the above-mentioned WAXs.

In the state of the sliding surface, the sliding surface coated with commercially available fluororesin-containing ski wax had the wax considerably peeled off, and the yellow sand adhering substance that changed the snow surface to black-brown was adsorbed and stained on the sliding surface. (See FIG. 3B, snowboard in the back). On the other hand, the ND-dispersed WAXLub-applied sliding surface of the present invention is not affected by wax peeling or black-brown yellow sand adhering material, and is not affected by yellow sand or yellow sand adhering substances even in such an environment (FIG. 3B). Snowboard in front.

Test Summary Date: April 23, 2011, Location: Naeba Kagura Ski Area, Weather: Rain. Test method: skated in several snowboard gliding course of about 1k m and glide assessment, also comprehensive evaluation of the state of the running surface.

Test environment: First of all , it was the first day of the 2012 season, and the test method was the above simple method because it was crowded with blankers on the course . This ski resort was just opened the day before, so the snow and ice surface was unique to artificial snow and the consumption of wax was intense, so the difference between specimens was clear.

“Sliding test 7: Comparison 2 with commercially available nano-diamond method” In this example, a dispersion consisting of a colloidal solution in which an additive composed of nano-diamond particles is first applied to a substrate, which is an important feature of the present invention. leave medium, the manufacturing method of dispersing the base material in the following direct or indirect operations that wait on the polarity of the substrate is the same nano-carbon nano diamond particles and essentially lack this important feature A sliding test was conducted for comparison with a conventional manufacturing method (see, for example, 0117) in which an additive composed of C60 fullerene was put into a base material which was heated and dissolved in a visible fine powder state.

Test environment: First, this ski resort was the first indoor ski resort to open in the Tokyo metropolitan area, and since it just opened in the 2013 season the previous day, it was very crowded with many ski and snowboarders waiting for the first slide. . For this reason, the inventor puts safety considerations for the surrounding ski and snowboard customers first, and the sliding test is made the above-described simplified method using the edge of the slope. The snow quality of our ski area, with artificial snow by the ICS, which is a characteristic close to the shaved ice rather than snow, surprisingly fast is the wax wear Although the course length 300m about. In addition, some say that the indoor ski area is believed to it from the outside air had warned or snow surface maintenance vehicle, from here because it is open there is no side wall, a variety of dirt was observed on the course.

Test results: In the sliding evaluation, ND-tBu-FT / ColdWAX showed the best sliding feeling when compared to the feeling of starting from the stopped state immediately after waxing, followed by ND-PAO-FT / HotWAX. And commercial product D were comparable, and thereafter, commercial product C, commercial product A, and CD / UDD ski wax No. 2 in that order. CD / UDD Ski Wax No. 2 had a feeling of being caught immediately after waxing, and it was found that this gradually disappeared due to wax consumption. In addition, the high-concentration fluorine-based (commercial product C, commercial product D) had a weak initial gliding feeling immediately after waxing . Next, in the comparison of the passing time between the two points, CD / UDD ski wax No. 2 was set with 6.88 seconds without ski wax as the reference passing time.
-0.06 seconds, commercial product C
-0.28 seconds, commercial product A
-0.29 seconds, commercial product D
-0.30 seconds, ND-tBu-FT / ColdWAX
-0.63 seconds, ND-PAO-FT / HotWAX
-0.69 seconds, each time shortened .

DISCUSSION: Without the important manufacturing features of the present invention, it was confirmed that the additive consisting of nanoparticles could not be ubiquitous in the ski wax substrate, but was even counterproductive. Although the No. 2 CD / UDD ski wax is the number evaluation exceeds the slightly wax-free construction, which is greatly affected by the street-watt box exhaustion of the above, if it is immediately after waxing, inferior to clear because there is caught feeling There wasn't. In addition, the commercial product D, which essentially contains the same nanocarbon C60 and a fluorine-based lubricant, has a large effect difference from the ND-dispersed WAXLub of the present invention. This is also the city Commercially available products D is in the range of extension on the production method of the prior art is considered that it is the reason.

Test results:
First the overall evaluation, the ND dispersion WAXLub of the present invention in a gliding from the summit without cold reluctant generation, especially specimens were constituting the substrate specifically for midwinter NDCP44 (olefinic hydrocarbon base materials) Showed good sliding performance near the summit. Next, in the reach distance test, the commercial product F stopped first for hot wax, the specimen NDCPFT stopped at a position 3.3 m ahead, and the specimen E stopped a further 2.2 m ahead. For cold waxing, the specimen NDCP44 stopped 4.5m before the specimen F, and the commercial product G stopped 3.6m before that.

Test Summary: Date: January 1, 2012, Location: Sapporo International Ski Resort, Hokkaido, Weather: Cloudy to light snow, wind slightly, temperature below freezing to 11 ° C below freezing. Snow quality: powder snow, snowfall 195cm. Test method: The vehicle was lifted from the bottom of the ski area and measured by the distance reached from the fixed position on the third side of the woody lift used in Example 18 to the stop position. In this test, it was confirmed that the tester was a ski beginner brother of elementary school students and college students, and that the tools were stored in accordance with the general reality, and that the ND-dispersed WAXLub of the present invention could be effective even in a so-called family ski layer.

Specimen: The equipment was in line with the general situation, and both testers dared to use unmaintained skis that had been left in the storeroom. However, in order to prevent children's injury, the inventor repaired and removed the burrs and burrs on the plate. Among the ND-dispersed WAXLubs of the present invention, the softest “ND-EG-PEG-2501 / SoftWAX” (Example 9, hereinafter abbreviated as ND2501) was used. For comparison, Holmenkol's Natural SkiwaxStick (hereinafter abbreviated as commercial product H) is available as a commercially available low-cost flexible NF product, and TOKO's DiblocHighFluoro Rub-onWax (hereinafter abbreviated as commercial product I) is available as a commercially available low-cost HF product. did. After the procedure the inventor of waxing at first co Rude wax before sliding test was observed by demonstration was also observed that working accuracy was performed testers both persons.

Test Description: Test Description: Date: 2012 February 25, Location: Nagano Prefecture Asama 2000 Ski, weather: weather: snow, temperature: from below freezing 4 0 ℃, snow temperature: below freezing 2 ℃ from below freezing 5. Snow quality: Slightly wet with fresh snow. Test method: In order for the tester to participate in the GS race, the ND dispersed WAXLub according to the present invention and the commercially available wax group for the competition are inspected (the race course preview run after explanation of the competition guide) and warm-up, etc. As a result of comparing both the skis with the construction, the performance of the ND-dispersed WAXLub multiple configuration according to the present invention is excellent, so this was used from the first in the race. Of course, since it is not possible to compare both times in the main game, we will consider based on the sensation of the entire day in the competition speed range of the competitor .

As a consideration, it was confirmed that the ND-dispersed WAXLub of the present invention is effective even in such a race condition and also has an effect on a ski edge that is a metal material. Again, since the lubrication system of the present invention depends on the “roller” rotation, as shown in Example 18 , on the low density powder snow, the “roller” rotation action decreases as the density decreases. With the same reasoning, it can be understood that the "roller" rotating action is strengthened in a race burner in which a snow surface hardener (also called snow cement or ammonium sulfate) is sprayed to maintain a high density. In addition, it seems that the same effect was seen in contrast as wax for ski edges.

Test Description: Test Description: Date: March 2012 18 days, Location: Nagano Prefecture Nomugitoge ski resorts, weather: cloudy, 5 ℃ from the temperature 1, snow temperature: 0.7 ℃, snow: wet snow. Test method: Since the tester participates in the GS race, this battle board is a ND-dispersed WAXLub application board according to the present invention that was used last time, replenished according to its wear, and a preliminary competition board for inspection and warm-up. Each of the skis with a plurality of wax groups was prepared and compared. Of course, since it is not possible to compare both times in the main game, we will consider based on the sensation of the entire day in the competition speed range of the competitor .

Specimen: The ND-dispersed WAXLub according to the present invention had the ND-dispersed WAXLub remaining on the board that was used in the previous race (see Section 0274). -PAO-PE400 / Hotwax (Example 6, hereinafter abbreviated as ND400), ND-EG-PEG-2501 / SoftWAX as the base solid on the ski side including the ski edge, and ND-PAO- 411 + 431 / Liquid (both Example 9) was respectively waxed. Contrasting products are a group of commercially available waxes on a spare board, and the rescue surface is a “Musou” made by Team Rescue (a so-called hard base wax made of LDPE, hereinafter abbreviated as “K”). "Q5" and "Q7" of so-called solid HF wax for starting) were used separately for comparison. On the ski side, a commercial product J (see 0274) was used as before.

Test results: In the sliding evaluation, in the trial sliding at the start point, the sliding performance was excellent in the order of Q5> Q7 ≧ ND400 , and Q7 and ND400 were almost equal. However, as described above, the sliding performance of the race course changed due to poor snow and ice surface conditions, and the preliminary board that was waxing the commercially available wax group significantly decreased the sliding performance by inspection alone. It was observed that Q5 and Q7 picked up and adsorbed much dirt on snow and ice. On the other hand, the ND dispersed WAXLub (ND400) according to the present invention did not significantly impair the sliding performance even in the final race and the subsequent two or three runs. In this configuration, ND-EG-PEG-2501 / SoftWAX, which was used as the base solid, became a resistance for the ski edge wax, and the comparison commercial product J slid more smoothly because the vibration was reduced.

As a consideration, the ND-dispersed WAXLub of the present invention is quite effective in such spring race conditions, and in particular, the contrasting products Q5 and Q7 made by Dominator are the most expensive among the current commercial competition waxes. is a (18900 yen) high-performance class, in particular given that there was a LDPE wax layer thereunder, ND400 of the present invention has also shown that commercially available athletic wax consists of a plurality configuration and evenly matched performance alone Become. The test results in the ski edge wax, commercially available Sukiwa box almost all products have in common is a lubricating initiative repellent emphasis be used in multiple configurations over other manufacturers and other varieties obtained enhancing effect On the other hand, in the case of the ND-dispersed WAXLub of the present invention, the concentration of the additive consisting of ND in the substrate is an ultra-dilute concentration of around 0.001 wt%, so almost 100% is the main component. It is. Therefore, when it was used in a composite configuration with the opposite bases of hydrophilicity and hydrophobicity as in this case, the possibility that the sliding effect was attenuated was shown.

Outline of the test: Outline of the test: Date of the first test : Date: March 20, 1990 Location: Honoki ski, Gifu Prefecture, Weather: Sunny weather, Temperature below 3 to 3 ° C, Snow temperature: Below 7 to 5 ° C 、 Snow quality: Tight snow mixed with artificial snow and natural snow. The second test date is the date: April 2012 14-15 both days, Location: Nagano Prefecture back Shiga Kogen ski area, weather: 14 days sleet snow, 15 days fine weather, temperature: 8 ℃ from minus 1, snow temperature: below freezing 2 To 0 ° C, snow quality: yellow sand fall on snow remaining in spring, snow surface hardener sprayed. Test method: The tester will be supplied with the ND-dispersed WAXLub application board according to the present invention and the commercially available product according to the effect and wear in each scene of practice, warm-up, qualifying, and main battle for the race for a total of three days. Each was compared.

Specimen: ND-dispersed WAXLub according to the present invention includes ND-PAO-411 + 431 / Liquid (Example 9; hereinafter abbreviated as ND411) on a plurality of ski sides composed of testers' race races and spare plates. (Hereinafter abbreviated as ND411), and as a comparison, commercially available ski edge wax, the same commercial product J as Example 20-21 , and the same performance-enhanced “skate cage” (hereinafter abbreviated as commercial product K) ) Were used separately for each. This commercial product K is considered to be obtained by increasing the viscosity of the commercial product J and adding a Ws2-based solid lubricant in order to cope with the skate use environment.

Test results: In the sliding evaluation, when the usage environment is negative , the improvement in sliding performance, which seems to be due to vibration absorption, is excellent in the order of commercial product K> commercial product J> ND411, and ND411> commercial product K for simple sliding speed. > Commercial product J was excellent in this order . In terms of durability, I felt that the commercial product K was about 3000m and the ND411 was about 2000m. Next, when the usage environment is a plus environment, the commercial products K and ND411 have almost the same level as the overall sliding performance, although the respective sliding feelings are different. Characteristically, ND411 increased its effect as wet snow and snow temperature increased, and was especially resistant to dirt on snow and ice.

As a consideration, it was confirmed that the ND-dispersed WAXLub of the present invention is effective even when used for various member parts provided on a snow and ice sliding / moving device made of metal or resin. The ski edge wax commercially J which contrasted is are made of so-called vacuum fluorine-based lubricant such as silicone oil and perfluoropolyethers according to public information, the main component similarly silicone OIL also ND411 Since ND is used as an additive, the contrast corresponds to the contrast between these high-performance fluorine-based lubricants and nanodiamond primary single crystal particles ND according to the present invention. It was confirmed that WAXLub is equivalent to these high-performance fluorine-based lubricants and satisfies the first problem to be solved by the present invention.

Test environment 1: On the day of the weather was the day of the warm spring, the first half of the already test course at the end of April is the plain of wet snow that dirty snow and ice surfaces, cruel to the snowboard beginners especially inferior level ground movement ability It was a serious situation. In addition to this, beech leaves and pollen from surrounding vegetation were scattered in the middle beech virgin forest. In the latter half of the wooded forest , a lot of yellow sand, pollen, leaves and leaves were scattered in the narrow sliding passages between the standing trees , and it was an inferior environment where it was forced to pass through places that were no longer snowy and ice.