JPH0820747A - Ski wax - Google Patents

Abstract

PURPOSE:To obtain a ski wax which, when applied to skis, can give persistent excellent sliding performance thereto irrespetive of conditions of use such as the quality of snow. CONSTITUTION:This wax contain cyclopentadiene-base petroleum resin such as a product of thermal polymerization of a cyclopentadiene, a product of thermal copolymerization of a cyclopentadiene with an alpha-olefin and/or a monovinylaromatic hydrocarbon, a product of hydrogenation thereof, or a mixture thereof.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to ski waxes. More specifically, the present invention relates to a ski wax containing a cyclopentadiene-based petroleum resin and capable of achieving excellent gliding properties for a long period of time by being applied to the skiing surface of a ski.

[0002]

2. Description of the Related Art Ski wax has been originally used as a material for improving the sliding property by applying it to the sliding surface of a ski. For example, in ski alpine competitions, it is essential to use ski wax in order to maximize the reduction of gliding time, and careful attention must be paid when selecting the wax. On the other hand, for general skiers, ski wax is applied to improve skiing comfort and technology, and the form of the ski wax has been found for a long time. There are a wide variety of materials, from solid ones that are applied and stretched, to semi-solid raw coating types, to liquids and paper sheets, which are simple in workability and coatability according to the requirements of the users. It is becoming popular.

Conventionally, paraffin wax of aliphatic hydrocarbons has been mainly used as ski wax, but this paraffin wax needs to be properly used depending on conditions such as operating temperature and snow quality. Until the last minute, the selection was troubled, and it became a factor for general skiers to make the waxing work complicated and to feel uneasy about the performance of the ski wax. In addition, this paraffin wax has poor durability, and depending on the conditions of use, it can be peeled off just by sliding a few hundred meters.
Lost. Therefore, in recent years, studies have been made on ski waxes in which various compounds are blended with paraffin wax or compounds that replace paraffin are used.
No. 0-112871, Japanese Patent Laid-Open No. 1-294873, Japanese Patent Laid-Open No. 3-157494, or Japanese Patent Laid-Open No.
Various proposals have been made in, for example, Japanese Patent Publication No. 211621.

[0004]

However, even if these can solve the problems of paraffin wax,
It does not sufficiently satisfy the performance required as a ski wax. For example, in Japanese Patent Laid-Open No. 1-294873, paraffin is mixed with gallium or molybdenum disulfide, or it is further added with II or II of the periodic table.
By blending alloys with Group I and IV metals, we are trying to improve gliding properties, durability, usage conditions, etc. However, on the other hand, the problem that the blended black inorganic compound does not come off when it adheres to clothes, etc. Alternatively, a new practical problem such as a problem that an inorganic compound is liberated during melt coating occurs.
Further, silicon, a fluorine-based compound, and the like, which have been proposed as compounds replacing paraffin wax, are extremely expensive and are disadvantageous in terms of economy. The present invention has been made in view of the situation of the above-mentioned conventional art, and an object thereof is to provide a ski wax having sufficient economical efficiency, practicality, and the like, and capable of maintaining excellent gliding properties for a long period of time. And

[0005]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies to solve the above problems and develop a ski wax having excellent performance, and as a result, contain a specific cyclopentadiene-based petroleum resin. It was found that ski wax has excellent performance capable of satisfying the purpose, and the present invention has been completed based on this finding.

That is, the present invention relates to a thermal polymerization product of cyclopentadiene, a thermal copolymerization product of cyclopentadiene and α-olefins and / or monovinylaromatic hydrocarbons, or a hydride thereof, or a product thereof. The present invention provides a ski wax containing a cyclopentadiene-based petroleum resin which is a mixture of Hereinafter, the present invention will be described in detail.

The cyclopentadiene-based petroleum resin used in the ski wax of the present invention is a thermal polymerization product of cyclopentadiene or a thermal copolymerization of cyclopentadiene with α-olefins and / or monovinyl aromatic hydrocarbons. It is a thing, or those hydrides. The cyclopentadiene includes cyclopentadiene, a multimer thereof, an alkyl-substituted product thereof, or a mixture thereof, and about 30% by weight of cyclopentadiene obtained by steam cracking such as naphtha is industrially used. Above, it is advantageous to use a cyclopentadiene-based fraction (CPD fraction) containing at least about 50% by weight. Further, the CPD fraction may contain an olefinic monomer copolymerizable with these alicyclic dienes. Examples of olefinic monomers include aliphatic diolefins such as isoprene, piperylene and butadiene, and alicyclic olefins such as cyclopentene. It is preferable that the concentration of these olefins is low, but it is acceptable if the concentration is about 10% by weight or less per cyclopentadiene.

Examples of the α-olefins as a raw material for polymerization with cyclopentadiene include α-olefins having 4 to 14 carbon atoms, preferably α-olefins having 4 to 10 carbon atoms and mixtures thereof, ethylene, A derivative such as propylene or 1-butene, or a decomposition product of paraffin wax is preferably used. This α-
Olefin is 4 per mole of cyclopentadiene
It is industrially preferable to add less than the molar amount.

Examples of monovinyl aromatic hydrocarbons which are another polymerization raw material include styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene and β-methylstyrene.
It is industrially preferable to add less than 3 mol of the monovinyl aromatic hydrocarbon per 1 mol of the cyclopentadiene. The monovinyl aromatic hydrocarbons are indene,
It is possible to include indenes such as methylindene or ethylindene, and industrially it is advantageous to use a so-called C ₉ fraction obtained by steam cracking such as naphtha. The number of moles of cyclopentadiene is calculated as 1 mole when a monomer such as cyclopentadiene is used as the cyclopentadiene and 2 moles when a dimer is used.

The cyclopentadiene-based petroleum resin is prepared by thermal polymerization of cyclopentadiene or thermal copolymerization of cyclopentadiene and α-olefin and / or monovinyl aromatic hydrocarbon, or by It can be obtained by hydrogenation. The following method is mentioned as one of the thermal polymerization or thermal copolymerization methods for obtaining a cyclopentadiene-based petroleum resin. First, these cyclopentadiene, or cyclopentadiene and α-olefins and / or monovinyl aromatic hydrocarbons are mixed in the presence or absence of a solvent, preferably under an inert gas atmosphere such as nitrogen gas. 160-300 ℃,
Preferably in the temperature range of about 180 to 280 ° C about 0.1 to
The raw material system is subjected to thermal polymerization or thermal copolymerization for 10 hours, preferably for about 0.5 to 6 hours under a pressure capable of maintaining the liquid phase.

Then, the inactive components in the raw materials, unreacted raw materials and, if necessary, the solvent are distilled off from the polymerization liquid under normal pressure, elevated pressure or reduced pressure, and then, if necessary, the reaction is continued. Two-stage polymerization under reduced pressure of about 160-2
A desired cyclopentadiene-based petroleum resin can be obtained by carrying out at 80 ° C. for about 0.5 to 4 hours. The hydrotreatment can be performed by a usual method. For example, using a hydrogenation catalyst such as nickel, palladium or platinum, in the presence or absence of a solvent, about 70 to 300 ° C.,
Preferably in the temperature range of about 100-250 ° C., hydrogen pressure of about 1
0 to 200 kg / cm ² (G), preferably about 20 to 1
The hydrotreatment may be performed under a pressure of 20 kg / cm ² (G) for about 0.5 to 20 hours, preferably about 1 to 10 hours.
After the hydrotreatment, the catalyst and, if necessary, the solvent are removed to obtain the desired hydrogenated cyclopentadiene-based petroleum resin.

The cyclopentadiene-based petroleum resin preferably has a softening point of 40 ° C. or higher and 180 ° C. or lower, and more preferably 50 ° C. or higher and 150 ° C. or lower. When the softening point of the cyclopentadiene-based petroleum resin is in the above range, preparation of the intended ski wax, melt coating on the ski running surface, and stretching become extremely easy, and the practical performance of the ski wax of the present invention is further improved. Can be improved. The present invention can be sufficiently achieved within the above range, but the softening point is 70 within this range.
If it is higher than 0 ° C, the durability is better, and if it is lower than 70 ° C, the sliding property is better. Further, the cyclopentadiene-based petroleum resin has a weight average molecular weight of 250 to 2,
The range of 000 is preferable, and 350 to 1,50 is particularly preferable.
Like the above-mentioned softening point, those having a range of 0 are preferable from the viewpoint of handling such as preparation property and coating property. The expression of the above-mentioned thermal polymer, thermal copolymer, or hydride thereof, or a mixture thereof is any of a thermal polymer, a thermally polymerized hydride, a thermal copolymer, and a thermally copolymerized hydride. This means that one kind may be used alone, or a mixture of two or more kinds may be used. Among these cyclopentadiene-based petroleum resins, unhydrogenated ones have residual unsaturated bonds, so that there is a concern that oxidation and polymerization may occur when left for a long period of time. Considering the influence on these colors and stability, it is preferable to use a hydride.

The ski wax of the present invention contains cyclopentadiene petroleum resin in an amount of 1 to 75% by weight, more preferably 5 to 60% by weight, and 2 parts of paraffin wax.
It is suitable to use it in an amount of 5 to 99% by weight, more preferably 40 to 95% by weight. Here, the paraffin wax referred, straight chain carbon atoms from 4 to 40, a mixture of branched-chain or cyclic aliphatic hydrocarbons, preferably the basic skeleton is represented by the general formula C _n H _{2n + 2} 15 carbons
Is a mixture of .about.40 linear aliphatic hydrocarbons. The ski wax of the present invention improves the practical performance such as prepareability, coatability, and economic efficiency by mixing with paraffin wax, and further exhibits improved and excellent gliding properties under a wide range of use conditions. To do.

The ski wax of the present invention contains the above-mentioned cyclopentadiene petroleum resin as an essential component, but can be prepared by adding various known additives, if necessary. As this kind of additive,
Examples include lubricants such as silicon and fluorine compounds, hardness modifiers such as polyethylene, silica, alumina and oils and fats, antistatic agents such as carbon, antioxidants such as zinc dithiophosphate, and colorants such as pigments and dyes. To be Further, the ski wax of the present invention can take any form such as solid, lip-like semi-solid, liquid, and paper sheet. For example, when the ski wax is solid, it is heated and melted by a heat source such as an iron to ski. It may be used by coating and stretching it on the sliding surface, and may be used in the form of a liquid dissolved and dispersed in a solvent such as acetone, or in the form of a sheet impregnated with paper or the like.

[0015]

The ski wax of the present invention is characterized in that it uses a specific cyclopentadiene-based petroleum resin. That is, the cyclopentadiene-based petroleum resin defined in the present invention does not exist in conventional ski waxes, and the ski sliding surface made of sintered polyethylene or the like and its pores are impregnated by the adhesive force due to its unique structure, Stick firmly. Furthermore, due to the high water repellency of cyclopentadiene-based petroleum resin and the extremely low temperature curability, increase in friction due to sticking of snow crystals, peeling of the formed ski wax layer, and roughening are prevented, resulting in excellent sliding performance. It is understood that sex can be maintained for a long time.

[0016]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples. The weight average molecular weight of the cyclopentadiene-based petroleum resin used in this example was determined by
Using polystyrene as a standard substance, the gel permeation chromatography was carried out and the result was expressed in terms of polystyrene. That is, in the present invention,
It is measured under the following analysis conditions using HLC-802 manufactured by Tosoh Corporation. Column: Tetrahydrofuran (THF) Column constant temperature bath temperature: 40 ° C. Flow rate: 1.2 ml / min Sample concentration: 0.005 g / ml THF Detector: Differential refractometer

Production Example 1 A CPD fraction 600 consisting of 75.0% by weight of dicyclopentadiene obtained by steam cracking of naphtha, 5.4% by weight of olefin, and most of the balance of saturated hydrocarbon.
g (cyclopentadiene 8.5 mol) and decene-1 9
250 g of a C ₁₀ fraction containing 6.5% by weight and the other fractions other than α-olefin (1.
7 mol) and 18 kg / cm in a nitrogen gas atmosphere
² (G) was thermally copolymerized at 260 ° C. for 3 hours. An inert fraction, unreacted raw materials and a solvent in the raw materials were first distilled off from the polymerization liquid under pressure and then under reduced pressure at 200 ° C. to give 420 g of cyclopentadiene petroleum resin (R-1) having a softening point of 52 ° C. Obtained. Next, 3% by weight of a nickel-based catalyst was added to 420 g of this cyclopentadiene-based petroleum resin and hydrogenated at a hydrogen pressure of 60 kg / cm ² (G) and a reaction temperature of 220 ° C. for 5 hours to obtain a hydrogenated cyclopentadiene-based petroleum resin (R −
2) was obtained. R-2 had a softening point of 58 ° C. and a weight average molecular weight of 590.

Production Example 2 600 g of the CPD fraction used in Production Example 1 and 400 g of xylene as a solvent were mixed in a nitrogen gas atmosphere at 18 kg / cm.
² (G) was thermally polymerized at 260 ° C. for 2 hours. Inert fraction in the raw material from the polymerization liquid, first under pressure unreacted raw material and solvent,
Subsequently, it was distilled off under reduced pressure at 160 ° C., and then further 50 Torr. The same temperature under reduced pressure for 1 hour,
Cyclopentadiene-based petroleum resin 380
g was obtained. Next, 3 wt% of a nickel catalyst was added to 380 g of this cyclopentadiene petroleum resin, and the hydrogen pressure was adjusted to 6
Hydrogenation was carried out at 0 kg / cm ² (G) and a reaction temperature of 220 ° C. for 5 hours to obtain the intended hydrogenated cyclopentadiene-based petroleum resin (R-3). R-3 had a softening point of 82 ° C. and a weight average molecular weight of 487.

Examples 1 to 4 Cyclopentadiene type petroleum resins (R-1, R-2 and R-3) obtained in Production Examples 1 and 2 and having 20 to 35 carbon atoms.
Then, each ski wax was prepared as shown in Table 1 using a paraffin wax consisting of n-paraffin having a maximum peak at 30 carbon atoms. In addition, in Examples 2 to 4, the improvement of the preparation property was recognized by the addition of the paraffin wax.

Comparative Example 1 Volacon Conquest Ski Wax currently on the market,
A pink collection (trade name, made in France) was used.
A skiing test and a durability test were carried out for each ski wax of Examples and Comparative Examples. The waxing of these ski waxes, the test conditions, and the evaluation method are as follows. These results are also shown in Table 1. (1) Waxing The ski waxes of Examples and Comparative Examples that were heated and melted were applied to the finished ski sliding surface, and uniformly stretched with an iron. After leaving the ski at 15 ° C. for 24 hours, excess ski wax was scraped off with a plastic scraper so that the coated surface was smooth, and the coated surface was finished with a nylon brush. In Examples 2 to 4, improvement in coating property was recognized by blending paraffin wax.

(2) Test conditions Weather: Cloudy, Temperature: -2 ° C, Snow temperature: -2 ° C, Snow quality: Simari snow (3) Evaluation method Sliding test: Using skis waxed as described above, 3 The average runner has an average slope of 15 degrees and a run distance of 2
The test course of 00 m was run 5 times, and the running performance was evaluated at the average time. Durability test: Using the skis waxed as described above, three skiers actually skied the test course with an average inclination of 20 degrees and a running distance of 1.7 km five times.
After the test, the average value of the remaining ratio of the ski wax remaining on the ski-sliding surface of the three skiers (the remaining area of the ski wax in the ski-sliding surface / the total area of the ski-sliding surface x 100,%) was calculated, and the durability was determined. The performance was evaluated. In this durability test, 0.1% by weight of azoxylene-4-azo-2-naphthol as a red colorant was added to each ski wax in order to improve the visibility of the remaining ski wax.

[0022]

[Table 1]

When the ski waxes of Examples 1 to 4 were used and the test conditions were changed as follows, the same test as the above test was conducted, and the same effect as that of Examples 1 to 4 was shown. It was Test conditions; weather: cloudy, air temperature: -8 ° C, snow temperature: -6 ° C,
Snow quality: Kawasaki snow

[0024]

EFFECTS OF THE INVENTION The ski wax of the present invention can maintain excellent gliding properties, which are not present in conventional skiwaxes, for a long period of time without being affected by use conditions such as snow quality. Therefore, it can be suitably used not only in alpine competitions but also in general skiing. Further, the ski wax of the present invention is a hydrocarbon-based compound like the conventional paraffin wax, has no practical problems, and has extremely high overall performance that is rich in economy.

Claims (1)

[Claims] 1. A thermal polymer of cyclopentadiene, a thermal copolymer of cyclopentadiene and α-olefins and / or monovinyl aromatic hydrocarbons, a hydride thereof, or a mixture thereof. A ski wax containing a cyclopentadiene-based petroleum resin.