JPH07300538A - Sintered hydrophilic moisture-permeable porous object of olefin polymer and refrigerator using same - Google Patents

Abstract

PURPOSE:To obtain the title object having high mechanical strengths and an excellent flexibility at a low cost by sintering a powder which is prepd. by soaking the surface layers of particles of a specific ethylene polymer with a specific surfactant to a high concn. CONSTITUTION:This object is obtd. by sintering a powder which is prepd. by soaking the surface layers of 100 pts.wt. particles of an olefin polymer having a density of 0.90-0.965g/ml, a melt index of 0.01-1.0g/10min, and an n-hexane extract of 10wt.% or lower with 1.5-2.5 pts.wt. sodium salt of a carboxylated polyoxyethylene alkyl ether of the formula (wherein m is 13-18; and n is 3-6) to a high concn. this object, low in cost and excellent in mechanical strengths, flexibility, retention of hydrophilicity, safety, antibacterial properties, and deodorizing effect and its retention, is suitable as a material for a high-humidity chilled room for food storage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic moisture-permeable porous olefin polymer sintered body and a refrigerator using the same, and more particularly to a high-humidity chilled chamber effective for storing highly hydrous foods. Particularly suitable hydrophilic moisture-permeable porous olefin polymer sintered body and method for producing the same, a high humidity chilled chamber having the sintered body as a part of its structure, a refrigerator incorporating the same and the high humidity chilled chamber or the refrigerator It relates to the method of storing food used.

[0002]

2. Description of the Related Art Since a porous sintered body produced by sintering a powder of an olefin polymer, for example, an ethylene polymer has air permeability, it has hitherto been used as a sheet, a plate, a pipe, a rod or a molded body. It has been used as a filter, an absorbent, a cushioning material, a carrier, a foaming material, an air diffuser, and the like. However, since the ethylene polymer is hydrophobic, it does not exhibit its function in applications requiring hydrophilicity, for example, a moisture permeable filter, a foaming material or a carrier used in water or a polar solution, and improvement is desired. It was

A method for imparting hydrophilicity to a porous sintered body produced from an ethylene resin is described in, for example, JP-A-57-57.
There is a method of sulfonation of a sintered porous body made of a polyolefin resin, as disclosed in Japanese Patent No. 109837, but oleum of fuming sulfuric acid, anhydrous sulfuric acid, hot concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide, etc. is sulfonated. Since it is used as an agent, not only the cost is increased, but also the working environment is deteriorated, and the resulting porous body is deteriorated by a strong acid, resulting in low mechanical strength. Therefore, in order to prevent this deterioration, high-density polyethylene must be selected as the material,
When flexibility or flexibility is required, the above material cannot be used, and there is no alternative but to use the medium and low density polyethylene at the sacrifice of the decrease in mechanical strength. The above-mentioned JP-A-5
7-109837 discloses another hydrophilizing method, such as a method of preliminarily wetting the surface of the porous body with an aqueous liquid such as alcohol and a method of treating with a surfactant, but these are temporary. However, it is also mentioned in the above publication that it has not been radically solved.

On the other hand, a high-humidity chilled chamber using the above-mentioned porous body and a refrigerator incorporating the same are known, but those porous bodies have a high cost or have a problem of hydrophilic sustainability. It was not possible to deal with the case where flexibility is required, and these solutions were desired.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention has been made in consideration of such circumstances and has low cost, high mechanical strength, excellent flexibility and flexibility, and durability and safety of hydrophilic effect. Highly hydrophilic hydrophilic moisture-permeable porous olefin-based polymer sintered body, hydrophilic moisture-permeable porous olefin having excellent mold resistance and deodorant properties in addition to the above-mentioned excellent properties (EN) Provided are a polymer-based polymer sintered body, a method for producing the same, and a high-humidity chilled chamber having the sintered body as a part of its structure and a refrigerator including the same. Another object of the present invention is to provide a method for preserving foods, especially highly hydrous foods, which utilizes these high humidity chilled rooms or refrigerators.

[0006]

The present inventors have heretofore found that when a surfactant is used for imparting hydrophilicity to an olefin-based polymer sintered body, its effect is temporary and its sustainability is short. Although it has been considered insufficient, a large number of surfactants were tested and examined, and as a result, it was found that a specific surfactant that had never been used for such purposes could be used as a powder composed of a specific olefin polymer. By soaking in a high concentration near the surface of the granules, it was found that the above-mentioned problems of the present invention can be solved, and in addition, the safety required for the high humidity chilled chamber olefin polymer sintered body (human body Regarding harmlessness) and deodorizing property under high humidity, it was found that, out of a large number of substances, specific bactericides and deodorants were superior in their effect persistence and safety, and further investigation was conducted. Stacked books Akira was completed.

That is, according to the present invention, the density is 0.90 to 0.
965 g / ml, melt index 0.01-1.0
The following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa was added in the vicinity of the surface of 100 parts by weight of a powder or granules made of an olefin polymer having an amount of g / 10 minutes and an extraction ratio of normal hexane of 10% by weight or less. (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
A powdered granule obtained by soaking 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether (hereinafter also referred to as a sodium salt of formula 1) represented by The present invention relates to a hydrophilic moisture-permeable porous olefin polymer sintered body obtained by sintering.

The present invention also provides, in the vicinity of the surface of 100 parts by weight of the above-mentioned olefin-based polymer powder and granules, 1.5 to 2.5 parts by weight of the sodium salt of the formula 1 and one or more of an antifungal agent and a deodorant. The present invention relates to a hydrophilic moisture-permeable porous olefin-based polymer sintered body obtained by sintering a powder or granular material obtained by soaking both of them in a high concentration.

According to the present invention, 1.5 to 2.5 parts by weight of the sodium salt of Formula 1 and 0.1 to 0. 8
Deodorant 0.1-2.
Hydrophilic and moisture-permeable porous material obtained by sintering a granular material in which 0.1 to 10 parts by weight of a porous inorganic powder having an average particle size of 0.1 to 10 μm adsorbed by 5 parts by weight is adhered and buried. It relates to an olefin polymer sintered body.

Further, according to the present invention, 1.5 to 2.5 parts by weight of the sodium salt of the formula 1 and 0.1 to 2. 5
By soaking the parts by weight to a high concentration, a mildew proofing agent 0.1
Hydrophilic moisture permeability obtained by sintering a granular material in which 0.1 to 10 parts by weight of a porous inorganic powder having an average particle size of 0.1 to 10 μm adsorbed 0.8 parts by weight is adhered and buried. The present invention relates to a porous olefin-based polymer sintered body.

Further, the present invention provides 1.5 to 2.5 parts by weight of the sodium salt of the formula 1 in the vicinity of the surface of 100 parts by weight of the above-mentioned olefin polymer powder and granules, and if necessary, an antifungal agent and One or both of the deodorants are soaked to a high concentration, and a porous inorganic powder having an average particle diameter of 0.1 to 10 μm 0.1
The present invention relates to a hydrophilic moisture-permeable porous olefin-based polymer sintered body obtained by sintering a powder or granular material having 10 parts by weight attached and buried therein.

In the present invention, the olefin polymer is ethylene or propylene homopolymer or a copolymer of ethylene or propylene and other α-olefin having the above physical properties. Examples of α-olefins include ethylene, propylene, butene-1, hexene-1, octene-1, decene-1, 4-methyl-pentene-1 and the like, and vinyl acetate, acrylic acid ester, styrene and other vinyl monomers. May be copolymerized to the extent that the properties of the polymer are not impaired. As a method for polymerizing the olefin polymer, high pressure (500 atm or more), medium pressure (80 to 300 atm) or low pressure (0 atm) in the presence of Ziegler catalyst, chromium catalyst, molybdenum catalyst, free radical generator, etc. Slurry polymerization method, gas phase polymerization method, high temperature melt polymerization method, etc.

The olefin polymer used in the present invention has a density in the range of 0.90 to 0.965 g / ml, but if the density is less than 0.90 g / ml, the mechanical strength decreases and The pores of the sintered body are fused to deteriorate air permeability and moisture permeability, which is not desirable, and the density is 0.965 g / m.
When it exceeds 1, the crystallinity is high and the melting point is high, so that the sodium salt of the formula 1 is not sufficiently soaked and the hydrophilicity is insufficiently expressed, which is not desirable. The melt index of the olefin polymer is 0.01 to 1.0 g.
/ 10 minutes, but less than 0.01 g / 10 minutes,
The sodium salt of Formula 1 is not sufficiently kneaded, the hydrophilicity is not expressed, and it becomes very difficult to mix an antifungal agent and a deodorant, which is not desirable. The strength is lowered, and the pores of the sintered body are fused to deteriorate air permeability and moisture permeability, which is not desirable. Further, the olefin polymer used in the present invention has a normal hexane extract content of 10% by weight or less.
If it exceeds the range, odor is generated from the sintered body, and the surface of the sintered body is fused to lose air permeability and moisture permeability, which is not desirable.

In this specification, the density is JIS
K7112 and melt index JIS K676
It is determined according to the regulations of 0-1976. Further, the normal hexane extract is put in 300 ml of normal hexane in a glass container and heated to 50 ° C.
3 g of a film sample of m cut into strips is put therein, left for 2 hours, taken out of the film sample, weighed, and calculated according to the following formula. Normal hexane extract (% by weight) = [initial film weight (g) -film weight after hexane extraction (g)] /
Initial film weight (g) x 100

The particle size of the above-mentioned olefin polymer is not particularly limited as long as it can be sintered, but the average particle size is preferably 10 μm or more and 1 cm or less. This is because when it is less than 10 μm, the moisture permeability and air permeability are deteriorated, and when it exceeds 1 cm, the thermal conductivity is deteriorated and the sintering may be difficult. Further, in the case of a sintered body used in a high humidity chilled chamber or a refrigerator having the chilled chamber built therein, it is desirable that the average particle size of the powdery particles is around 100 μm.

Next, the carboxylated sodium polyoxyethylene alkyl ether used in the present invention is a surfactant represented by the above formula 1. When m in Formula 1 is less than 13, the sustainability of the hydrophilic effect is insufficient,
When it exceeds 18, the hydrophilic effect becomes insufficient, which is not desirable, and when n is less than 3, the hydrophilic effect becomes insufficient, and when it exceeds 6, the hydrophilic effect does not last sufficiently, which is not desirable. The sodium salt of the above formula 1 is used in an amount of 1.5 to 2.5 parts by weight with respect to 100 parts by weight of the olefin polymer, and if it is less than 1.5 parts by weight, the hydrophilic effect becomes insufficient, If it exceeds 2.5 parts by weight, bleeding of antifungal agents and deodorants is caused, and the effects of these additives are reduced, which is not desirable. It has not been reported until now that a surfactant such as the above-mentioned sodium salt imparts a hydrophilic sustaining effect to the sintered body, and the present inventors have first found out.

Examples of the fungicides used in the present invention include sulfur compounds, bromine compounds, aniline derivatives and thiabendazole compounds.
N- (fluorodichloromethylthio) -phthalimide,
N-dimethyl-N'-phenol-N '-(fluorodichloromethylthio) -sulfamide, 10,10'-oxybisphenoxyaldine, 2-pyridinethiol-
There are 1-oxide (metal salt), 4-methoxytrifluoroisophthalonitrile, 4-ethoxytrifluoroisophthalonitrile, tetrafluoroisophthalic acid, hinokitiol (salt) and the like. Among these, thiabendazole compounds are preferable, and particularly the following formula: 2- (4-thiazolyl) -benzimidazole represented by the formula is superior in antifungal effect and its durability, 1987
Approved by the Ministry of Health and Welfare as a food additive in the year, extremely high safety is guaranteed, which is preferable. In the present invention,
The amount of the antifungal agent is preferably 0.1 to 0.8 parts by weight with respect to 100 parts by weight of the olefin polymer.
If the amount is less than 0.1 part by weight, the antifungal effect is insufficient, and if the amount exceeds 0.8 parts by weight, the antifungal effect cannot be expected to be improved, resulting in an increase in cost, and the surface of the sintered body. May bleed.

In the present invention, the deodorant is an organic compound such as a flavonoid compound, a terpene compound (phytoncide), and a wood vinegar component, which can be soaked with an olefin polymer. Flavonoid compounds are preferred in the present invention. Further, the deodorant in the present invention is a plant containing the above compound as a component, for example, a tea plant, a mountain tea flower, a camellia, a sakaki, a Japanese camellia plant such as Hisaki,
Lauraceae, laurel, camphoraceae plants such as camphoraceae, primroses, poplars, chinensis, botanical, bayberry,
It may be extracted from whole plants of flowers such as Pinus, Eucalyptus, sumac, pomelo and lemon, flowers, tree materials, heartwood, leaves, fruit skins and the like. The deodorant is preferably added in an amount of 0.1 to 2.5 parts by weight based on 100 parts by weight of the olefin polymer. If it is less than 0.1 part by weight, the deodorizing effect is insufficient, and if it exceeds 2.5 parts by weight, the surface of the sintered body may bleed and the mechanical strength may decrease.

In the present invention, the porous inorganic powder means cristobalite, zeolite, silica gel, alumina gel, silica alumina gel, silica magnesium gel, hydrotalcite, dawsonite, fly ash, vermiculite, palygorskite, attapulgite, sepiolite, mordenite, Clinobuchirolite, chabazite, tobermorite, brandite, affrite, zonotolite, gyrolite, shirasu foam, coral fine powder, acid clay, Kanuma soil, allophane, Oya stone, barley stone, perlite, charcoal powder, etc., Iron (II) compounds such as ferrous sulfate, ferrous chloride or ferrous nitrate, L-ascorbic acid, antibacterial metal ions and the like may be added to these. As the porous inorganic powder in the present invention, cristobalite, zeolite and silica gel are particularly preferable from the viewpoint of improvement of mechanical strength and antifungal / deodorant sustaining effect. In the present invention, when the above-mentioned porous inorganic powder is used, its blending amount is olefin polymer 1
It is 0.1 to 10 parts by weight with respect to 00 parts by weight. 0.1
If the amount is less than the amount by weight, the amount of carboxylated sodium polyoxyethylene alkyl ether, fungicide or deodorant adsorbed or occluded on the inside or the surface of the porous inorganic powder is small, and the sustainability of the effect is not so great. Not expressed,
There is no point in adding a trace amount of less than 0.1 part by weight, which is time-consuming and costly, and when an amount exceeding 10 parts by weight is added, the amount of the inorganic powder relative to the amount of the resin (the amount of the olefin-based polymer) Too much, the surface of the resin powder granules is almost entirely covered with the inorganic powder, and even if the temperature is increased and sintering is attempted, the resin component does not exist near the surface, so the sintered body is manufactured. Not possible and not desirable.

When the porous inorganic powder is used in the present invention, the effects of hydrophilicity, antifungal property and deodorant property are maintained and the mechanical strength of the sintered body is remarkably improved. This is because the porous inorganic powder occludes the sodium salt of formula 1 (surfactant), antifungal agent and deodorant, prevents sudden bleeding, and gradually releases them,
It is considered that the sustainability of each effect is maintained. Therefore, in the present invention, when the antifungal agent and / or deodorant is used in combination with the porous inorganic powder, durability of the antifungal and / or deodorant effect is increased, and the porous inorganic powder itself is also used. Since it has a deodorizing effect, the deodorizing effect is further increased. Furthermore, since the porous inorganic powder prevents bleeding of the fungicide and deodorant, it is possible to avoid sintering failure due to bleeding.

The porous inorganic powder in the present invention has an average particle size of 0.1 to 10 μm. If it is less than 0.1 μm, they agglomerate and cannot be evenly adhered / embedded in the vicinity of the surface of the powder or granular material. If it exceeds 10 μm, most of it only adheres to the surface of the powder or granular material and is embedded inside. However, the effects of the antifungal agent and / or deodorant adsorbed on the porous inorganic powder or the porous inorganic powder itself are not exhibited, which is not desirable. Further, it is desirable that the average particle size of the porous inorganic powder is 1/10 or less of the average particle size of the powder or granular material made of the olefin polymer. If it exceeds 1/10, the ratio of the embedded porous inorganic powder becomes low, and most of the particles are present on the surface, and the fusion of the olefin polymers is hindered during sintering. , Undesired.

In the present invention, as a method of soaking the sodium salt of formula 1 (surfactant) and / or antifungal agent and / or deodorant in the vicinity of the surface of the granular material made of an olefin polymer at a high concentration Spray the above-mentioned substance to be soaked onto the above-mentioned powder and granules to 70-105 ° C.
There is a method in which the mixture is allowed to stand in the temperature range of, or is stirred in this temperature range by a static mixer, a tumbler, a Henschel mixer, or the like. It should be noted that when the soaking of the sodium salt of Formula 1 and the soaking of the fungicide and / or deodorant are carried out, they may be carried out simultaneously or separately. When carried out separately, the order is not limited, but the sodium salt of the formula 1 promotes the soaking of the antifungal agent and the deodorant, so that the sodium salt of the formula 1 is preferably soaked first.

In the present invention, the surfactant is soaked at a high concentration in the vicinity of the surface of the granular material, and is present at a very low concentration inside the granular material. Compared with the above, since the surfactant acts on the sintered body efficiently, the cost is reduced, and the obtained sintered body has high hydrophilicity and moisture permeability and is excellent in its durability. Further, when the antifungal agent and / or deodorant is further soaked, more effective antifungal agent and / or
Or the deodorant effect is obtained and their durability is excellent.

The porous inorganic powder alone or the porous inorganic powder having a fungicide and / or deodorant adsorbed thereto is simply mixed with a powder or granular material made of an olefin polymer and allowed to stand. Since both do not bond, and are only weakly attached to the surface of the powder or granular material, in order to attach or bury the porous inorganic powder near the surface of the powder or granular material as in the present invention. Is, for example, both are supplied to a high-speed stirring device such as a Henschel mixer, and by friction and collision between the particles or particles and the porous inorganic powder, the surface of the particles is melted, It is necessary to adhere the porous inorganic powder to the melted portion and further bury the porous inorganic powder near the surface of the granular material by continuing friction and collision. Further, the soaking operation and the adhesion / burying operation of the porous inorganic powder may be carried out simultaneously or separately, and in the case of being carried out separately, the order thereof does not matter.

In the present invention, the vicinity of the surface of the granular material made of an olefin polymer means a range of about 30% by volume from the surface of the granular material toward the inside. Therefore, in the present invention, most of the surfactants, fungicides, deodorants and porous inorganic powders are present in the range of about 30% by volume from the surface to the inside of the granular material. Should be understood. In the heat kneading method using a Banbury mixer or the like, all the components are almost evenly dispersed, and it is impossible to allow the above substances to exist in a high concentration only near the surface as in the present invention.

The hydrophilic moisture-permeable porous olefin-based polymer sintered body of the present invention is obtained by adding the sodium salt of the formula 1 to the powder and granules of the olefin-based polymer as described above, and optionally an antifungal agent and / or a deodorant. Put the powder or granules after soaking the odorant or the soaking and adhesion of the porous inorganic powder (adsorbing antifungal agent and / or deodorant as the case may be) into the mold, 0.5-10kg / at room temperature
by pressurizing to cm ² and then raising the temperature of the olefin-based polymer used in the sintering furnace to the softening point or melting point + 5 ° C. while sintering the powder in the mold. Manufactured. Here, the sintering temperature is short (for example, 1 to 2).
Even if it is 0 minutes), it is preferable that the melting point of the olefin-based polymer is equal to or higher than the above, because the mechanical strength of the sintered body is increased. However, if the sintering is performed at a temperature equal to or higher than the melting point of the olefin-based polymer for a long time (for example, 30 to 60 minutes), air permeability, moisture permeability, etc. are deteriorated, which is not desirable. The time required for sintering is appropriately determined depending on the thickness of the sintered body, the components, the sintering temperature, etc., but is usually 1 to 60 minutes, preferably 10 to 30 minutes.

The hydrophilic moisture-permeable porous olefin polymer sintered body of the present invention as described above is used as a moisturizer, a humidifier, a dehumidifier, a dew condensation preventer, a humidity controller, a heat exchanger, an air diffuser, It can be used as a foam plate, a printing roller, a filter material, a stamping table, a water purification filter, a felt pen core material, etc., but especially those containing a fungicide or a deodorant are suitably used as a high humidity chilled chamber. It In these applications, the sintered body of the present invention is appropriately mixed with or without an antifungal agent or deodorant in consideration of the necessity of antifungal property and / or deodorant property. To be selected. The olefin-based polymer sintered body of the present invention may be used in combination with other materials such as a hydrophobic breathable moisture-permeable porous membrane placed thereon. Therefore, the present invention further uses the above-described antifungal agent, deodorant or porous inorganic powder blended olefin polymer sintered body of the present invention as a ceiling part, wall surface or at least a part of the bottom surface. Humidity chilled room. Further, the sintered body of the present invention is not only used in a high-humidity chilled chamber but also a hydrophilic porous sintered body for a vegetable storage container of a refrigerator that has been conventionally used (for example, the one described in Japanese Patent Publication No. 5-16816). It can also be used as a body. Also,
The present invention also relates to a refrigerator incorporating the above-mentioned high humidity chilled chamber of the present invention.

In the present invention, the high-humidity chilled chamber is a closed container having an internal volume of 0.1 to ⁵ m ³ , and at least a part of the ceiling portion, wall surface or bottom surface is made of the olefin polymer sintered body of the present invention. It means a food storage room which is replaced to allow moisture, air, generated gas from food, etc. to freely permeate the inside and outside of the container. The high-humidity chilled chamber of the present invention can be entirely composed of the sintered body of the present invention, but it is preferable that only a part of the high-humidity chilled chamber is composed of the sintered body, and the remaining portion is made of ordinary plastics. , For example, polycarbonate or the like. This high-humidity chilled room stores food, 0-10 ° C,
Desirably, it is necessary to maintain the temperature at 0 to 1 ° C and the humidity at 80 to 90%.
It is necessary to flow cold air at ℃ to +7 ℃, preferably 3 to 5 ℃.

The olefin polymer sintered body of the present invention is preferably applied to a high humidity chilled chamber in the form of a sheet, and the thickness and area in that case are not particularly limited, but the thickness Is preferably 1 to 100 μm, particularly preferably 2 to 5 μm, and the area is 5 to 5000 cm ² , particularly 1.
It is preferably from 0 to 500 cm ² , but the thickness and area are appropriately selected and determined depending on the shape, the capacity of the high-humidity chilled chamber, the amount of food stored, the temperature outside, and the amount of cold air circulated outside. To be done.

In the above-mentioned high humidity chilled chamber and refrigerator of the present invention, an apparent specific gravity of 0.5 to 0.7 g / ml, a water absorption rate of 2 cm or more, a water drop absorption property of 4 seconds or less, and water absorption as an olefin polymer sintered body. 25% or more, tensile strength 30 kg /
cm ² or more, tensile elongation at break 15% or more, flexural modulus 17
00kg / cm ² or more, bending strength 35 kg / cm ² or more, moisture permeability 1200g / m ² · 24 hours or more, the creep deformation than 6mm (80 ° C.) and 3mm or less (23
C.), dimensional change rate of 1% or less, and porosity of 28% or more are particularly preferably used.

In the present specification, the above various characteristic values are determined according to the following measuring methods. Apparent specific gravity: A test piece having a width of 70 mm and a length of 70 mm is cut out from the sheet, and the weight (W) and volume (V) of the test piece are measured and calculated by the following formula. Apparent specific gravity (g / cm ³ ) = W (g) / V (cm ³ ) Water absorption rate: A test piece with a width of 2 cm and a length of 10 cm was cut out from the sheet, the test piece was erected vertically in the longitudinal direction, and the lower end was 2
Immerse 0 mm in water. The rising water level in the test piece 1 minute after the start of immersion is read, and the value is taken as the water absorption rate. Water drop absorbency: Place the sheet horizontally and hang one drop (about 50-60 mg) of the drop using a dropper. The time until the water droplet is absorbed by the sheet is measured. Select six test points on the front and back sides almost evenly from the entire sheet. The average value of the water absorption time is taken as the water drop absorbency value. Water absorption: A test piece having a width of 70 mm and a length of 70 mm is cut out from the sheet, the weight of the test piece is measured, and then the test piece is gradually immersed in water. After soaking in water for about 2 minutes, pull up at a speed that allows water to drain naturally, hold for about 30 seconds to drain water,
The weight is measured again, and the amount of water contained in the test piece is calculated by the following formula. Water absorption amount (%) = [weight after water absorption (g) -weight before water absorption (g)] / weight after water absorption (g) × 100 Tensile strength, tensile elongation at break: JIS K630 from sheet
The No. 2 dumbbell of 1 was punched out and used as a test piece. The test conditions are according to JIS K7113, the chuck distance is 50 mm, and the pulling speed is 10 mm / min. The minimum number of tests is three, and the tensile strength is the maximum strength during tension.
The standard value shall be the average value and the minimum value. Flexural modulus, flexural strength: width 25 mm, length 1 from the sheet
A 25 mm test piece is cut out, and a test is performed under conditions based on JIS K7203 (bending test method for hard plastics) at a span distance of 30 mm and a bending speed of 5 mm / min to obtain bending strength and bending elastic modulus. The minimum number of tests is three, the bending strength is the maximum bending strength, and the flexural modulus is the initial flexural modulus. Water vapor transmission rate: A disk-shaped test piece with a diameter of about 70 mm is cut out from the sheet, and the weight (g) of water vapor passing in 24 hours is measured in accordance with JIS Z0208 [Moisture vapor transmission rate test method for moisture-proof packaging material (cup method)]. The value converted per 1 m ^{2 of} sheet is taken as the moisture vapor transmission rate. The test is performed under constant temperature and humidity conditions of a temperature of 25 ° C. and a humidity of 90% RH. Creep deformation: 25mm width and 136mm length from the sheet
The test piece is cut off, one end is sandwiched between clamps, and the length protruding from the clamp is set to 100 mm. This is left for 24 hours in an atmosphere having a temperature of 23 ° C. and 80 ° C., and the bending amount of the tip of the test piece is measured. Dimensional change rate: After the sheet is left at 23 ° C. and 50% RH for 24 hours, the vertical and horizontal three-point dimensions are measured. This is -30 ℃
After leaving it in the atmosphere for 3 hours, it is immediately taken out, and the same dimension as the dimension is measured in advance is measured up to 0.1 mm, and the dimensional change rate is calculated by the following formula. Also, the dimensional change rate is similarly obtained under the conditions of 60 ° C. and 3 hours. Dimensional change rate (%) = [(dimension before test)-(dimension after test)] / (dimension before test) × 100 Porosity: apparent specific gravity (g / c) determined by the above method
The porosity is calculated by the following equation from m ³ ) and the true specific gravity of the material of 0.956 (g / cm ³ ). Porosity (%) = [true specific gravity (g / cm ³ ) −apparent specific gravity (g / cm ³ )] / true specific gravity (g / cm ³ ) × 100

When the food containing a large amount of water is stored in the high humidity chilled room, the humidity in the chilled room rises to 80% or more, the food does not dry, the freshness is maintained, and the food can be stored for a long time. However, when the water content in the food is too high, the water content is condensed and adheres to the lid body, and water drops directly fall on the food such as vegetables, sashimi and ham in the chilled room, which damages the food. However, since the specific sinter is used in the high humidity chilled chamber of the present invention, the humidity in the chilled chamber is 90%.
%, The excess water is taken into the sintered body by a capillary phenomenon and evaporated outside the chilled chamber to keep the chilled chamber at a proper humidity of 80 to 90%. On the other hand, when the humidity in the chilled chamber drops to 80% or less, the water stored in the sintered body until then is released into the chilled chamber to prevent the inside of the chamber from drying.

Accordingly, the present invention provides a food, preferably a high water content food, in the high humidity chilled room of the present invention or in a high humidity chilled room of a refrigerator having the same incorporated therein [food having a high water content, such as various kinds of sashimi, meat, Vegetables, paste products (ham, kamaboko, etc.)
Etc.] and the outside of the high humidity chilled chamber is cooled with a cold air flow (preferably -2 ° C. to + 7 ° C., particularly 3 to 5 ° C.).

[0034]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. Example 1 Density 0.919 g / ml, melt index 0.3 g
High pressure low density polyethylene (manufactured by Nippon Unicar Co., Ltd., base resin) having a normal hexane extract content of 7.3% by weight for 10 minutes was crushed into particles having an average particle size of 70 μm by a crusher crushing method. 1.7 parts by weight of sodium carboxylated polyoxyethylene (n = 3) tridecyl ether (manufactured by Nikko Chemical Co., Ltd., trade name NIKKOL) was added to the parts by weight at room temperature, and the mixture was stirred to adhere the latter to the surface of the former. . Then, it was put in a container kept at 87 ° C., kept for 30 minutes and soaked. Next, the soaked powder and granules are put into a mold, pressurized to 1.2 kg / cm ² at 20 ° C. for 5 minutes by a press molding machine, then put into a sintering furnace together with the mold, and at 102 ° C. for 7 minutes. Sintering was performed to obtain a sheet-shaped sintered body (dimensions: length 20 cm × width 25 cm × thickness 5 mm). The measured physical properties of the obtained sintered body were as follows. In addition, the surface-active agent is 30
It was confirmed that 78% was present in the volume% range.

Example 2 In Example 1, after soaking the surface-active agent into powder and granules, 0.15 parts by weight of antifungal agent [N-fluorodichloromethyl) -phthalimide] and deodorant (1,8 -Cineol, 1,4-cineole, a terpene-based compound mixture consisting of monoterpenes) 0.5 part by weight, and 70 ° C
Soaking was carried out for 30 minutes in a tumbler while stirring at a rotation speed of 4 rpm. Antifungal test A sintered body sheet produced from the soaked powder and granules was cut into a size of 5 cm square, placed on a potato dextrose agar medium, and 1 ml of the mixed spore suspension of fungi was sprinkled evenly on it. Then, the cells were cultured at 28 ° C. for 100 days, but no mold was found. Deodorization Test Further, the above-mentioned sintered body sheet was cut into a circle having a diameter of 4.5 cm, and the lid was closed as an inner lid of a closed bottle (internal volume 30 ml) accommodating 180 garlic naked tablets. After 100 days, the inner lid was taken out, but no garlic odor was felt. In the powder and granular material after the soaking, the volume of the powder is increased from the surface to the inside in the range of 30% by volume.
% Were antifungal and deodorant present.

Example 3 In Example 1, after soaking the surface active agent in a granular form, 0.15 parts by weight of an antifungal agent [N-fluorodichloromethyl) -phthalimide] was used under the same conditions as in Example 2. I was allowed to soak. Next, 0.5 part by weight of the same deodorant as in Example 2 was adsorbed on 5 parts by weight of zeolite having an average particle size of 5 μm, added to the soaking body, stirred at room temperature, put in a Henschel mixer, and rotated. High-speed forced agitation was performed at a speed of 2300 rpm for 2 minutes to deposit and bury the zeolite near the particle surface of the soaking body. The antifungal test and the deodorant test were conducted in the same manner as in Example 2, but no generation of mold was observed even after 300 days, and no garlic odor was felt. In addition, regarding the persistence of the hydrophilic effect,
The sintered body was put in water for 100 days and then taken out, and the water absorption rate, the water drop absorbency, and the water absorption amount were measured according to the methods described above. The results were 3.1 cm, 0.3 seconds, and 56%, respectively, which are very good. It was the result. The zeolite powder was present in an amount of 2.1 parts by weight on the surface of the ethylene-based polymer powder and 2.4 parts by weight in the range of 30% by volume from the surface to the inside of the powder.

Example 4 In Example 3, the mixing order of the antifungal agent and the deodorant was exchanged, that is, after the deodorant was soaked, the zeolite adsorbing the antifungal agent was adhered and buried. As in Example 3, it was confirmed that the effects of hydrophilicity, antifungal properties and deodorant properties were improved and maintained.

Example 5 8 parts by weight of silica gel powder having an average particle size of 0.5 μm was added to 100 parts by weight of the ethylene-based polymer powder granulated with the surfactant, antifungal agent and deodorant prepared in Example 2. The parts were mixed and stirred with a Henschel mixer at a rotation speed of 3000 rpm for 1 minute, and then at a rotation speed of 1000 rpm for 5 minutes. Then, a sintered body was manufactured under the same conditions as in Example 1 and evaluated. The antifungal test and the deodorant test were carried out in the same manner as in Example 2, but no generation of mold was observed even after 500 days, and no garlic odor was felt. Further, regarding the durability of the hydrophilic effect, the sintered body was put in water for 200 days and then taken out, and the water absorption rate, the water drop absorbency and the water absorption amount were measured by the above-mentioned methods.
It was 9 cm, 0.2 seconds, and 61%, which was a very good result. The silica gel powder was present in an amount of 2.8 parts by weight on the surface of the ethylene-based polymer powder and 4.3 parts by weight in the range of 30% by volume from the surface to the inside of the powder.

Example 6 Granules of ethylene-butene-1 copolymer produced by the vapor phase low pressure method (manufactured by Nippon Unicar, trade name GS-650, density 0.920 g / ml, melt index 0.55 g /
10 minutes, normal hexane extract 4.7% by weight, average particle size 100 μm, melting point 117 ° C.) 100 parts by weight, and carboxylated polyoxyethylene (n = 6) octadecyl ether sodium (manufactured by Nikko Chemical, trade name NIKKO
L) 1.5 parts by weight, thiabendazole (Merck, Mitsubishi Petroleum Sales, trade name San Aisol) 0.2 parts by weight and flavonoid (Shiraimatsu Shinyaku Co., Ltd. trade name Fresh Rimatu) 0.8 parts by weight to a Henschel mixer. 3000r
The mixture was stirred at pm for 2 minutes, and then soaked at 80 ° C. for 30 minutes. Put the soaked powder into the mold,
1.2kg / cm for 5 minutes at 20 ℃ by press molding machine
Pressurize to ² , then put the whole mold into a sintering furnace, 121 ℃
Sintered for 30 minutes, and then sinter the sheet (Dimension: length 20 cm
X width 25 cm x thickness 5 mm) was obtained. The physical properties of this sintered body were as follows.

Manufacture of a high humidity chilled chamber A rectangular parallelepiped box having a width of 30 cm, a length of 50 cm and a height of 15 cm is manufactured from a polycarbonate sheet having a thickness of 3 mm, and a notch having a width of 25 cm and a length of 20 cm is formed at the upper end of the box. A portion was provided, and the above-mentioned sintered body sheet was fitted into the cutout portion to form a high humidity chilled chamber. Evaluation of high humidity chilled room Put 3 kg of tuna sashimi in the high humidity chilled room,
When cold air of −2 ° C. was circulated outside the chilled room, the temperature in the high humidity chilled room was kept at 0.7 ° C. and the humidity was 89%.
Five days later, the weight loss rate of tuna sashimi was measured, and the result was 5
%, The color and gloss did not change, and the samples were tasted, but no deterioration in taste or freshness was observed. Also, throughout the storage period,
No foul odor was felt. Furthermore, after a certain period of time has passed since the sintered sheet was manufactured (6 months, 1 year)
When we also evaluated the chilled room in which
The effect similar to the above was acquired. Refrigerator with a built-in high-humidity chilled chamber The above-mentioned high-humidity chilled chamber is built into a refrigerator with an internal volume of 1000 liters, and the inside of the refrigerator is kept at 5 ° C. Allowed cold air to pass through. In addition, 5 kg of broccoli was stored in the chilled chamber. The broccoli was taken out on the 7th day and the weight loss rate was measured. As a result, it was as low as 1.7%, and there was no change in color or freshness, and it was tasted, but the taste and freshness were lower than those before storage. I couldn't do it. In addition, no mold was generated and no foul odor was felt during the storage period. Further, when a chilled chamber in which a sintered body sheet was manufactured and a certain period of time has passed (6 months, 1 year) was also evaluated, the same effect as above was obtained.

Example 7 Polypropylene powder (manufactured by Tonen Kagaku, trade name BJ30)
1 in the form of powder, density 0.91 g / ml, melt index 0.33 g / 10 min, normal hexane extract 3.2 wt%, average particle size 200 μm) 100 parts by weight of carboxylated polyoxyethylene (N = 3) Sodium tridecyl ether (Nikko Chemical, trade name N
2.3 parts by weight of IKKOL) was added at room temperature and stirred to deposit the latter on the surface of the former. Then, this is 115 ℃
Put it in a container kept warm and keep it at that temperature for 30 minutes,
I was allowed to soak. Next, the soaked powder and granules are put into a mold and pressed by a press molding machine at 20 ° C. for 5 minutes to give 5.3
The pressure was applied to kg / cm ² , and then the mold was put into a sintering furnace and sintered at 156 ° C. for 20 minutes to obtain a sheet-shaped sintered body (dimensions: length 20 cm × width 25 cm × thickness 5 mm). The physical properties of this sintered body were as follows. In addition, the surface-active agent is 30
It was confirmed that 84% was present in the volume% range.

Example 8 In Example 7, after the surfactant was soaked into powder and granules, 0.15 parts by weight of an antifungal agent [N-fluorodichloromethyl) -phthalimide] and a deodorant (1,8) were used. -Cineol, 1,4-cineole, a terpene-based compound mixture consisting of monoterpenes) 0.5 part by weight, and 70 ° C
Soaking was carried out for 30 minutes in a tumbler while stirring at a rotation speed of 4 rpm. Antifungal test A sintered body sheet produced from the soaked powder and granules was cut into a size of 5 cm square, placed on a potato dextrose agar medium, and 1 ml of the mixed spore suspension of fungi was sprinkled evenly on it. Then, the cells were cultured at 28 ° C. for 100 days, but no mold was found. Deodorization Test Further, the above-mentioned sintered body sheet was cut into a circle having a diameter of 4.5 cm, and the lid was closed as an inner lid of a closed bottle (internal volume 30 ml) accommodating 180 garlic naked tablets. After 100 days, the inner lid was taken out, but no garlic odor was felt. In addition, in the powder and granules after the soaking, the volume of the powder and granules in the range from the surface to the inside is 30% by volume.
% Were antifungal and deodorant present.

Example 9 In Example 7, after soaking the surface active agent in a granular form, 0.15 parts by weight of an antifungal agent [N-fluorodichloromethyl) -phthalimide] was used under the same conditions as in Example 8. I was allowed to soak. Next, 0.5 part by weight of the same deodorant as in Example 8 was adsorbed on 5 parts by weight of zeolite having an average particle size of 5 μm, added to the soaking body, stirred at room temperature, put in a Henschel mixer, and rotated. High-speed forced agitation was performed at a speed of 2300 rpm for 2 minutes to deposit and bury the zeolite near the particle surface of the soaking body. The antifungal test and the deodorant test were carried out in the same manner as in Example 8, but no generation of mold was observed even after 300 days, and no garlic odor was felt. In addition, regarding the persistence of the hydrophilic effect,
The sintered body was put in water for 100 days and then taken out, and the water absorption rate, water drop absorbency, and water absorption were measured according to the above-mentioned methods. The results were 3.8 cm, 0.2 seconds, and 48%, respectively, which are very good. It was the result. The zeolite powder was present in an amount of 2.3 parts by weight on the surface of the propylene-based polymer powder and 2.5 parts by weight in the range of 30% by volume from the surface of the powder and granules toward the inside.

Example 10 In Example 9, the mixing order of the antifungal agent and the deodorant was exchanged, that is, after the deodorant was soaked, the zeolite adsorbed with the antifungal agent was adhered and buried. As in Example 9, it was confirmed that the hydrophilicity, antifungal properties and deodorant effects were improved and maintained.

Example 11 8 parts by weight of silica gel powder having an average particle size of 0.5 μm was added to 100 parts by weight of the propylene-based polymer powder soaked with the surfactant, antifungal agent and deodorant prepared in Example 8. The parts were mixed and stirred with a Henschel mixer at a rotation speed of 3000 rpm for 1 minute, and then at a rotation speed of 1000 rpm for 5 minutes. Then, a sintered body was manufactured under the same conditions as in Example 7 and evaluated. The antifungal test and the deodorant test were conducted in the same manner as in Example 8, but even after 500 days had elapsed, no generation of mold was observed and no garlic odor was felt at all. Further, regarding the sustainability of the hydrophilic effect, the sintered body was put in water for 200 days and then taken out, and the water absorption rate, the water drop absorbency and the water absorption amount were measured by the above-mentioned methods.
The result was 1 cm, 0.1 seconds, and 63%, which was a very good result. The silica gel powder was present in an amount of 3.4 parts by weight on the surface of the propylene polymer powder and 4.2 parts by weight in the range of 30% by volume from the surface of the powder and granules toward the inside. Further, using the sintered body produced in Example 11, a high-humidity chilled chamber and a refrigerator incorporating the same were prepared in the same manner as in Example 6 and evaluated in the same manner. As a result, Example 6 was obtained. Good results were obtained.

Example 12 Instead of the granular material having an average particle size of 70 μm in Example 1,
The same experiment as in Example 1 was performed except that pellets having a diameter of 5 mm and a length of 5 mm were used. As a result, a sintered body having excellent mechanical strength was obtained.

Comparative Example 1 The melt index in Example 6 was 0.55 g / 1.
Instead of the ethylene-butene-1 copolymer (manufactured by Nippon Unicar, trade name NUCG-5651) which is 0 minutes, the ethylene-butene-1 copolymer (manufactured by Nippon Unicar) whose melt index is 4.0 g / 10 minutes. , Product name NUCG-08
The same experiment as in Example 6 was carried out except that 51) was used. As a result, a sintered body having extremely low air permeability and moisture permeability was obtained. The color and gloss were significantly deteriorated, the taste and the freshness were also clearly deteriorated, and a bad odor was generated during the storage period, and the freshness retention effect was insufficient.

Comparative Example 2 Instead of sodium carboxylated polyoxyethylene (n = 6) octadecyl ether in Example 6,
The same experiment as in Example 6 was carried out except that sodium carboxylated oxyethylene (n = 1) tridecyl ether was used, and the obtained sintered body was inferior in hydrophilicity and moisture permeability and was used. In the high-humidity chilled room, the color and luster of tuna sashimi were markedly deteriorated, and the taste and freshness of the tuna were obviously reduced, and the effect of maintaining freshness was insufficient.

Comparative Example 3 In place of the carboxylated polyoxyethylene (n = 6) octadecyl ether sodium in Example 6,
An experiment similar to that in Example 6 was conducted, except that sodium carboxylated polyoxyethylene (n = 8) tridecyl ether was used, and the obtained sintered body initially showed hydrophilicity, but the passage of time In addition, the hydrophilic effect diminishes, and in a high humidity chilled room that has been used for 6 months, the color and luster of the tuna sashimi are markedly deteriorated, the taste and freshness are obviously reduced, and the freshness retention effect is unsatisfactory. Was enough.

Comparative Example 4 In place of the carboxylated polyoxyethylene (n = 6) octadecyl ether sodium in Example 6,
An experiment similar to that of Example 6 was carried out except that sodium carboxylated polyoxyethylene (n = 3) decyl ether was used. The obtained sintered body initially showed hydrophilicity, but with the passage of time, Hydrophilic effect is reduced and 3
In a high-humidity chilled room that had been used for a month, the color and luster of tuna sashimi deteriorated markedly, and the taste and freshness also decreased, and the freshness preservation effect was insufficient.

Comparative Example 5 Instead of the carboxylated polyoxyethylene (n = 6) octadecyl ether sodium in Example 6,
The same experiment as in Example 6 was carried out except that sodium carboxylated polyoxyethylene (n = 3) eicosyl ether was used, and the obtained sintered body had insufficient hydrophilicity. In the high-humidity chilled room, the color and luster of the tuna sashimi were markedly deteriorated, and the taste and freshness of the tuna were obviously deteriorated, and the freshness retention effect was insufficient.

Comparative Example 6 Instead of sodium carboxylated polyoxyethylene (n = 6) octadecyl ether in Example 6,
An experiment similar to that in Example 6 was carried out except that polyoxyethylene (n = 3) hexadecyl ether was used.
The obtained sintered body has insufficient hydrophilicity, and in a high humidity chilled room using this, the color and gloss of tuna sashimi markedly deteriorated, the taste and freshness obviously decreased, and the freshness retention effect Was insufficient.

Comparative Example 7 In place of the carboxylated polyoxyethylene (n = 6) octadecyl ether sodium in Example 6,
An experiment similar to that in Example 6 was conducted except that polyoxyethylene (n = 3) stearate was used.
The obtained sintered body has insufficient hydrophilicity, and in a high humidity chilled room using this, the color and gloss of tuna sashimi markedly deteriorated, the taste and freshness obviously decreased, and the freshness retention effect Was insufficient.

Comparative Example 8 Instead of the ethylene-butene-1 copolymer having a density of 0.920 g / ml in Example 6, a density of 0.890 was obtained.
The same experiment as in Example 6 was carried out except that an ethylene-butene-1 copolymer of g / ml was used. As a result, a sintered body having very low air permeability, moisture permeability and mechanical strength was obtained. , Unsuitable for a high humidity chilled room.

Comparative Example 9 Instead of the ethylene-butene-1 copolymer having a density of 0.920 g / ml in Example 6, a density of 0.970 was obtained.
The same experiment as in Example 6 was carried out except that an ethylene-butene-1 copolymer having a concentration of g / ml was used. It was unsuitable for the room.

Comparative Example 10 The melt index in Example 6 was 0.55 g / 1.
An experiment similar to that in Example 6 was performed, except that an ethylene-butene-1 copolymer having a melt index of 0.005 g / 10 minutes was used instead of the ethylene-butene-1 copolymer having 0 minutes. As a result, a sintered body having a poor hydrophilicity retaining effect was obtained, which was unsuitable for a high humidity chilled chamber.

Comparative Example 11 Pressurization after placing powder for sintering in a mold was 0.3 at room temperature.
The same experiment as in Example 6 was carried out except that the experiment was conducted at a pressure of kg / cm ² , and the obtained sintered body had too high air permeability and moisture permeability and, conversely, had low mechanical strength and was used in a high humidity chilled chamber. It did not meet the standard for use.

Comparative Example 12 Pressurization after the powder for sintering was put in the mold was carried out at room temperature for 15 k.
The same experiment as in Example 6 was carried out except that the test was conducted at g / cm ² , and the obtained sintered body had too low air permeability and moisture permeability, and did not meet the standard for use in a high humidity chilled chamber. It was

Comparative Example 13 The powder for sintering was put in a mold and then immediately put into a sintering furnace without being pressed, and was sintered at 121 ° C. for 30 minutes under a pressure of 1.2 kg / cm ^2. When the same experiment as in Example 6 was carried out except that it was carried out, the obtained sintered body had extremely low air permeability and moisture permeability, and did not meet the standard for use in a high humidity chilled chamber.

Comparative Example 14 A test was conducted in the same manner as in Example 6 except that the sintering temperature was changed from 121 ° C. in Example 6 to 95 ° C. Was obtained, the breathability and the moisture permeability were too high, the mechanical strength was low, and the specification for use in a high humidity chilled room was not satisfied.

Comparative Example 15 Instead of the sintering temperature of 121 ° C. in Example 6, 132 ° C.
The same experiment as in Example 6 was performed except that the sintering was performed in Example 1. The obtained sintered body had excessive sintering, and had too low air permeability and moisture permeability, and was used for a high humidity chilled chamber. Did not meet the standard.

[0062]

Industrial Applicability As described in detail above, the hydrophilic moisture-permeable porous olefin of the present invention obtained from a granular material obtained by soaking a specific surfactant in a granular material made of a specific olefin polymer. The cost of the system polymer sintered body is low,
It has high mechanical strength, excellent flexibility and flexibility, and high durability and safety of hydrophilicity. Also,
Soaked with a specific surface active agent, antifungal agent and / or deodorant in the granular material made of a specific olefin-based polymer, or a porous inorganic powder adhered to it.
The hydrophilic moisture-permeable porous olefin of the present invention obtained by burying, or by adsorbing a fungicide and / or deodorant on a porous inorganic powder and adhering to and burying in the powder The system polymer sintered body is further improved in the above-mentioned respective properties, and is further excellent in antifungal property and deodorant property, and moreover, the hydrophilicity, antifungal property and deodorant property are particularly high in durability. A high-humidity chilled chamber having at least a part of the structure of the sintered body of the present invention having the above various excellent properties can maintain the chamber at an appropriate high humidity, and foods, particularly containing a large amount of water, can be dried. It is particularly suitable for storing undesired highly hydrous foods such as sashimi, vegetables, and paste products after opening. Therefore, the refrigerator incorporating the high-humidity chilled chamber of the present invention is also particularly suitable for storing highly hydrous foods. Further, according to the method for producing a sintered body of the present invention, the sintered body can be produced reliably and efficiently. In the method of the present invention, a conventional mold, a sintering furnace or the like can be applied as it is at the time of producing a sintered body, so that the operation is easy and the production cost can be reduced.

Claims (14)

[Claims] 1. 100 parts by weight of a powdery or granular material comprising an olefin polymer having a density of 0.90 to 0.965 g / ml, a melt index of 0.01 to 1.0 g / 10 min, and a normal hexane extract content of 10% by weight or less. Near the surface of the following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
A hydrophilic moisture-permeable porous material obtained by sintering a granular material obtained by soaking 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether represented by Olefin polymer sintered body. 2. 100 parts by weight of a powdery or granular material comprising an olefin polymer having a density of 0.90 to 0.965 g / ml, a melt index of 0.01 to 1.0 g / 10 min, and a normal hexane extractable content of 10% by weight or less. Near the surface of the following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
Represented by an integer of 6) 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether and one or both of an antifungal agent and a deodorant are soaked in a high concentration to obtain a granular material. A hydrophilic moisture-permeable porous olefin-based polymer sintered body obtained by sintering. 3. 100 parts by weight of powder and granules made of an olefin polymer having a density of 0.90 to 0.965 g / ml, a melt index of 0.01 to 1.0 g / 10 minutes, and a normal hexane extraction content of 10% by weight or less. Near the surface of the following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
The deodorant is obtained by soaking 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether represented by the formula (6) and 0.1 to 0.8 parts by weight of a fungicide to a high concentration. Porous inorganic powder having an average particle size of 0.1 to 10 μm and adsorbed with 0.1 to 2.5 parts by weight
A hydrophilic moisture-permeable porous olefin-based polymer sintered body obtained by sintering a powder or granular material in which parts by weight are adhered and buried. 4. 100 parts by weight of powder and granules made of an olefin polymer having a density of 0.90 to 0.965 g / ml, a melt index of 0.01 to 1.0 g / 10 minutes, and a normal hexane extraction content of 10% by weight or less. Near the surface of the following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
Representing an integer of 6) 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether and 0.1 to 2.5 parts by weight of a deodorant are soaked to a high concentration to form an antifungal agent. 0.1 to 10 parts by weight of porous inorganic powder having an average particle diameter of 0.1 to 10 μm
A hydrophilic moisture-permeable porous olefin-based polymer sintered body obtained by sintering a powder or granular material in which parts by weight are adhered and buried. 5. 100 parts by weight of a powdery or granular material comprising an olefin polymer having a density of 0.90 to 0.965 g / ml, a melt index of 0.01 to 1.0 g / 10 minutes, and a normal hexane extraction content of 10% by weight or less. Near the surface of the following formula 1: C _m H _{2m + 1} (OCH ₂ CH ₂ ) _n OCH ₂ COONa (1) (In the formula, m represents an integer of 13 to 18, and n is 3 to
Represented by an integer of 6) and 1.5 to 2.5 parts by weight of sodium carboxylated polyoxyethylene alkyl ether represented by the formula (1) and, if necessary, one or both of an antifungal agent and a deodorant are soaked to a high concentration. , Average particle size 0.1-1
A hydrophilic, moisture-permeable porous olefin-based polymer sintered body obtained by sintering a powder or granular material in which 0.1 to 10 parts by weight of a 0 μm porous inorganic powder is adhered and embedded. 6. The hydrophilic moisture-permeable porous olefin polymer sintered body according to claim 2, wherein the antifungal agent is a thiabendazole compound and the deodorant is a flavonoid compound. . 7. The hydrophilic moisture-permeable porous olefin polymer sintered body according to any one of claims 3 to 5, wherein the porous inorganic powder is zeolite, cristobalite or silica gel. 8. A high humidity chilled chamber using the hydrophilic moisture-permeable porous olefin-based polymer sintered body according to any one of claims 2 to 7 as at least a part of a ceiling portion, a wall surface or a bottom surface. 9. The sintered body used has an apparent specific gravity of 0.5 to
0.7 g / ml, water absorption rate 2 cm or more, water drop absorption 4 seconds or less, water absorption 25% or more, tensile strength 30 kg / cm ² or more, tensile elongation at break 15% or more, flexural modulus 1700 kg
/ Cm ² or more, bending strength 35 kg / cm ² or more, moisture permeability 1200 g / m ² · 24 hours or more, creep deformation 6 mm
The high-humidity chilled chamber according to claim 8, which has the following (80 ° C) and 3 mm or less (23 ° C), a dimensional change rate of 1% or less and a porosity of 28% or more. 10. A refrigerator incorporating the high humidity chilled chamber according to claim 8. 11. The sintered body used has an apparent specific gravity of 0.5.
~ 0.7g / ml, water absorption rate 2cm or more, water drop absorption 4
Seconds or less, water absorption 25% or more, tensile strength 30 kg / cm ²
Above, tensile elongation at break 15% or more, flexural modulus 1700k
g / cm ² or more, flexural strength 35 kg / cm ² or more, moisture vapor transmission rate 1200 g / m ² , 24 hours or more, creep deformation 6 m
The refrigerator according to claim 10, which has m or less (80 ° C) and 3 mm or less (23 ° C), a dimensional change rate of 1% or less, and a porosity of 28% or more. 12. A high-humidity chilled chamber according to claim 8 or 9, or a high-humidity chilled chamber of a refrigerator according to claim 10 or 11, wherein food is placed and the outside of the high-humidity chilled chamber is cooled with a cold air flow. How to store food. 13. The food according to claim 12, which is a highly hydrous food.
How to store the foods described. 14. A powder or granular material after soaking according to claim 1 or 2 or a powder or granular material after soaking according to claim 3, 4 or 5 and adhering / embedding is placed in a mold, and 0.5 to 0.5 at room temperature. Pressurized to 10 kg / cm ² , and then, while keeping the powder and granules in the mold, raise the temperature to the softening point or melting point + 5 ° C of the olefin polymer used in the sintering furnace and burn. A method for producing a hydrophilic moisture-permeable porous olefin-based polymer sintered body, which comprises binding.