CA2036667C - Artificial snow granule, snow quality improver and method for making the same - Google Patents

Abstract

The present invention provides artificial snow granules comprising a super absorbent polymer as a nucleus, and an ice layer surrounding the nucleus. An aggregate form is provided by linkage of adjacent ice layers and/or granules. A snow granule quality improver, and a method for making the snow granules in granular or aggregate form are also provided. The present products are useful in the skiing industry and have improved qualities over prior art products.

Description

Artificial Snow Granule, Snow Quality Improver And Method For Making The Same The present invention relates t:o artificial snow in granular or aggregate form and a novel method for making the same, and more particularly to artificial snow in granular or aggregate form suitable for skiing. The artificial snow has a particle strucaure similar to that of compact natural snow in granular form. The method of the to present invention comprises absorbing water into a super absorbent polymer in granular form which retains its granular form after absorption of water without the granules sticking to each other, and. freezing the water-swollen super absorbent polymer.
Further, the present invention relates to a snow quality improver to control snow conditions freely so as to provide artificial snow suitable for skiing by blending it with natural snow, artificial snow made by a snow machine or icy snow made by shattering ice blocks to fragments.
2o The invention will be described in greater detail with reference to the accompanying photographs, wherein Photograph No. 1 is a microscopic photograph showing the structure of fresh natural snow in granule form;

Photograph No. 2 is a microscopic photograph showing the structure of compact natural snow;
Photograph No. 3 is a microscopic photograph showing the structure of artificial snow made by use of a water-swellable polymer;
Photograph No. 4 is a microscopic photograph showing the structure of artificial snow made by use of a conventional absorbent polymer;
Photograph No. 5 is a microscopic photograph showing 1o the structure of artificial snow made by use of another conventional absorbent polymer; and Photograph No. 6 is a microscopic photograph showing the structure of artificial snow of the present invention in granular form and an aggregate form of snow granules made by use of a super absorbent po:Lymer of the invention.
- la -',.~'. ,'1 -a In recent years, there have been marked decreases in snowfall and accumulation, as a result, it has been very difficult for many ski areas to remain open. Furthermore, it is necessary to pack the snow on a slope several times by tracksetter in order to prepare a well-groomed packed slope for skiing because newly fallen natural snow is too soft and is not suitable for smooth skiing. On the other hand a tracksetter-groomed trail is not suitable for a ski racing competition and the trail ha:> to be groomed by a method comprising treading the slope underfoot, then spraying water on spread snow.
The snow conditions of runs prepared by such methods are very susceptible to influences from the outside air temperature, and change from compact: snow into corn snow with the passage of time. Said change is caused by the fact that sublimation and condensation of water molecules of snow cause a change in snow granules.
It is.not easy for skiers to slide smoothly on skis on a slope covered by corn snow, and thus frequent grooming, 2o for example, breaking the crust snow, is necessary. These attempts, however, still give poor simulation of natural snow conditions.

2036fifi7 In recent years, installation of snow machines has become popular in many ski areas to prolong the overall skiing season. Conventional snow machines fall into two groups consisting mainly of "gun" type or "fan" type machine.
A method for making artificial snow by use of those snow machines comprises atomizing compressed water into a subzero atmosphere to make fine ice particles with the aid of adiabatic expansion of compressed air or cooling air. The artificial snow thus produced contains 10% by weight or more of water, and has a density of about 0.3 to about 0.4 g/cm3 with a mechanical strength of less 'than about 1 kg/cm2. The slope covered by such artificial snow is still not skiable without being packed. Such artificial snow changes its quality more quickly than natural snow and in certain cases, forms corn snow having an average outer diameter of about 1 to 5 mm in a few days. As mentioned above, corn snow is troublesome to skiers and hence a measure similar to the aforesaid is required to resolve the situation.
The methods for producing artificial snow and apparatus are dislosed in U.S. Patent Nos. 3,716,190, February 13, 1973: 3,010,660, November 28, 1961; 3,301,485, January 31, 1967; 3,298,612, January 17, 1967: 3,761,020, September 25, 1973; 3,774,843, November 27, 1973; 3,774,842, November 27, 1973; 3,945,567, March 23, 1976; 4,004,732, January 25, 1977:
4,083,492, April 11, 1978; 4,105,161, August 8, 1978;

3,733,029, May 15, 1973; Australian Published Patent Applications Nos. 77956/75, August 12, 1976 and 12534/83, September 29, 1983.
Another art references disclose methods comprising supplying water-particles into the .a current of air from a fan (U. S. Patent Nos. 3,760,598, September 25, 1973;
2,968,164, July 12, 1983), freezing the particles with the addition of ice crystals (U. S. Patent No. 3,596,476, August 3, 1971) or bacteria (U.S. Patent No. 4,200,228, April 29, 1980) as a nucleus to accelerate the formation of snow flakes or snow crystals.
International Publication W086,/07373, December 18, 1983 discloses a method for making artificial snow which comprises mixing water with an absorbent material which swells upon absorbing water, and exposing thereafter the resulting water-swollen material to the air followed by freezing. The snow produced thereby has a density of albout 0.4 to 0.9 g/cm3 with a mechanical strength of about 10 to several 100 kg/cm2.
These ranges show that density and mechanical strength of the snow vary widely depending on the conditions of snow being exposed and frozen. Such product has a stiff, fine ice form, i.e. and "Eisbhn" in quality, rather than snow. Therefore, when artificial snow suitable for u;se to cover ski slopes is made from the water-swellable material alone, addition of a surfactant, regulation of particle aizes and water content, and frequent grooming of slopes are necessary to prevent an excessive agglomeration of frozen particles. Such snow is rated among the most difficult snow to handle for ski hill operators. U.S. Patent Nos. 3,247,171, April 19, 1966;
3,022,279, February 20, 1962: 3,022,280, February 20, 1962;
3,251,194, May 17, 1966: GB Published Application No.
2127005, April 4, 1984; and Australian Patent No. 464077, July 19, 1973 disclose the aforesaid absorbent materials.
As snow conditions on ski slopes are susceptible to influences from the weather, indoor artificial skiing slopes have become popular in recent= years. A snow cover for indoor ski slopes is also made by using the above-mentioned artificial snow, artificial ice granules, snow fragments or artificial snow made f~__°om a water absorbent material which swells upon absorbing water. In this instance, the aforesaid problems still remain unsolved.
to Another indoor ski slope is produced by a method comprising covering the slope with a material in paste form which is a mixture of an absorbent polymer with water (blending ratio - about 1/80 to about 1/100), freezing the cover surface of the slope, and subsequently grooming the frozen cover surface by scraping it off to make artificial snow. In addition to the aforesaid problems, such slope has an inherent problem in that planting a ski pole is not easy in this type of snow, because there is an ice layer like "Eisbahn" underneath the artificial snow.
2o Natural fresh fallen snow on ski slopes contains over __ 2036667 90 ~ by volume of a void space and :is not suitable for skiing. Such fresh snow compacted by itself or groomed by a tracksetter is the most appropriate snow for skiing.
Accordingly, microscopic photographs of fresh, compact and artificial snow were compared to one another.
Photograph No. 1, showing granules like stars, is a microscopic photograph of a structure of natural fresh snow in which several parts of the six branches of a snow crystal are narrow so as to form sm<~11 ice beads, some of 1o the adjacent beads aggregating togei=her to form a bottle gourd.
Photograph No. 2 is a microscopic photograph of a structure of natural compact snow which shows no snow granules like stars any more but many bottle gourds formed by aggregation of most of the adjacE~nt ice beads so as to provide a snow aggregate. It is observed that there is still a relatively small amount of ~;roid space but it is distributed uniformly all over among the ice phases of these bottle gourds.
2o Photograph No. 3 is a microscopic photograph of a structure of the aforesaid artifici<~1 snow in which frozen water-swollen polymer granules (black regions) and ice constitute a harmonious whole. The polymer granules can not be distinguished from the ice phase in which water-swollen polymer granules, in bare si=ate, appear on the surfaces of snow granules. Most of the void spaces are unevenly distributed to form large voids (white regions).
This type of snow structure has no ice beads or bottle gourds which exist in the snow, structure of compact natural snow.
1o Photograph No. 4 and 5 are mic~__°oscopic photographs of structures of artificial snow made by freezing conventional absorbent polymers after absorption of water. Photograph No. 4 shows a structure of a conventional water-swollen polymer frozen in the original granular form in a similar way shown in Photograph No. 3. Photograph No. 5 shows a structure of another conventional water-swollen polymer in granular form (spherical regions) frozen in the original swollen form and it seems to have a somewhat different structure from that of the snow shown in Photograph No. 3, 2o but in fact there are many scars (black dendritic regions) on the surface of the polymer granule caused by breaking -r ~, of the ice surrounding the polymer granule and the bare surfaces of the polymer uncovered with ice appear on the surfaces of snow granules. There is little void space in the structure, which is also entire:Ly different from the structure of compact natural snow.
The artificial snow, having structures shown in photographs Nos. 3 to 5, is poorly suited for skiing. The reasons why these structures of artificial snow give poor results are summarized as follows:
1o (a) Such artificial snow, having entirely different structures from that of packed natural snow, may provide rough and fine icy snow, corn snow or snow like "Eisbahn", wherein frozen polymer and ice constitute a harmonious whole. Most of the small void spaces are unevenly distributed so as to give a large void space, or said structure includes little void space and broken polymer granules or granules themselves in bare appearing state on the surfaces of snow granules.
(b) When the absorbent polymer granules in bare state 2o appear on the surfaces of snow granules, friction may increase as a result of direct contact between soles of _ g _ ~r~;

skis and the absorbent polymer.
Because of this, artificial snow in granular or aggregate form, having the structure similar to that of compact snow shown in Photograph No. 2, may provide good snow quality for skiing.
Some of the problems associated with natural snow or artificial snow used to cover ski slopes include the following.
(a) Packing procedures are ne~~essary to prepare well-1o groomed trails for skiing.
(b) It is not easy to make snow having a desired density and strength, i.e. it is difficult to freely adjust the snow conditions to match skier's abilities, performances or preferences.
(c) Snow conditions vary widely with the passage of time. Therefore, it is difficult to maintain the snow quality in good conditions on ski slopes for a relatively long time period.
(d) Investment and maintenance costs for an 2o artificial slope are too expensive.
_ g _ '~,~n (e) Artificial snow produced by freezing water and a water-swollen material forms an ice block. Therefore, crushing of the ice block is required.
Inventors have found that a novel method of the present invention can produce artificial snow in granular or aggregate form having a structure similar to that of compact snow in which said method comprises absorbing water into a super absorbent polymer which can retain its granular form after absorption of water without the io granules sticking to each other, and freezing the water-swollen polymer. Moreover, they have found that when a snow quality improver of the present. invention is blended with natural, artificial or icy snow, snow conditions may be improved freely so as to provide artificial snow suitable for skiing.
An aspect of this invention is artificial snow in granular form comprising a super ab:>orbent polymer in granular form as a nucleus and an ic:e layer surrounding the nucleus.
2o Another aspect of this invention is artificial snow in aggregate form comprising super absorbent polymers as ~~-'~, _ 2036667 nuclei and ice layers surrounding t:he nuclei in which said aggregation is caused by the linkag~s of the adjacent ice layers and/or snow granules.
A further aspect of this invention is a snow quality improver comprising a super absorbent polymer in granular form in which the absorbent polymer has the following characteristics:
(a) the polymer can retain its original granular form after absorption of water without g~_anules sticking to each other;
(b) the polymer has a deionized-water absorbability of 30 to 500 times the weight of thE~ dried polymer;
(c) the polymer has an average particle size of 20 to 500 ~.m before water absorption; and (d) the polymer has an average particle size of 0.05 to 5 mm after water absorption.
Another aspect of this invention is a method for making artificial snow in a granular- form having an average particle size of 0.05 to 5 mm which comprises the steps:
(a) absorbing water into a super absorbent polymer in .,;' -w 2036fi67 granular form which retains its granular form after absorption of water without granule; sticking to each other, has a deionized-water absorbability of 30 to 500 times the weight of-the dried polymer, and has an average particle size of 20 to 500 ~m before water absorption so as to provide a water-swollen polymer having an average particle size of 0.05 to 5 mm; and (b) freezing the water-swollen super absorbent polymer by mixing it with a coolant.
1o Artificial snow in granular or aggregate form of the present invention may be produced by a method comprising absorbing water into a super absorbent polymer in granular form to swell the polymer, and freezing the resulting water-swollen polymer by mixing it with a coolant such as liquid nitrogen, dried ice or liquid carbon dioxide, or placing it in a layer on a substrate cooled below -5°C in a refrigerator.
Inventors of the present invent=ion have found the following facts. When the water-swollen super absorbent 2o polymer in granular form of the present invention is frozen without being exposed to the air in advance, the water absorbed is oozed out of the surface of the granule without breakage of the granule, and at the same time the volume of the granule is decreased. Opon proceeding the freezing process, an ice ~, .?036667 layer surrounding the surface of the granule acts as a nu-clews like an ice bead, around which the artificial snow granule forms. Then, t.wo of the adjacent beads link together through the ice phase to form bottle gourds distributed ho-mogeneously all over fi.he snow structure and as a result,ar-tificial snow in an aggregate form o~f snow granules is pro-vided. At the time, voidspaces are f,istributed homogeneously among the bottle gourds is formed. ~~uch artificial snow in granule or an aggregate form of snow graneles has a struc-ture similar to that of compact natural snow and has been found to be suitable for use to covE;r indoor ski slopes in good conditions for sliding on skis (Photograph No.6).
Although the reasons why the artificial snow similar to compact natural snow is obtained in the present invention have not been necessarily known in details, it is supposed that artificial snow in granule or an aggregate form of snow granules may be produced without any air-exposure steps be-fore freezing, because in the present process fine void spaces distribute automatically and homogeneously all over the structure of the snow aggregate in the course of for-oration of said aggregate. Of course., it is to be understood that the aforesaid process of the present invention is inten ded in an illustrative rather than 9:n a limiting sense.
Photogrph No. 6 is the micros<:opic photograph of a structure of artificial snow of the present invention in granule and an aggregate forms. The photograph shows arti-ficial snow in ice-granule form made by complete cover of the surface of a super absorbent polymer in granule form with an ice layer, and also artificial snow in an aggregate form of snow granules in which there is a void space distri-bated uniformly among bottle gourds formed by aggregation of most of the adjacent ice-granules through the ice phase. In accordance with a field testing, such artificial snow in granule or an aggegate form of snow granules have been found to be most suitable for use to cover indoor ski slopes to give good conditions for sliding on skis.
A super absorbent po 1 ymer i n ~;ranu 1 a form, used f or making artificial snow in granule or an aggregate form in-eludes starch, cellulose, a polymer., a copolymer or a terpol ymer of acrylic acid, acrylic acid salt, methacrylic acid salt, styrene, vinyl Pther and the lilte. Of these (co)poly-mers,a polyacrylic acid salt producE:d by means of a reversed -Phase suspension polymerization in an organic solvent, a vinylalcohol-acrylic acid salt copolymer or a partially saponified isobutylene-malefic anhydride copolymer are most appropriate.
These preferred polymers or copolymers are obtained in a spherical form.
The preferable particle size of the super absorbent .?036667 polymer of the present invention is in a range of about 0.05 mm to 5 mm after water' absorption, with a range of about 20 to 500u m before water absorption. l9hen the particle size is less than about 20I~ m before absorption of water, hard snow is obtained because the particles are too fine. When the narticle size is more than about 50i)u m, artificial snow in corn state is obtained which is unpreferable.
Further, in the present invention a super absorbent polymer in granule form which can retain its original gran-ule form and its flowability even after water absorption without becoming sticky is preferable. An absorbent polymer is also known in the market which bE:comes sticky and pasty when it absorbs water. Such a paste forms a large block of ice when it is frozen,for which such block can not provide a good snow for sl~i slopes unless it is aftertreated. The structure of such snow granules is similar to that shown in Photographs 3 and 4.
In order to keep its granule 'form and good fluidabili-ty of the dried polymer even after water absorption, it is necessary to increase the degree of cure of the polymer by reacting the polymer with a multi-epoxy or multi-amine group -containing curing agent to such an extent that the water absorbability of the polymer matches the above-mentioned range. When the degree of cure is too high, the water absorbability of the polymer decreases unpreferably.

Deionized water ahsorbability ~of the present polymer is in a range of about 30 to 500 times the weight of the dried polymer, preferably about 50 to 200 times the weight of the dried polymer used. then the water ;absorbability is less than about 30 times, the amount of the polymer to be blended is increased uneconomically,and when the water absorbability is more than about 500 times, the gel-strength after water absorption is impaired, and fragility of the water swollen polymers against pressure is increased unpreferably.
In the present super polymer, the amount of water to be absorbed is up to its maximum water absorbability, speci-fically it is about 50 to 100 times the weight of the dried polymer, which is expressed here by ,~ water absorption ratio.
lYhen a soft aggregate of snow granules is desired, a water absorption ratio of about 5 to 50 times the weight of the polymer is appropriate, and when a hard aggregate of snow granules is desired a water absorption ratio of about 30 to 100 times the weight of the dried polymer is preferable.
In the present polymer, a water absorption ratio should be less than it; maximum water absorbability of the polymer, and thus in this way the frozen polymer in granule form still has waterabsorbability. Therefore, the artificial snow can further absorb liquid phase water formed by melting snow under the influence of atmospheric l~emperature, with the result that theski slope can be rel~ained in its original _ 203667 good snow conditions for skiing for a relatively long time period.
However, even when water in an amount exceeding its maximum water absorbability is absorbed by said super absorbent polymer, the water absorbed is oozed out of the polymer granule upon freezing the swollen polymer and an ice layer surrounding completely the surface of the granule forms as a nucleus. The artificial snow thus formed in gran-ule or anaggregate form can further absorb water produced by melting of snow. In this case, the amount of water absorbed by the polymer is about 100 to 120 %. by weight, preferably about 100 to 110% by weight of its maximum water absorb-ability. l9hen water in an amount of over 120 % is absorbed, artificial snow in aggregate form made by freezing said water-swollen polymer has less void space and forms hard and rough snow which is unpreferabe. For example, when hard and heavy snow is desired, about 20 to 1501.~m of a relatively small average size of the dried polymer, and about 30 to 80 of a relatively higher ratio of (wat.er absorbed) / (water absorbability of the dried polymer) are used preferably. On the contrary,,when a soft aggregate of snow granules is de-sired, about 150 to 500 ,u m of a large average size of the dried polymer, and about 10 to 50 of a relatively lower ratio of (water absot~bed)/(water absorbability of the dried poly-mer ) are used pref erab 1 y .

Artificial snow of the present invention has a density of about 0.3 to 0.8g/cm3, and a mechanical strength of about 1 to 20kg/cm2. The mo~:t preferable strength of snow is about 1 kg/cm2 for beginners, and it reaches a strength of about lOkg/cm2 for experts on the order of an international skiing racer. These ranges are included in the present invention, and artificial snow having these ranges may be produced freely by the method of the present invention. Any densities or strengths may be possible, if necessary.
Any method for absorbing water into an absorbent poly-mer may be acceptable. For example, a Cimple method consist-ing of feeding the polymer in granule form into water with stirring followed by allowing to stand for several minutes depending on the desired amount of water to be absorbed.
As the water-swollen polymer can keep water initially absorbed without any water release for a long period of time upon allowing to stand, there is no adverse effect on the water swollen polymer if there is plenty of time (for ex-ample, over about 2 months) before it is frozen. In freezing a water-swollen polymer, any methods such as a manual control device or a machine controlled operation system may be acceptable. Among them,a method for making a snow cover in a plate state which can cover or easily coat indoor ski slopes is recommended wherein said method comprises:
covering or filling up a sheet, plate, wave plate or 2.036667 woven cloth, or a case. panel or box made of plastics, metals or metal-alloys such as aluminium, ceramics, concrete with artificial snow, and then freezing the snow in a layer to give a snow cover prod-act in a plate state. Therefore, ii; is convenient to cover or coat an indoor slope or plain wii;h said snow cover prod-acts in a form which suits to irregularity of the surface of the slope.
In order to unite or adhere the ad3acent snow cover products to each other, any process of making the two covers so as to engage together, any after-processing of the snow covers to make them s~~itable for covering slopes smoothly, or any chemical or mechanical devicE;s to be attached may be accept-able in the manufacturing stages.
Dlaterials for making a ski slope and/or flat base for artificial snow are not limited to earths, concrete, metals, woods, plastics, ceramics and the lil!;e. Thermal insulators, refrigerating or cooling system may be equipped with. When the indoor skiing is maintained in good conditions for a long term, it is recommended to install a thermal insulating, cooling or refrigerating system.
To prevent slipping of the snow cover on the surface of slope, any mechanical or chemical dE:vices may be acceptable to he equipped with.
In one preferable embodiment, a method of the present 2036 6~7 invention comprises:
covering an indoor snow ski slope with the hard arti-ficial snow covers of the present invention as a continuous snow cover; and coating said snow covers in an appropriate depth with powdery artificial snow of the present invention.
By using said method, an indoor slope having a good conditions for skiing can be made w(th no problems aforesaid including difficulty of sticking stocks into the snow. Such ski slopes created by this method are equivalent to natural ski slopes in skiing or sliding performance.
Regeneration of a super absorbent, polymer of the pres-ent invention may be possible, if nc:cessary,in which the re-generation process includes the step of separation of snow, water and soils from the polymer followed by drying the re-covered polymer for reuse. It is environmentally safe to dispose the old polymer because the super polymer itself is light-degradable and biodegradable. However, if early deg-radation of the waste particles is desired , an addition, blending, impregnation or coating of such a chemical selected from the group consisting of accerel'.ators, catalysts, or ad-ditives for promoting light degradai;ion or biodegradation of the particles may be effective for l;he purposes.
As the polymer particles are free from danger to human health,it is also preferable to select chemicals for the purpose of taking the safety into consideration.
Artificial snow in granule or an aggregate form of the present invention may be mono- and/or mufti-colored with known pigments or dy~tuffs.The colored snow looks beautiful, and a commercial value may be added to the artificial snow.
For example, each slope for beginners, experts or intermediate skiers may be covered by a different cot.ored artificial snow to add more fun.
In the present artificial snow in granule or an aggre-gate form as well as a super absorbent polymer of the pres-ent invention, various additives can be used, in so far as they do not deviate from the gist of the present invention.
Examples of such additives include perfumes, odorants,aromas to give~odor. Further, other additives such as antioxidants, ultraviolet absorbers, fluorescent ;~dditives,bacteria to ac-cerelate the formation of snow crystals, nuclei, extending agents, friction improvers,and the like may be added, blend-ed,coated or impregnated to a super absopbent polymer of the invention.
Any known methods may be used :for freezing the water-swollen absorbent polymer of the invention. Examples of such usable methods include a method comprising mixing the poly-mer with dried ice, liquid nitrogen, liquid air, liquid carbon dioxide follov~ed by freezing the resulting mixture, a method comprising freezing the polymer placed on metal pipes or sheets cooled by use of a cooling medium,a method comprising freezing the polymer in a refrigerator, and a method com-prising making snow by use of a snow machine or~ a machine for producing snow. hlost preferred method may be adopted depending on the use of the snow obtained.
The method for p~~oducing snow in granule form or powder snow is different from the method far producing snow in an a ggregate form.
Hhen snow in granule form or powder snow is desirable, the method comprising directly mixing a water-swollen poly-mer with dried ice, liquid nitrogen, liquid air, liquid carbon dioxide followed by rapid freezing of the resulting mixture is preferable rather than the method comprising making snow by using a snow machine or a machine for producing snow.
A more preferable method comprises mixing directly a water-swollen polymer with powdery or crushed dried ice. Any amount of these coolants and any length of time may be acceptable.
Preferable temperature of snow produced is within the range of about 0 to - 30°C depending on the purpose of the use of snow. It is preferable to proceed rapidly and homogeneously freezing process because a mixing state varies with the size of dried ice or mixing velocity.
The method comprising freezing' the polymer by use of liquid nitrogen, liquid air, liquid c:aubon dioxide or equiv-alent as a coolant may be useful because such coolant in liquid phase car. be mixed easily with a water-swollen absorbent polymer with the result that said water-swollen absorbent polymer may be frozen rapidly and effectively with the aid of latent heat of these coolants. Although other similar liquid phase coolants may bE: also acceptable, above-mentioned liquid phase coolant or coolants are more prefer-able and practical because of excellent cooling capability, inexpensiveness, availability, and :simple handling thereof.
In one of preferred embodiment:; of the invention, a method comprises:
absorbing water into a super absorbent polymer in gra-pule form having particle sizes of about 20 to 500,u m before water absorption and a deionized-water absorbability of 30 to 500 times the weight of the drieel poylmer, and a non-ad-hering property after absorption of water without losing its original granular form after water absorption, swelling the polymer until the polymer granule having an average par-title size of about 0.05 to 5 mm is obtained, mixing (or without mixing) the water-swollen polymer with natural snow, artificial snow made by use of a snow machine or icy snow made by bursting ice blocks into fragments, followed by freezing the resulting mixture by mixing it with liquid carbon dioxide.
Conventional liquid phase carbon dioxide may be accept-able. Carbon dioxide has a latent heat of evaporation of 5.1 2C1366G~
Kcal./ kg at 30 °C, 4~.1 Kcal./ kg at 10°C , 56.1 kcal./kg at 0 °C and hence may be used for cooling and effectively freezing a water-swollen super absorbent polymer of the in-vention.
Liquid carbon dioxide is obtained by liquefaction of vapor phase carbon dioxide at a pressure of about 40 atm.
Resources of carbon dioxide are off-gases from liquefied natural gas, ammonium, petroleum refining or ethylene pro-duction facilities. Other off-gases or' tail gases evolved in petrochemical plants or steel works may be used as the source.
The method for making snow in a.n aggregate form of snow granules comprises absorbing water into a super absorbent polymer in granule form having a particle size of about 20 to 500, m before water absorption anal a deionized-water absorbability of 30 to 500 times the: weight of the dried polymer, and a uon-adhering property after absorption of water without losing its original granular form,swelling the polymer until the polymer granules having an average parti-cle size of about 0.05 to 5 mm is obtained, mixing (or' with-out mixing)the water-swollen polymer with snow selected from the group consisting of natural snow,artificial snow made by use of a snow machine, icy snow made by crushing ice blocks, and/or with dried ice, followed by freezing the resulting mixture.

2~0366fi7 In another embodiment, a method for making snow cover products is provided which comprises freezing water-swollen super absorbent iuolymer placed in a layer on a substrate such as pipe, sheet or plate by using a coolant at a temper-ature of below about -40°C . A lower temperature range gives harder snow.
Further in another embodiment of the present invention, a method is provided which comprises freezing a water-swollen super absorbent polymer in a layer having a thick-ness of under 6 cm in a refrigerator cooled at a temperature of about - 5 to -30 °C .
Artificial snow made by freezing a water-swollen absorbent polymer or a mixture of said polymer with natural snow or dried ice in a layer having a thickness of over about 6 mm in a refrigerator at a temperature of - 5 to - 30°C does not have an aggregate form of snow articles but an ice block form like "Eisbahn" which does not suit for use to cover artificial ski slopes as well as for use as an artificial continuous snow cover on indoor ski slopes with-out pre-treatment before using.
Judging from the fact that the upper part of the layer contains snow in aggregate form in some extent but lower part thereof is formed mainly from ice block, in which case said ice block like "Eisbahn" seems to be formed by action of the gravitation. Therefore, when freezing a mixture of 20366~~
the water-swollen polymer with natural snow or dried ice in a layer, the thickness of said layer is no more than 6 cm, preferably about 2 to 4 cm.
Any method for freezing a water'-swollen super absorbent polymer in a layer to make snow cover products is acceptable in the invention. Examples of such method include manual or automatic operation by use of a machine, However, a method comprising freezing the artificial snow in an aggregate form of the invention in a layer on or in a sheet, wave or corru-gated sheet, woven fabric, case, panel, box or the eqivalent made of plastics, metals or metal alloys such as aluminum, ceramics, concrete, cement, and wood is preferred so as to provide snow cover products in a plate state suitable for use to cover indoor ski slopes.
Any refrigeration facilities having a refrigeration ca-pacity may be acceptable which are capable of water-swollen polymer placed in a layer at a temperature of about -5 to -30 °C. Examples of such facilities include a mobile refrig-erator trailer (van),a fixed refrigerator and the like.
Any known method for mixing the water-swollen super absorbent polymer in granule form with natural snow and / or dried ice may be used.A blend ratio in weight of the polymer to snow is in a range of 99:1 to 50 . 50, preferably 99 . 2 to 70 . 30 depending on the use being proposed. Powdered or crushed dried ice may be preferred as a coolant.

20366~~
Further, the present invention provides a snow quality improver which is able to improve snow conditions freely so as to give snow most suitable for sh:iing by blending said improver with natural snow, artificial snow or icy snow.
The snow quality improver of the invention comprises a super absorbent polymer having a non-sticky properties after vt~ater absorption without sticking to each other, a deionized grater absorbability of about 30 to 50U times the weight of the dried polymer,a particle size of about 20 to 500,u m and a particle size of about 0.05 to 5mm after water absorption.
A water-swollen polymer having water in advance 5 to 100 times the weight of the dried polymer may be preferable, providing the water content is not necessarily limited to the range.
The reasons why a snow quality improver in granule form is preferred are as follows:
(a) easy to blend with snow homogeneouly;
(b) " ice bridges" among snow granules produced are dispersed homogeneously and not too hard; and (c) exposed polymer granules on the snow surface have not an adverse effect on good sliding on skis because said polymer granules have a spherical form.
The preferable particle size of said snow quality im-prover of the invention is in a range of about 0.05mm to 5mm after water absorption, and with a ranke of about 20 to about 203fi6fi7 500 ,u m before water absorption to give a homogeneous mix-ture with snow. When the particle size is under about 20u m, it is difficult to obtain a homogeneous mixture with snow, because the particles are too fine. On the contrary, if the particle size is more than about 500~u m,larger particles are mixed with snow in an isolated state unpreferably, Deionized-water absorbability of said snow quality improver is in a range of about 30 t.o 500 times, preferably about 50 to about 200 times the weight of the dried polymer used. When the water absorbability is under about 30 times, the amount of the improver to be blended is increased un-economically, and when the water absorbability is over 500 times, the gel-strength after water absorption is impaired, and fragility of the water-swollen i:mprover against pressure is increased unpreferably.
A preferable blending ratio of the present snow quality improver to 100 parts by weight of natural snow, artificial snow made by a snow machine or icy snow made by bursting or crushing ice blocks is about 0.1 to 1(!.0 parts by weight.
To obtain artificial snow having a desired density or strength, about 0.1 to 10.0 parts b;r weight of the present snow quality improver in dried statf: are blended with 100 parts by weight of snow so as to absorb water in an amount of about 5 to 100 times the weight of the dried iroprover within the upper limits of about 201) parts by weight of the water-swollen improves.
It is observed under a microscope that when the artific ial snow containing a snow quality improves in granule form of the invention is frozen by a latent heat of the snow and cooling air, water inside the granules is oozed out of the water swollen granules and frozen on the surfaces of gra-nules so as to form "icE: bridges" among snow granules.
The inventors have found that when the amount of water oozed out of the water'-swollen granules is properly cont-rolled, i.e. when the number of "ice bridges" is adjusted, artificial snow having a desired density or strength is ob-to ined. That is; by varying parameters such as an average particle size of improver,the ratio of (water absorbed) /
(water absorbability of the improver).and parts by weight of the water-swollen snow quality improves and the like, the amount of water oozed out of the granules may be controlled with a result that artificial snow having any desired den-sits or strength may be obtained.
For example, when hard and heavy snow is desired, about 20 to 150 a m of a relatively smaller average particle size of the improves in granule form about 30 to 80 of relatively higher ratio of(water absorbed)/(water absorbahility of the improver),and about 30 to 200 parts by weight of a relative-ly higher amount of water-swollen granules are used prefera-bly. On the contrary, when a soft aggregate of snow granules .....

is desired, about 150 to 500,u m of ;~ large average particles ize of the improver in granule form about 10 to 50 of a relatively lower ratio of (water absorbed) / (water absor-ability of the imprower), and about 10 to 80 parts by weight ~f a relatively lower amount of water-swollen granules are used pref erzb 1 y .
Further, it has now been found that in order to retain the original snow quality for a lon;~er term, the water absorption ratio should be less than the water absorbability of the dried improver or enhancer, in which case, the water-swollen improver or enhancer granul~as still have some water absorbability. Therefore, they can further absorb liquid phase water formed by melting snow 'under the influence of atmospheric temperature, with the r~asult that the ski slope can retain its original good conditions for skiing through a relatively longer term.
In general, the snow newly prepared by use of a snow machine is a mixture of about 60 to 90 % by weight of ice particles with about 40 to 10 % of liquid phase water. Such wet snow is troublesome for beginners or intermediate skiers to slide on ski~.When a snow quality improver of the present invention in granule form is blended with such snow, the wet snow changes itself into dry powder snow much suitable for sliding on skis for beginners or intermediate skiers.
In an early spring or a warmer sunny day in a winter, for example, when snow becomes so-called wet snow containing liquid phase water, such degradation of snow (wet snow) can be prevented effectively by blending said snow quality improver in granule form of the present invention with said wet snow.
An amount of a snow quality imp~rover to 100 parts of snow is in a range of about 0.1 to 10.0 parts by weight, preferably in a range of about 1.0 to about 10.0 parts by weight for remarkably wet snow, whereas a preferable range for slightly wet snow is about 0.1 to 1.0 parts by weight.
Any known methods for mixing the snow improver of the invention with snow may be applied for. Among them, a method has been provided wherein the snow quality improver contain-ed in a~vessel Pquipped with a spreading or distributing means underneath carried on a maintenance track and the like are spread over skiing area or ski slopes through a nozzle means attached to said device, and mixed with snow during maintenance operation for ski area or ski slopes. In such method, both natural snow and artificial snow may be used.
A gun-type or fa~~-type snow machine equipped with means capable of spreading or distributing over said snow quality improver in granule form by the aid of compressed air can be used in which the granules are spread simultaneously with spreading artificial snow.
Another blending method comprises the step of mixing said improver in granuleform transferred by the aid of air flow to a snow machine with hot or cold water, and then spreading the hater-swollengranules into the air by using compressed air simultaneously with spreading of artificial snow made by the snow machine to give a snow mixture.
Regeneration of said snow quality improver of the pre-sent invention may be possible, if necessary, in which the regeneration process includes a step of separation of snow, water and soils from the improver followed by drying the re-covered polymer for reuse. It is environmentally safe to dispose the used improver because tlhe improver itself is light-degradable and biodegradable. However, if early degra-elation of the waste ganules is desirable, an addition, blend-ing, impregnation or coating of one of chemicals selected from the group consisting of accerelators, catalysts or ad-ditives for promoting light degradation or hiodegradation of the garnules may be effective.
As the improver granules are free from danger for human health, it is preferable to select the chemicals for this purpose taking the safety into consideration. The snow qual-ity improver of the present invention may ba colored with known pigments or dystuffs.
As an aggregate of snow granules made from a colored improver looks beautiful, and a commercial value may be added to the snow aggregate. For example, a discrimination of ski runs by coloration for beginners, intermediate skiers or ex-perts may add a more fun.
Further, other additives such as antioxidants, ultra-~~~iolet absorbers, flusorescent additives and/or bacteria to accerelate the formation of~snow crystals, nuclei, extending agents,friction improrers,and the like may be added, blended, coated or impregnated to the snow quality imprnver of the present invention.
The invention is further illusi;rated by the following examples which are set forth by way of illustration only and not by way of limitation.
Performance test procedures in the examples are as follows:
Deionized water absorbability About 0.5 grams of a dried super absorbent polymer in granule form are dispersed in 1000 ml of deionized-water and allowed to stand for about 24 hrs, followed by filtration through a 60-mesh wire net. The water-swollen polymer gran-ales are weighed to determine the weight (W). The weight of dried granules = Wo.
Absurbabilities (Table 1) are 'then calculated as follows:
W
Absorbability -Wo Flowability after water absorption About 1.0 grams of a dried super absorbent polymer are added to about 50m1 of deionized-water to absorb completely.
Flowabilities (Table 1) are evaluated visually under gentle vibration and reported as O X or D .
Density of frozen artificial snow Frozen snow with known volume is weighed and then den-cities (Table I) are calculated as grams of frozen snow per volumes(cm3) of said snow. When the snow is hard, the volume calculated by measuring dimensions of a snow cube made by~
cutting frozen snow is used instead.
Strength of frozen at~tificial snow Release a disk in an adapter to fall straight on the sample snow. Repeat the procedure by use of a "Kinoshita hardness tester" (trade name), changing the adapter so that the disk sinks to depth of about 7 to 30 mm under the snow.
Calculate the strength by use of a conversion table. The feeling of snow is denoted, for example, by "powdery".
Preparation of super absorbent polymer in granule form A 500 ml-separable flash equipped with a stirrer, a reflex condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, was charged wit:h 150 grams of deionized -water, followed by addition of 0.2 grams of a partially sa-ponified polyvinyl alcohol (trade name GH-23, made by Nippon 203fi667 Syn. Chemical Co.,Ltd.). After melting the contents, the flask was purged with a nitrogen stream.
Separately, an Erlenmyer flask was charged with 22.5 grams of a mixed ester of lauryl acrylate and dodecyl acryl-ate(trade name LTA, made by Osaka Organic Chem.Co,Ltd.),10.0 grams of hydroxyethyl methacrylate, 17,5 grams of methyl-methacrylate,l.0 grams of azobis dimethyl valeronitrile,and the resulting solution was added dropwise into the above separable flask for about an hour under a bubbling of nitro-gen. The heating was continued until the reaction neared completion while the contents were maintained at about 65 °C
for 5 hours after cooling, and the resulting solids were filtered, washed, dried in vacuo to give a dispersant in bead state.
A 1000 ml-separable flask was charged with 360.7 grams of n-hexane,4.32 grams of the above-mentioned dispersant,and the resulting mixture was heated to 50°C to dissolve the dispersant and the atmosphere was replaced with nitrogen.
Separately, 72.0 grams of acrylic acid was partially neutralized with 32.2 grams of natrium hydroxide dissolved in 103.6 grams of deionized-water and 0.24grams of potassium persulphate were added at the room temperature. The resulting monomer solution was added dropwise to the above-mentioned separable flask with stirring of 300 r.p.m over a period of I hour under the bubbling of nitrogen. After refluxing fon~ 2 -....
?.036667 hrs., 0.1 grams of 30% hydrogen peroxide solution was added and the refluxing was continued for a period of 1 hr. to com-plete the polymerization. Thereafter, 0.73 grams of ethylne-glycol diglycidylether were added, ;end the contents was de-hydrated by azeotropic distillation, filtered and dried in vacuo so as to give a super absorbent polymer in white bead state.
The super absorbent polymer in bead form obtained had an average particle size of about 100 ,u m with a good flow-ability. Plhen absorbing water with stirring at the room tem-perature for 19 seconds,a water-swollen polymer in bead form having water 50 times the dried poymer and an average parti-cle size of about 0.4 mm with a good flowability was ob-tained. The resulting polymer beads could retain the water without releasing water even after allowing them to stand at the room temperature.
The deioni~ed-water absorbability was 100 times the weight of the dried polymer. Table 1 shows conventional absorbent polymers and some of the super absorbent polymers of the present invention which are denoted by "PQ Polymer", their particle sizes, and water absorbabilities.
Example 1 Preparation of artificial snow in granule and an aggregate form hater-swollen polymers in granule form made from conventional absorbent polymers (see the follo~~ing table) in which case each of the water-swollen polymer (at about 19 °C) have water 50 times the dried weight of the polymer and a water-swollen absorbent polymer made from a super absorb-ent polymer of the invention (trade name PQ Polymer-BL-100) were filled fully individually in a wooden box, and freozen at a temperature of about - 30°C for' a period of about 1 to 2 hrs. so as to give artificial snow in granule or an aggre-gate form. The following table give~> the results.
Absorbent Polymers Absorption Artificial Snow in granula form Ratio DE;nsity Strength ( t i mes ) (,~/cm~__( Kg/cm2 ) PQ Polymer BL-100 50 (1.5 10 Aqualic CA-19 50 (1.8 at least 20 at least Sumica Gel S-50 50 (1.8 at lest 20 at least Parma Snow Polymer 50 (1.8 at least 20 at least Photographs attached are the transmission-type micro-scopic photographs (X=15) of the structures of these artifi-cial snow in granule or an aggregatE; form.
Photograph No. 6 is the microscopic photograph of a structure of the artificial snow in granule and an aggregate forms of the present invention made from PQ Polymer BL-100 -3?-in which ice layers surrounding completely the frozen absorbent polymer granules forms together ice granules which aggregate each other so as to give bottle gourds, among them fine, precise voidspaces being distributing uniformly all over. There is a close resemblance between the granule struc-ture of this artificial snow and the one of packed natural snow.
On the other hand, Photograph No. 3 is the microscopic photograph of an artificial snow made from Parma Snow (trade mark) polymer in which frozen water-swollen polymer granules (black regions) and ice constitute a harmonious whole and the polymer granules can not be distinguished from the ice phase. In this case, water-swollen polymer granules in bare state appears on the surfaces of snow granules and most of t he void spaces are unevenly distribvuted in a large void (white regions). There are no bottle gourds formed from ice beads which ex it in the natural snow in an aggregate form.
Such astructure is entirely different from that of compact natural snow.
Photograph No. 4 is the microscopic photograph of an artificial snow made from Aqualic CA-W (trade name) in which frozen water-swollen polymer granules(black regions) and ice constitute a harmonious whole and the polymer granules can not distinguish from the ice phase. The snow structure seems like the structure shown in Photograph 3 as a whole.

Photograph No.5 is the microscopic photograph of a structure of artificial snow made from Sumica-gel S-50(trade name) in which water-swollen polymer granules (spherical re-gions) has been frozen as it is.The artificial snow seems to have somewhat different structure from that of snow shown in Photograph No. 3, but in fact there are many scars on the surface (black dendritic regions) ~of the polymer granule caused by breakage of the ice surru:nding the polymer granule and bare surfaces of the polymer granules uncovered with ice appear on the surfaces of snow graneles.There is little void space in the structure. The structure is also entirely dif-ferent from the one of compact natural snow.
After storing the artificial snow in an aggregate form made from PQ Polymer BL-100 at about - 1°C , changes in appearances with the passage of time are observed. The orig-final state of the freshly prepared snow aggregate could re-lain intact.
Example 2 Preparation of artificial snow (1) in an aggregate form After placing dried ice under an aluminum plate having a thickness of 5 cm. cooled to below -40°C , a water-swollen super absorbent polymer(at about 19°C) in bead form was pla ced on the plate over an area 10 cm. X 10 cm., and frozen at the room temperature of -8.3°C for ;~ period of about 1 to 2 hrs. 'fable 2 gives the results.The microscopic photograph of the structure of this snow in an aggregate form is given in Photograph No. 6.
Changes of the external appearance with the passage of time at -1°C were observed visually. The appearance of the polymer freshly prepared could still be retained after about a month.
Example 3 Preparation of artificial snow (2) in ranule form A water-swollen super absorbent polymer in bead form having water 50 times the weight of the dried polymer (at about 19°C) in a quantity of 100 parts by weight was mixed with over 60 parts by weight of dried ice in granule form and resulting mixture was frozen at a room temperature of -8.3°C for 155 minutes with stirring using mechanical mixer (trade name Hitachi Band-mixer HF-330, made by Hitachi Co., Ltd.) so as to give artificial snow in granule form. Table 3 shows the results. Photograph No. 6 gives the microscopic structure of the snow granules. Changes of the external appearnce with the passage of time at -1°C were observed visually. Upon allowing to stand, the appearance of the snow freshly prepared could still be retained after about one month.

Example 4 Colored artificial snow in an aggregate form A water-swollen super absorbent polymer (made from PQ
BL-100) in bead form colored pink with a dystuff and having water 50 times the weight of the dried polymer (at about 19 °C) was frozen according to Example 3 so as to give powdery artificial snow in an aggregate form.Art.ificial snow vividly colored pink was obtained.
Example 5 Colored and odored artificial snow in an aggregate form A water-swollen super absorbent polymer (made from PQ
BL-100) in bead form colored pink with a dystuff and odored with a perfume of rose, having water 50 times the weight of the dried polymer (at about 19°C) was frozen according to Example 3 so as to give powdery artificial snow in an aggre-gate form. Artificial snow vividly colored pink and having an odor of rose was obtained.
Example 6 Preparation of artificial snow in an aggregate form (3) A water-swollen super absorbent polymer in bead form having water 50 times the weight of tire dried polymer (at about 19°C) in a quantity of 100 parts by weight was mixed with 100parts by weight of liquid carbon dioxide and result-ing mixture was frozen at. a room temperature of - 8.3 °C for about 155 minutes. with stirring by using a mechanical mixer Grade name Hitachi Hand-mixer HF-330,made by Hitachi and Co.,Ltd.)so as to give artificial snow in an aggregate form.
Powdery artificial snow having a density of 0.33 g/cm3 and a temperature of -9.7 °C was obtained.
A mixture of a water-swollen super absorbent polymer in granule form having water 50 times the weight of the dried polymer (at about 19°C ) with icy snow (blending ratio of 25:
75) in a quant-ity of 100 parts by weight was mixed with 200 parts by weight of liquid carbon dioxide and resulting mix-ture was frozen in a similar manner for about one minutes with stirring so as to give artificial snow. Powdery artifi-vial snow having a density of 0.31 g/cm3 and a temperature of -10°C was obtained. Photograph No. 6 shows the microscopic structure of the snow granules. Changes of the external ap-pearance with the passage of time at -1 °C were observed visually. The apperaance of the polymer freshly prepared could still be retained after about one month.
Example 7 Preparation of artificial snow covers used to cover ski slope A water-swollen super absorbent polymer in granule form obtained in the method aforesaid which has water of about 50 2036fifi7 times the weight of the dried polymer at about 19 °C , or a mixture of said polymer with icy snow or dried ice was fill-ed fully in a wooden hox having a dimension of 3 cm depth,30 cm length and 20 cm width, and the contents were frozen at a temperature of about -30°C in a refrigirator fora period of about 1 to 2 hrs. to give artificial snow covers used to be cover ski slopes. Photograph No. 6 gives the microscopic structure of the snow granules.
The snow was allowed to stand .at a temperature of - 0°C
for about one month, and changes with the passage of time were observed. The initial state of snow could be retained intact even after about one month.
Comparative exam lp a 1 A water swollen super absorbent polymer in granule form in Example 6 or a mixture of said polymer with icy snow or dried ice was filled fully in a wooden box having a dimen-lion of 20 cm width, 30cm length, 6 cm. depth arid in a con-ventional basket in fully, and frozen in a refrigerator at a temperature of -30°C for about 1 to~ 2 hrs. As the results, artificial snow in an aggregate form was not obtained, but an ice block or a crust of snow in "Eisbahn" state was ob-tamed.

e~036667 Example 8 Creation of artificial snow slope for skiing About 20 kg of dried ice in fine fragments were scatter ed over a wooden ski slope covered Writh a foamed polystyrene {3cm thickness)comprising a~slope sE:ction (about 40cm width, a tilt angle of 10 deg.,about 4 m lE:ngth and a plain section of about 2 m length) continuously extending from said slope section. Thereafter, the dried ice layer was covered all over with the snow covers made in Example 6 (about 20 cm width, abort 30cm len~th, about 3.3 em thickness each)so as to make a continuous snow coyer on the slope.
Separately, a mixture of about 100 parts by weight of a water swollen super absorbent polymer in granule form hav-ing water 50 times the weight of the dried polymer with 60 parts by weight of dried ice in fragments were frozen with stirring for about 5 minutes at a room temperature of -8.3 °C . The continuous snow cover aforesaid was covered with the resulting powdery and crispy artificial snow all over in de-pth of ahout 4 cm to make an artificial snow slope for ski-ing. The sliding conditions for skiing on the slope were evaluated at an outside temperaturE: of about 21 °C and a temperature of the snow of about -:l0 to -30 °C. The snow conditions for skiing on the artificial slope were found to ue excellent anal sliding accerelation properties were essen-tially the same as that of tha slope covered with natural 203fi667 powder snow. The excellent sliding conditions for skiing could still be retained even when a temperature of the snow varied widely from about - 10 to - 30 °C and even after the surface snow became partially gelatinaized by melting.
It was difficult for a skier to~ step up the slope with-out using ski poles. Ilowever,a ski pole firmly sticking to the snow was possible. The skis's edges gripped firmly in the snow and the artificial snow under the skis gave a sound "SQUEAKING" when treading by skis on the snow. When the sur-face of the artificial snow was partially melted and formed a gel, an addition of dried ice in fragments could make the surface powdery in snow quality again. The repetition of the process could keep the slope in good skiing conditions for a longer term.
The evaluation was repeated by using commercial absorbent polymers, for example, Aqualic CA-W, Sumica Gel S-50 and Parma Snow Polymer. 1'he resulting snow was icy and the sliding properties on that snow were poor.
Example 9 Type of super absorbent polymer used to make snow guality improver Water-swollen super absorbent polymer in granule form having a water content of 50 times the weight of the dried super absorbent polymer (snow quality improver) was blended 203fi6fi7 with icy snow (about 16 mesh) made by crushing an ice block into fragments in a weight ratio of 33 . 100, followed by freezing at -5°C. After 16 hrs., the densities and strengths of the snow compositions were measured. Table 1 shows the results. The microscopic photograph of the structure of this artificial snow in an aggregate form was similar to that shown in Photograph No. 6 (as well as the snow obtained in the following Examples).
Example 10 Average particle diameter of snow Quality improver The same procedure of Example SI was repeated to give an artificial snow except that average particle diameter of the super absorbent polymer in granule 'form was changed.
Table 6 shows the results.
Example 11 Water absorbability of snow Quality improver The same procedure of Example 9 was repeated to give artificial snow except that water absorbability of the super absorbent polymer was changed. Table 7 gives the results.
Example 12 Weight ratio of snow QualitYimprover 20~666~
The same procedure of Example 9 was repeated to give artificial snow except that weight ratio of the water-swol-1 en polymer to icy snow was changed. The results are shown in Table 8.
Example 13 Sliding test on a slope at Teine Ski Area in Hokkaido(Japan) An artificial ski slope(3 meter:> width, l5 meters length, l5cm depth)was covered with a homogeneous mixture of about33 parts by weight of a water-swollen super absorbent polymer in granule form(made from "PQ Polymer BL-151",trade name) containing water about 50times the weight of the dried poly-mer and~about 100 parts by weight of natural snow. After all owing to stand for about 14 hrs at -5 to -12°C ,the density, strength and suitability for sliding were measured and eval-uated. Table 9 gives the results.
Example 14 Super absorbent polymer before water absorption A super absorbent polymer before water absorption was blended with icy snow made by crushing an ice block (about IG mesh passing) and a change of th.e density as well as the strength with the passage of time were measured after stor-age at about -1 °C. The results arE; shown in Table 10.

2.436667 Example 15 Colored super absorbent polymer Icy snow (16 mesh) made by bursting ice blocks into fragments was blended in a weight ratio of 33 . 100 with a water-swollen super absorbent polymer colored pink with an artificial dystuff wherein said polymer contained water 50 times the weight of the dried polymE:r.When freezing the mix-tore, artificial snow lightly colored pink was obtained. The density and strength ~,ere the same as those obtained in Ex-ample 9.

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Claims (27)

1. An artificial snow granule comprising:
a nucleus consisting of a super absorbent polymer in granular form; and an ice layer surrounding said nucleus.

2. The artificial snow granule according to claim 1, wherein said super absorbent polymer retains its original granular form after water absorption without granules sticking to each other, has a deionized-water absorbability of 30 to 500 times the weight of the dry polymer, has an average particle size of 20 to 500 µm before water absorption, and has an average particle size of 0.05 to 5 mm after water absorption.

3. The artificial snow granule according to claim 1 or 2, wherein said super absorbent polymer has an average particle size of 0.05 to 5 mm after water absorption, and a weight ratio of ice to said super absorbent polymer is 5 to 100.

4. The artificial snow granule according to claim 1, 2 or 3, wherein said super absorbent. polymer is selected from the group consisting of light degradable polymers and biodegradable polymers.

5. The artificial snow granule according to claim 1, 2 or 3, wherein said super absorbent. polymer is selected from the group consisting of polyacrylic acid salts, vinyl alcohol-acrylic acid salt copolymer;, and saponified isobutylene-maleic anhydride copolymers.

6. The artificial snow granule according to any one of claims 1 to 5, wherein said super absorbent polymer is either odored or colored.

7. The artificial snow granule according to any one of claims 1 to 6, wherein said granule constitutes a component of a mixture with a component selected from the group consisting of natural snow, conventional artificial snow and icy snow.

8. Artificial snow of snow granules in an aggregate form, said artificial snow comprising:
a plurality of nuclei each of which is a super absorbent polymer in granule form; and ice layers surrounding said nuclei;
wherein the artificial snow is aggregated by linkage of adjacent ice layers.

9. The artificial snow in an .aggregate form of snow granules according to claim 8, wherein said aggregate constitutes a component of a mixture with a component selected from the group consisting of natural snow, conventional artificial snow and icy snow.

10. The artificial snow in an aggregate form of snow granules according to claim 8 or 9, wherein said super absorbent polymer:
retains its original granular form after water absorption without granules sticking to each other;
has a deionized water absorbability of 30 to 500 times the weight of the dry polymer;
has an average particle size of 20 to 500 um before water absorption; and has an average particle size of 0.05 to 5 mm after water absorption.

11. The artificial snow in an aggregate form of snow granules according to claim 8, 9 or 10, wherein said super absorbent polymer has an average particle size of 0.05 to 5 mm after water absorption and a weight ratio of ice to said super absorbent polymer is 5 to 100.

12. The artificial snow in an aggregate form of snow granules according to any one of claims 8 to 11, wherein said super absorbent polymer is selected from the group consisting of light degradable polymers and biodegradable polymers.

13. The artificial snow in an aggregate form of snow granules according to any one of claims 8 to 11, wherein said super absorbent polymer is selected from the group consisting of polyacrylic acid salts, vinyl alcohol-acrylic acid salt copolymers and saponified isobutylene-maleic anhydride copolymers.

14. The artificial snow in an aggregate form of snow granules according to any one of claims 8 to 13, wherein said super absorbent polymer is either odored or colored.

15. A snow quality improver comprising a super absorbent polymer in granular form wherein said super absorbent polymer has the following characteristics:
(a) said polymer retains its original granular form after water absorption without granules sticking to each other;
(b) said polymer has a deionized-water absorbability of 30 to 500 times the weight of the dry polymer;

(c) said polymer has an average particle size of 20 to 500 um before water absorption; and (d) said polymer has an average particle size of 0.05 to 5 mm after water absorption.

16. The snow quality improver according to claim 15, wherein said super absorbent polymer is a water-swollen super absorbent polymer.

17. The snow quality improver according to claim 15, wherein said super absorbent polymer is a dry super water absorbent polymer.

18. The snow quality improver according to claim 15, 16 or 17, wherein said super absorbent polymer is either light-degradable or biodegradable.

19. The snow quality improver according to claim 15, wherein said super absorbent polymer is selected from the group consisting of acrylic acid salt polymers, vinyl alcohol-acrylic acid salt copolymers and saponified isobutylene anhydride copolymers.

20. The snow quality improver according to any one of claims 15 to 19, wherein said super absorbent polymer is either odored or colored.

21. A method for making artificial snow in granular form having an average particle size of 0.05 to 5 mm which method comprises the steps:
(a) absorbing water into a super absorbent polymer in granular form which retains the granular form after absorption of water without granules sticking to each other, has a deionized-water absorbability of 30 to 500 times the weight of the dry polymer, and has an average particle size of 20 to 500 µm before water absorption so as to provide a water-swollen super absorbent polymer having an average particle size of 0.05 to 5 mm; and (b) freezing said water-swollen super absorbent polymer while mixing the polymer with a coolant with stirring.

22. The method for making artificial snow in granular form according to claim 21, wherein said coolant is selected from the group consisting of dry ice, liquid nitrogen, liquid air and liquid carbon dioxide.

23. The method for making artificial snow in granular form according to claim 21 or 22, wherein said method comprises the steps:
blending said water-swollen super absorbent polymer with natural snow, artificial snow made by a snow machine or icy snow made by shattering ice blocks into fragments; and freezing the resulting mixture.

24. The method for making artificial snow in granular form according to claim 21, 22 or 23, wherein said super absorbent polymer is selected from the group consisting of acrylic acid salt polymers, vinyl alcohol-acrylic acid salt copolymers and saponified isobutylene-maleic anhydride copolymers.

25. A method for making an artificial snow cover used to cover ski slopes which method comprises the steps:
(a) absorbing water in a super absorbent polymer in granular form which retains the original granular form after absorption of water without granules sticking to each other, has a deionized-water absorbability of 30 to 500 times the weight of the dried polymer, and has an average particle size of 20 to 500 µm before water absorption so as to give a water swollen polymer having an average particle size of 0.05 to 5 mm; and (b) freezing said water-swollen super absorbent polymer.

26. The method for making an artificial snow cover used to cover ski slopes according to claim 25, wherein said freezing is carried out by freezing said water-swollen super absorbent polymer on a substrate, which is cooled by use of a coolant.

27. The method for making an artificial snow cover used to cover ski slopes according to claim 25, wherein said freezing is carried out by freezing said water-swollen super absorbent polymer in a layer having a thickness of 6 cm or less.