JPH0525465A - Artificial snow seed and production of artificial snow - Google Patents

Abstract

PURPOSE:To provide artificial snow seeds which can be made into an excellent artificial snow free from defects of conventional artificial snow, especially an artificial snow suited for a slope of an indoor skiing ground and a process for producing an artificial snow by using the same. CONSTITUTION:Artificial snow seeds comprising highly water-absorptive resin flakes which can remain flaky and nonsticky even after absorption of water, has a water absorptivity of 30-500 times for deionized water and has specified lengths before and after absorption of water. These seeds after absorption of water are frozen with dry ice, liquefied carbon dioxide or the like, and the frozen seeds can be used as such as an artificial snow.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial snow species made of highly water-absorbent resin strips and a method for producing artificial snow.
More specifically, it is a piece of artificial snow that is swollen by absorbing water or swelling it with water-absorbent resin pieces that are non-adhesive to each other and retain their shape even after absorbing water. If not, it is related to the seeds of artificial snow that can be made into strip-shaped or darts-like artificial snow by freezing it and freezing it, and the artificial snow manufacturing method using it. Snow can control snow quality and make it suitable for skiing. Furthermore, it has photodegradability and / or biodegradability, and has a fragrance and / or
It also relates to colored artificial snow species.

[0002]

[Prior art]

(Natural snow) In recent years, the amount of snow has decreased year by year, which has hindered the opening of ski areas. Moreover, the natural snow on the ground is too soft and the skis are not slippery. As it is, it is not suitable as a slope, so you have to compress the snow many times with a snow plow. In addition, compression with a snow crusher is not suitable for competitions, and people adopt the "pots" that are only stepped on by shoes or a method of spraying water on the snow. The slope made up in this way is greatly affected by the temperature of the outside air, and the quality of snow changes with the passage of time. This is because sublimation / condensation occurs inside the snow and the change of the snow crystals progresses, and progresses from "snow snow" to "rough snow." Rough snow is very slippery snow for skiers, and therefore, the work of breaking the snow, that is, grooming must be frequently performed, but it is still not sufficiently effective.

(Artificial Snow) Recently, artificial snowfall devices have been actively introduced even at ski resorts in Japan in order to speed up or extend the gliding season. There are roughly two types of artificial snowfall devices, a gun type and a fan type. The method of making snow with these devices is a method of making fine ice by using adiabatic expansion of compressed air of high-pressure water in the atmosphere at 0 ° C. or lower, or by using cold air. The artificial snow thus made contains 10% or more of water and has a density of 0.3.
~0.4g / cm ^3, the strength is at 1Kg / cm ² or less, not suitable for skiing to be compacted snow. In addition, compared with natural snow, such snow has a rapid change in snow quality, and after several days, it may progress to rough snow with an outer diameter of about 1 to 5 mm. As described above, rough snow is a troublesome snow quality for skis, and the same measures as those described above are taken. In addition, an artificial snowmaking machine that freezes water into ice blocks and crushes it by physical impact to form ice particles or snowflakes is also introduced, but this is also a troublesome snow quality such as shaved ice or rough snow. There is a drawback that can only be obtained, and the same measures as described above are taken. In addition, Japanese Patent Publication No. 2-3663
In the case of artificial snow made by mixing (absorbing water) a water-swellable material (water-absorbent resin) and aerating and then freezing as disclosed in Japanese Patent Publication No. 5, the density and strength of the snow are aerated. The density tends to vary depending on the conditions and freezing conditions, and the density is 0.4 to 0.9.
g / cm ³ and strength of 10 to several 100 kg / cm ² . Rather than snow, such snow is more like lumpy ice or ice burn. Those in the same state as ice burn have to be subjected to physical impact as described above to be crushed into ice particles or snowflakes, and only rough snowflakes are obtained. Therefore, when making artificial snow only with water-swellable materials, in order to make it suitable for skiing, add surfactants or adjust the particle size and water absorption ratio so that frozen particles do not combine more than necessary. And grooming must be done frequently. It can be said that such snow is very difficult for ski resorts to use.

Further, since the outdoor ski area is affected by the weather, the indoor ski area that can be used throughout the four seasons is becoming more popular. An artificial ski slope in an indoor ski resort is also made by arranging artificial snow, artificial ice particles, snowflakes, etc., or artificial snow made from a water-swellable material (water-absorbent resin) and water on an artificial slope. However, indoor ski resorts constructed by these methods also have the same problem as described above. In addition, the water-swellable material (water-absorbent resin) and water are mixed in an artificial slope of an indoor ski resort (weight ratio, about 1/80 to
There is also an artificial slope where a 1/100) paste-like thing is arranged, and once the entire surface is frozen like a skating rink, only the surface is groomed and the ice is scraped off to make artificial snow. In addition to the above-mentioned problems even in the indoor ski resorts built by this method, there is also a problem that the stock does not stand because there is an ice layer like ice bun under artificial snow.
Further, the water-absorbent resin granules developed by the present inventors are used to absorb water with or without water absorption, and natural snow, or artificial snow made by an artificial snowfall device or artificial snowmaking machine is used. Although the above problem can be solved by using artificial snow made by mixing with frozen ice and freezing, artificial snow made by this method is suitable for outdoor use, and when used in indoor ski areas, it is natural snow. What is desired is one that can easily obtain excellent artificial snow by simply freezing it without mixing it with artificial snow or ice made by other methods, and that can easily maintain a slope suitable for skiing.

[0005]

Conventional natural snow and artificial snow have the following problems, and are not suitable for the slopes of indoor ski resorts. You have to squeeze. You can't get snow of any density and intensity, depending on the skier's level and taste. It is difficult to maintain the condition of the slope because the snow quality changes significantly over time. High slope construction and maintenance costs. It must be mixed with various types of snow such as natural snow and artificial snow. Artificial snow made by freezing from a water-swellable material (water-absorbent resin) and water becomes ice blocks, so it must be crushed once.

[0006]

As a result of intensive studies conducted by the present inventors to solve the conventional problems, the first object of the present invention is to keep them in a strip shape even after absorbing water and to prevent them from sticking to each other. The present invention provides highly water-absorbent resin strips that are water-soluble, or strip-shaped artificial snow species that have been made to absorb water and swollen. Alternatively, it can be made into falling snow-like artificial snow, and the artificial snow is suitable for indoor skiing slopes without the above problems. Further, a second object of the present invention is to provide an artificial snow species which is photodegradable and / or biodegradable and which is scented and / or colored. Further, a third object of the present invention is to provide a method for producing artificial snow by freezing striped artificial snow species that have been made to absorb water and swollen.

[0007] The invention of claim 1 of the present invention is an artificial snow species consisting of highly water-absorbent resin strips having the following characteristics. Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, have a water absorption capacity for deionized water of 30 to 500 times, a longer length of the strips before water absorption is 50 to 5000 μm, The longer length is 0.1-10 mm. The invention according to claim 2 of the present invention is the artificial snow species according to claim 1, wherein water is absorbed 5 to 100 times in advance. The invention of claim 3 of the present invention is the artificial snow species according to claim 1, which has not been previously made to absorb water. The invention according to claim 4 of the present invention is the artificial snow species according to claim 1, which has photodegradability and / or biodegradability. The invention according to claim 5 of the present invention is the artificial snow species according to claim 1, which is aromatized and / or colored.
The invention of claim 6 of the present invention is characterized in that the highly water-absorbent resin strip is contained in an aqueous solution of a monomer containing acrylic acid and an ammonium salt of acrylic acid or an alkali metal salt in an amount of 0.1 to 10% by weight.
A cross-linked highly water-absorbent resin obtained by adding a polyvalent organic metal ion cross-linking agent, polymerizing in an aqueous solution, and drying.
Alternatively, a crosslinked highly water-absorbing material obtained by post-crosslinking a copolymer of acrylic acid and an ammonium salt or an alkali metal salt of acrylic acid with 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent. The artificial snow species according to claim 1, which is a resin.

The invention of claim 7 of the present invention is a method for manufacturing artificial snow, which comprises the following steps (a) and (b). (A) Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, have a water absorption capacity of about 30 to 500 times against deionized water, and have a long length of the strips before absorption of 50 to 5000 μm. A step of allowing the water-absorbent resin strip to absorb water and swelling until the long side of the strip becomes 0.1 to 10 mm. (B) A step of mixing the swollen super absorbent polymer strip with liquefied carbonic acid and freezing. The invention of claim 8 of the present invention is a method for manufacturing artificial snow, which includes the following steps (a), (b) and (c). (A) Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, have a water absorption capacity of about 30 to 500 times against deionized water, and have a long length of the strips before absorption of 50 to 5000 μm. A step of allowing the water-absorbent resin strip to absorb water and swelling until the long side of the strip becomes 0.1 to 10 mm. (B) A step of mixing the swollen superabsorbent resin particles with natural snow, artificial snow made by an artificial snowfall device, or ice snow obtained by crushing ice blocks. (C) A step of mixing the mixture with liquefied carbonic acid and freezing. In the invention of claim 9 of the present invention, the highly water-absorbent resin strip is 0.1 to 10% by weight in an aqueous solution of a monomer containing acrylic acid and an ammonium salt of acrylic acid or an alkali metal salt.
A cross-linked highly water-absorbent resin obtained by adding a polyvalent organic metal ion cross-linking agent, polymerizing in an aqueous solution, and drying.
Alternatively, a crosslinked highly water-absorbing material obtained by post-crosslinking a copolymer of acrylic acid and an ammonium salt or an alkali metal salt of acrylic acid with 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent. It is a resin, It is a manufacturing method of the artificial snow of Claim 7 and 8 characterized by the above-mentioned.

The super absorbent resin used in the present invention includes:
Examples include starch-based, cellulose-based, acrylamide, acrylic acid, acrylic acid, methacrylic acid, styrene, vinyl ether, and other polymers, copolymers, terpolymers, and other synthetic resin-based materials. In an aqueous solution of a monomer containing an acid and an ammonium salt or an alkali metal salt of acrylic acid,
A moderately crosslinked superabsorbent resin obtained by adding 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent, polymerizing in an aqueous solution, and drying, or an ammonium salt of acrylic acid and acrylic acid, or an alkali metal. It is preferable that the moderately cross-linked highly water-absorbent resin is obtained by post-crosslinking a copolymer with a salt with 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent.

The cross-linking agent may be methylene bis acrylamide, diglycidyl ether or the like, but the use of the above polyvalent organic metal ion cross-linking agent is preferable because it improves gel strength, tackiness, water absorption capacity, water retention capacity and the like. Aluminum acetate normal salt as a polyvalent organic metal ion cross-linking agent: AL (CH ₃ CO ₂ ) ₃ , basic salt: AL (OH) (CH ₃ CO ₂ ) ₂ , AL ₂ O
_{(CH 3 CO 2) 4,} AL (CH 3 CO 2) 3 · 2ALO (CH 3 CO 2) , and the like. The alkali metal is an alkali metal such as potassium, sodium or lithium and is not particularly limited. In order to maintain the fluidity in the form of strips even after the superabsorbent resin used in the present invention has absorbed water, and to make them non-adhesive to each other, it is sufficient to increase the degree of crosslinking using these crosslinking agents. However, if water is cross-linked too much, the water absorption capacity will decrease, so it is important to adjust the amount of the cross-linking agent so that the water absorption becomes appropriate.

The superabsorbent resin used in the present invention is in the form of a strip, and the longer length of the strip before water absorption is 50 to 5.
000 μm, the longer length of the strip after absorbing water is 0.1 to 1
It is preferably about 0 mm. If the longer length of the strip is less than about 50 μm before absorbing water, it will be too fine and the artificial snow will become too hard, and if it is over 5000 μm, the artificial snow will be rough, which is not preferable. The reason why the strip-shaped highly water-absorbent resin is preferable is that it is easy to handle, artificial snow obtained by freezing also becomes strip-shaped, does not deteriorate ski skiing, and is easily mixed with natural snow. It is believed that the super absorbent polymer used in the present invention retains fluidity in the form of strips even after absorbing water, because the amount of adhering water between the adsorbed strips is small and the particles slip with each other to form voids. Be done. Some superabsorbent resins become paste-like when they absorb water, but when they become paste-like, they become one big ice mass when frozen and cannot be used as artificial snow for skis unless they are crushed finely. This artificial snow is not preferable because it is difficult to maintain it suitable for skiing as described above.

The artificial snow obtained by freezing the water-absorbed artificial snow species of the present invention is finely and uniformly dispersed depending on the freezing method, the size of the flakes, the water absorption capacity, the water absorption capacity, etc. For example, a "falling geese-like" confectionery can be created where the strips are lightly adhered to each other. The superabsorbent resin used in the present invention has a water absorption capacity of 30 to 5 for deionized water.
00 times, preferably 50 to 200 times. When the water absorption capacity is less than 30 times, the water absorption capacity of the artificial snow obtained is low, so that it becomes difficult to absorb the liquid water generated by melting the artificial snow and maintain the desired snow quality. On the other hand, 500
If it is more than twice, the gel strength when absorbing water is weak and it is easily broken when pressure is applied, which is not preferable. The artificial snow species of the present invention may or may not have been previously absorbed. The amount of water absorbed is usually not more than the maximum water retention capacity of the superabsorbent resin, and in some cases, may be not less than the maximum water retention capacity of the superabsorbent resin. When it is more than the maximum water retention amount, it is about 100 to 120% of the maximum water retention amount. The water absorption ratio is about 5 to 100 times. It is preferably about 5 to 50 times when obtaining soft artificial snow, and about 30 to 100 times when obtaining hard artificial snow. The artificial snow of the present invention still has a water absorption capacity, and it is possible to maintain the quality of the snow under the target conditions without changing by absorbing the liquid water generated by the melting of the artificial snow due to a rise in the outside temperature.

For example, if you want to obtain hard and heavy snow quality,
Before absorption of water, the longer length of the strip is as small as 50 to 1000 μm, and the ratio of water absorption capacity / water absorption capacity is large (30 to 80 μm).
%) On the contrary, when it is desired to obtain soft and light snow, the longer length of the strip before water absorption is as large as 500 to 5000 μm, and the ratio of water absorption capacity / water absorption capacity is small (10 to 50 μm).
%)do it. The density of the artificial snow of the present invention is about 0.3-
0.8 (g / cm ³ ), strength about 1-20 (Kg / cm
² ) For general skiers, the slippery strength is about 1 Kg / cm ² for beginners, and as it progresses, it shifts to hard snow, and for an athlete of the Olympic class, hard snow of about 10 Kg / cm ² or more is required. The density and strength of the artificial snow of the present invention include these ranges, and artificial snow having any density and strength can be used as necessary. Any method may be used for allowing the superabsorbent resin to absorb water. For example, it is sufficient to put the strip into stirred water and leave it for a few minutes depending on the water absorption capacity. The water absorption rate is affected by the water temperature, and at low temperatures the water absorption rate is slow,
Since the higher the temperature, the faster the temperature tends to be. Therefore, when the water temperature is, for example, 10 ° C. or lower, it is desirable to appropriately heat and absorb the water. Even if the superabsorbent resin that has absorbed water is left at room temperature as it is, it does not release water and can be kept stable for a long time, so even if there is a certain period of time before it is frozen and artificial snow is made (for example, (1 hour or more) There is no particular adverse effect. Since the highly water-absorbent resin itself is water-absorbent, it is desirable to store it in a closed container so that it does not absorb moisture when it is stored.

The method of freezing the artificial snow species of the present invention is not particularly limited. Using dry ice, liquid nitrogen, liquid air, liquefied carbonic acid, etc., a method of freezing by stirring in a known manner, a method of cooling by placing on a metal pipe or sheet cooled by a refrigerant, Any method such as using an artificial snowfall machine or an artificial snowmaking machine may be used. Since the artificial snow quality changes depending on the freezing method, it is preferable to select a freezing method that can obtain the desired snow quality. The reason why the artificial snow of the present invention can be produced without aeration is not clear, but water absorption, swelling, and freezing of an artificial snow species consisting of highly water-absorbent resin strips make it hard to have the above density and strength. It can make snow and soft, light artificial snow without the need for artificial aeration. The method of freezing using liquid nitrogen, liquid air, liquefied carbonic acid, etc. is easy to mix with the superabsorbent resin fine particles swollen by swelling due to the fact that they are liquids. This is a preferable method because the artificial snow species can be frozen efficiently in time. Other than liquid nitrogen, liquid air, liquefied carbonic acid, etc., any substance having the same effect can be used. However, among these, the use of liquefied carbonic acid is preferable from the viewpoints of freezing effect, economical efficiency, easy availability, easy handling, and the like. In order to produce artificial snow by the method of the present invention, first, after absorbing water, they remain in the form of strips and are non-adhesive to each other, and have a water absorption capacity for deionized water of about 30.
~ 500 times, the longer length of the strip before water absorption is 50-50
The superabsorbent resin strip having a size of 00 μm is allowed to absorb water, and the strip is swollen until the longer length thereof becomes 0.1 to 10 mm, and then the swollen superabsorbent resin strip is used as it is, Alternatively, natural snow, artificial snow made by an artificial snowfall device, or ice lumps are mixed with crushed ice snow, and then mixed with liquefied carbonic acid and frozen.

Commercially available liquefied carbonic acid can be used. The latent heat of vaporization of liquefied carbonic acid is 15.1 Kcal at 30 ° C.
/ Kg, 48.1Kcal / Kg at 10 ℃, 56.1Kcal at 0 ℃
/ Kg, etc., and can be effectively used for cooling and freezing. Liquefied carbonic acid is produced by compressing and cooling carbon dioxide to approximately 40 atm, and the sources of carbon dioxide are offgas from natural gas and ammonia plants, offgas from petroleum refining and ethylene decomposition, and other chemicals. There are surplus gas and by-product gas from manufacturers and steel manufacturers, and any of them can be used. The method of mixing and freezing the liquefied carbonic acid and the super absorbent polymer particles swollen by absorbing water, and arranging the obtained free-flowing artificial snow on the slope of an artificial ski resort can be done manually or by using a machine. It is also possible to use an automatic method. The above-mentioned artificial snowfall machine or artificial snowmaking machine may be used, but preferably a method of rapidly freezing while stirring and mixing with liquefied carbonic acid under direct contact is used. The amount of liquefied carbonic acid and the mixing time are not particularly limited. The temperature of the frozen artificial snow is preferably set to about 0 to −30 ° C., but it depends on various conditions and is appropriately selected.

A known method can be used as a method of mixing the highly water-absorbent resin particles swollen by water absorption with natural snow or the like. The mixing ratio of both is 99/1 to 1/99 by weight,
It is preferably 99/2 to 20/80, and is appropriately selected depending on the purpose of use. The artificial snow made from the artificial snow species of the present invention can be used as it is for a slope. An artificial ski resort can be easily constructed by using it alone, and it is also easy to maintain. However, natural snow, artificial snow produced by methods other than the present invention, ice snow, and the like may be appropriately mixed and used. The mixing ratio may be arbitrary. When making a ski slope, for example, if you put a "falling geese-like thing" underneath and put a "free-flowing thing" on it and construct each with an appropriate thickness, it is suitable for skis without the above problems. It is possible to build a slope and there is no problem such as stock not standing. The artificial snow species of the present invention can be separated and collected by an appropriate method, dried, and reused.
Since the artificial snow species of the present invention itself have photodegradability and biodegradability, there is no problem in discarding after use, but especially when early photodegradation or biodegradation is desired, the artificial snow of the present invention is used. The seed may be blended, added, impregnated or coated with a known accelerator, catalyst, additive or the like for photodegradation or biodegradation. Since the artificial snow species of the present invention itself is safe for the human body, it is preferable to select these additives in consideration of safety.

The artificial snow species of the present invention may be colored by a known method using a pigment, a dye or the like. Artificial snow made from colored artificial snow species is beautifully colored and can add new commercial value. For example, the ski can be used more effectively because it can be used for distinguishing the ski slope for advanced skiers, the ski slope for beginners, etc. by color. Perfume can be added to the artificial snow species of the present invention using known perfumes, aromatic agents, fragrances, etc. to add new commercial value. Antioxidants, ultraviolet absorbers, fluorescent agents, nucleating agents, extenders, substances having a low coefficient of friction, other additives and the like added to the artificial snow species of the present invention within a range that does not impair the gist of the present invention, blending, It may be applied or impregnated.

[0018]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
The water absorption capacity, fluidity, density and strength of artificial snow after freezing in the following examples are determined by the following operations. (Water absorption capacity for deionized water) 0.5 g of the dried polymer was dispersed in 1 liter of deionized water and left standing for 24 hours.
Weight (W) of water swelling body obtained by filtration with 0 mesh wire mesh
Is measured, and this value is obtained by dividing this value by the initial dry polymer (W ₀ ). (Fluidity after Water Absorption) After adding 50 cc of deionized water to 1.0 g of dry polymer to absorb water completely, the water swelling body was observed while moving, and the fluidity was indicated by ◯, ×, and Δ. The angle of repose was measured. (Density of artificial snow after freezing) The snow of which the volume is known is taken out, weighed, and the weight is divided by the volume. Unit is g / cm
³ . When the snow is soft, a thin stainless steel box with a known internal volume can be inserted into the snow to remove the snow with a known volume. In the case of hard snow, cut the snow into squares with a saw and measure the dimensions with a ruler to calculate the volume.

(Strength of artificial snow after freezing) With a Kinoshita hardness meter, a weight is dropped on the artificial snow to measure the drop strength.
The unit is kg / cm ² . Replace the adapter so that the disk sinks into the artificial snow within 7 to 30 mm, and calculate the strength from the conversion table.
In the case of light snow, it was expressed by touch. (Synthesis example of super absorbent resin strip) Acrylic acid (14.4 g) was dissolved in deionized water (6.0 g), and 96% potassium hydroxide (8.18 g) was added thereto to prepare a 70% partially neutralized solution of acrylic acid. Prepared. This basic aluminum acetate (manufactured by Wako Pure Chemical Industries, Ltd., Chemical for) 0.688 g was added and thoroughly stirred to prepare a homogeneous slurry solution, 2,2 from warmed to 50 ° C., as initiator ^'- azobis 0.04 g of (2-amidinopropane) hydrochloride dissolved in 0.5 g of deionized water was added. This solution was transferred into a Teflon box container preheated to 75 ° C. to initiate polymerization. The polymerization reaction proceeded promptly in about 2 minutes, and most of the water was evaporated by the heat of polymerization. Then, the temperature was raised to 100 ° C., and the mixture was heated for 2 hours and dried to obtain a porous white solid powdery polymer. 0.5 g of a nonionic surfactant and 1.0 g of hydrotalcite were added to 10 g of the powdery polymer, which was further heat treated at 100 ° C. for 2 hours and pulverized to obtain a strip-shaped water-absorbing polymer.

Example 1 In the above-mentioned strip-shaped highly water-absorbent resin, the longer length of the strip before water absorption is 20 to 1000 μm.
And shows excellent fluidity. The water absorption capacity for deionized water is 197 times, the water absorption speed is 7 seconds, and the bulk density of the swollen body that has absorbed water 50 times by stirring in normal temperature water is 0.65.
And also showed excellent fluidity. The longer length of the strip after absorbing water is 60 to 3000 μm. The water-absorbed strip-shaped highly water-absorbent resin was left standing at room temperature for 1 hour or more, but could be stably held without being discharged. (Example 2): Production example 1 of artificial snow: Dry ice was placed under an aluminum plate having a thickness of 1 mm, cooled to -40 ° C or lower, and then swollen by absorbing water 50 times on the plate and swelling. A water absorbent resin (temperature: about 19 ° C.) was placed (10 cm × 10 cm) and frozen at room temperature of −8.3 ° C. for about 1-2 hours. As a result, layer thickness 28-31m
m, a density of 0.41 g / cm ³ , and a strength of about 5 Kg / cm ² were obtained. The artificial snow thus obtained was stored at -1 ° C and examined for changes over time, but the state immediately after the production was still maintained even after one month.

Example 3 Manufacture example 2 of artificial snow 2 The above-mentioned strip-shaped highly water-absorbent resin 10 absorbed and swollen with water 50 times.
0 parts by weight and 60 parts by weight or more of strip-shaped dry ice,
A hand mixer for home use (Hitachi Hand Mixer HF-330) was mixed for 155 minutes at room temperature of -8.3 ° C, and the mixture was frozen to prepare artificial snow. As a result, the density is 0.33 g /
cm ³ of free-flowing artificial snow was obtained. The artificial snow thus obtained was stored at -1 ° C and examined for changes over time, but the state immediately after the production was still maintained even after one month. (Example 4) (Colored artificial snow) The above-mentioned strip-shaped highly water-absorbent resin was made to absorb 50 times of water to form a water swelling body, which was impregnated with a pink dye and colored, and Example 3 was used. I made artificial snow that was frozen and free flowing in the same manner as in. Beautiful snow colored pink. (Example 5) (Artificial snow colored and perfumed) The above-mentioned strip-shaped superabsorbent resin was made to absorb 50 times water to form a water swelling body and impregnated with a pink dye and a fragrance with a rose scent. What was colored and perfumed was frozen and free-flowing artificial snow was made in the same manner as in Example 3. Beautiful snow with pink color and rose scent was created.

Example 6 Production Example 3 of Artificial Snow 100 parts by weight of the above-mentioned strip-shaped super absorbent resin strips absorbed by water 50 times and swollen and 100 parts by weight of liquefied carbonic acid were -8.3 ° C.
Container with a mixer at room temperature (Hitachi Hand Mixer HF-
330) was mixed and frozen for about 1 minute to produce artificial snow. The free-flowing artificial snow had a density of 0.33 g / cm ³ and a temperature of −9.7 ° C. Mixture of highly water-absorbent resin particles swollen with 50 times water and ice and snow (weight ratio 25/75) 100
Approximately 1 part by weight of liquefied carbonic acid and 200 parts by weight of the same method
It was mixed and frozen for a minute to make artificial snow. Density 0.3
It was free-flowing artificial snow at 1 g / cm3 and a temperature of -10 ° C. Each of the obtained artificial snows was stored at -1 ° C and examined for changes over time, but the state immediately after the production was still maintained even after one month.

[0023]

INDUSTRIAL APPLICABILITY The present invention is a highly water-absorbent resin strip capable of producing excellent artificial snow which is improved from the drawbacks of conventional natural snow and artificial snow, especially artificial snow suitable for the slopes of indoor ski areas. The present invention provides an artificial snow species consisting of and an artificial snow manufacturing method using the same. It is possible to freeze the absorbed artificial snow species with dry ice or liquefied carbonic acid, and make it as it is.This artificial snow does not have to be pressed and the snow quality does not change over time, so the condition of the slope can be maintained. It can be made easier, cheaper and easier to handle. The artificial snow species of the present invention can be recovered and reused. Further, the present invention has photodegradability and / or biodegradability,
Provided are artificial snow species that are free from pollution problems after use and artificial snow species that are colored and / or perfumed.

   ─────────────────────────────────────────────────── ─── Continued front page    (71) Applicant 000221627             Tonen Chemical Co., Ltd.             4-1-1 Tsukiji, Chuo-ku, Tokyo (71) Applicant 391014088             Masahisa Otsuka             2-15-17 Jonouchi, Oizumi-cho, Ora-gun, Gunma Prefecture (71) Applicant 000001889             Sanyo Electric Co., Ltd.             2-18 Keihan Hondori, Moriguchi City, Osaka Prefecture (72) Inventor Yuichiro Miura             1-10-34 Jingumae, Shibuya-ku, Tokyo (72) Inventor Kazuo Hirano             1-1-1 Hitotsubashi, Chiyoda-ku, Tokyo East             In Moe Co., Ltd. (72) Inventor Taiji Kamibayashi             6-4 Kuranomiyacho, Yamatotakada City, Nara Prefecture (72) Takayuki Nate             4-1-1 Tsukiji, Chuo-ku, Tokyo Tonika             Gaku Co., Ltd. (72) Inventor Masataka Otsuka             2-15-17 Jonouchi, Oizumi-cho, Ora-gun, Gunma Prefecture (72) Inventor Toshitake Nagai             Sanyo, 2-18, Keihanhondori, Moriguchi City, Osaka Prefecture             Electric Co., Ltd.

Claims (9)

[Claims] 1. An artificial snow species consisting of highly water-absorbent resin strips having the following characteristics. Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, the water absorption capacity for deionized water is 30 to 500 times, the longer length of the strips before water absorption is 50 to 5000 μm, The longer length is 0.1-10 mm. 2. The artificial snow species according to claim 1, wherein water is absorbed 5 to 100 times in advance. 3. The artificial snow species according to claim 1, which has not been previously absorbed with water. 4. The artificial snow species according to claim 1, which has photodegradability and / or biodegradability. 5. The artificial snow species according to claim 1, which is aromatized and / or colored. 6. A highly water-absorbent resin strip is prepared by adding 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent to an aqueous solution of a monomer containing acrylic acid and an ammonium salt of acrylic acid or an alkali metal salt. 0.1-10% by weight of polyvalent organic metal in a cross-linked highly water-absorbent resin obtained by polymerizing with an aqueous solution and drying, or a copolymer of acrylic acid and ammonium salt of acrylic acid or alkali metal salt. The artificial snow species according to claim 1, which is a cross-linked highly water-absorbent resin obtained by post-cross-linking with an ionic cross-linking agent. 7. A method for manufacturing artificial snow, which comprises the following steps (a) and (b): (A) Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, have a water absorption capacity of about 30 to 500 times against deionized water, and have a long length of the strips before absorption of 50 to 5000 μm. A step of allowing the water-absorbent resin strip to absorb water and swelling until the long side of the strip becomes 0.1 to 10 mm. (B) A step of mixing the swollen super absorbent polymer strip with liquefied carbonic acid and freezing. 8. A method for manufacturing artificial snow, which comprises the following steps (a), (b) and (c): (A) Even after absorbing water, they remain in the form of strips and are non-adhesive to each other, have a water absorption capacity of about 30 to 500 times against deionized water, and have a long length of the strips before absorption of 50 to 5000 μm. A step of allowing the water-absorbent resin strip to absorb water and swelling until the long side of the strip becomes 0.1 to 10 mm. (B) A step of mixing the swollen superabsorbent resin particles with natural snow, artificial snow made by an artificial snowfall device, or ice snow obtained by crushing ice blocks. (C) A step of mixing the mixture with liquefied carbonic acid and freezing. 9. A highly water-absorbent resin strip is prepared by adding 0.1 to 10% by weight of a polyvalent organic metal ion crosslinking agent to an aqueous solution of a monomer containing acrylic acid and an ammonium salt of acrylic acid or an alkali metal salt. 0.1-10% by weight of polyvalent organic metal in a cross-linked highly water-absorbent resin obtained by polymerizing with an aqueous solution and drying, or a copolymer of acrylic acid and ammonium salt of acrylic acid or alkali metal salt. The method for producing artificial snow according to claim 7 or 8, which is a crosslinked superabsorbent resin obtained by postcrosslinking using an ionic crosslinking agent.