JPH10235122A - Composite material having filtration and ion-exchange functions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove simply various ionic substances in liquid or gas, offensive odor substances of animals or plants, or fine powder such as duct, pollen, and mold by allowing a polyurethane foam to hold an ion-exchange resin. SOLUTION: A polyurethane foam is a foam including at least urethane bond and/or urea bond inside molecules. Either an open cell type or a closed type is favorable for the polyurethane foam and a micro-cellular type is included. The open cell polyurethane foam is particularly favorable because of the possession of gas permeability and/or water transmissiveness. The polyurethane foam is manufactured by reacting an active hydrogen compound with organic polyisocyanate. As the ion-exchange resin, disclosed acidic groups capable of ion-exchange and, besides resin having metal salt groups or basic groups of them, cation-exchange resin or anion-exchange resin already used, collected, and recycled can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite which has a filtering and ion-exchanging function and is capable of removing various impurities and harmful substances from liquids and gases, and exhibiting deodorant, antibacterial and antifungal properties. About the material.

[0002]

2. Description of the Related Art Generally, an ion exchange resin is used as a cation exchange resin or an anion exchange resin for removing various ionic impurities in raw water to improve the hardness of the raw water or to produce pure water. In addition, it is also applied to gas adsorption. Ion-exchange resin is usually used as a column packed in a resin tube or glass tube in granular or powder form, or as a porous ion-exchange resin filter formed by molding a porous fine powder of ion-exchange resin into a predetermined shape with a binder. , And is used in industrial applications by incorporating it into a predetermined device.

[0003]

However, the ion-exchange resin incorporated in such an industrial apparatus is efficient when producing a large amount of pure water or soft water, but is limited to homes and hospital rooms. In limited spaces, on the go, hiking, or in emergencies such as a disaster, a limited amount of sewage or raw water needs to be treated to provide pure water or soft water. It is difficult to say that it is possible to cope with such cases. Similarly, when removing harmful and odorous gases in the air, and fine particles such as dust, dust, pollen, bacteria, and mold, use large-scale facilities and plants to use ion-exchange resin columns and filters. While industrial processing is possible and efficient, it is practically very difficult in confined spaces, on the go, or in emergencies.

[0004] The present invention provides various ionic substances, various harmful substances, and odorous substances such as animals and plants, which are present in liquids and gases, regardless of large facilities and equipment. Another object of the present invention is to provide a composite material which can be easily used for filtering, ion-exchanging, or further removing fine particles such as garbage, dust, pollen of cedar and cypress, bacteria, fungi and the like by adsorption. I do.

[0005]

In order to achieve the above object, a composite material having a filtration and ion exchange function according to the present invention is characterized in that a polyurethane foam holds an ion exchange resin.

The composite material having the functions of adsorption, filtration and ion exchange according to the present invention is characterized in that a polyurethane foam holds an ion exchange resin and activated carbon.

Further, the deodorant, antibacterial or antifungal material of the present invention is characterized by comprising the above-mentioned respective composite materials.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polyurethane foam of the present invention includes any known foam having at least a urethane bond and / or a urea bond in a molecule, such as a polyurethane foam, a polyurethane uretonimine foam, and a polyisocyanolate foam. It is a flexible, semi-rigid or rigid foam. The polyurethane foam may be of an open cell type or a closed cell type, and includes microcellular. Open cell polyurethane-based foams are particularly advantageous for removing impurities and harmful substances from liquids and gases because they are breathable and / or water-permeable. Closed cell polyurethane foam
Since it gradually permeates liquids and gases, it can be used in the present invention. Further, the polyurethane-based foam in the present invention may be in a foamed form such as a slab foam, a mold foam, a sprayed foam, or a liquid injection foam into a face material space by injection or laydown.

The polyurethane foam of the present invention can be produced by reacting an active hydrogen compound with an organic polyisocyanate in the presence of a foaming agent and, if necessary, a catalyst or an additive. As this active hydrogen compound,
Polymer polyols and polyamines having a molecular weight of more than 500, and combinations thereof with low-molecular polyols having a molecular weight of 18 to 500, low-molecular polyamines, low-molecular amino alcohols, and chain extenders such as water; , A monoamine and a reaction terminator such as a monoamine. Examples of the polymer polyol and polymer polyamine include polyether polyol, polyester polyol, polyether polyamine, polyether ester polyol, lactone polyester polyol, polycarbonate polyol, acrylic polyol, polybutadiene polyol, phosphorus-containing polyol, P
IPA polyol, epoxy-modified polyol, acrylonitrile styrene graft copolymerized suspension polyol, acrylonitrile graft copolymerized suspended polyol, PIPA
Examples of the polyol include a polyurea-dispersed polyol and a styrene bead-dispersed polyether polyol. Examples of the low-molecular polyol and low-molecular polyamine include, for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexane glycol, neopentyl glycol, trimethylolpropane, hexane glycol, glycerin, sorbitol, ethylenediamine, And ethylene oxide adducts of ethylenediamine, wood-decomposed polyols, pulp-decomposed polyols, and starch-decomposed polyols. Examples of the organic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate (MDI), isophorone diisocyanate, lysine diisocyanate,
Hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isomers, mixtures of isomers, crude products, polymeric forms, uretonimine forms, burette forms, allohanate forms, prepolymers and coagulated prepolymers thereof are also included. As the foaming agent,
For example, water, air, carbon dioxide, nitrogen gas, methylene chloride, fluorocarbon compounds (CFC-11, HCFC
141b, HFC245fa, HCFC22, HFC1
34a, 143aHCF-365mfc, etc.) and pentane. These are selected and used depending on the kind of the intended polyurethane-based foam, required physical properties, blending method and the like. Examples of the catalyst include organometallic compounds such as stannas octoate and dibutyltin dilaurate, and amine compounds such as triethylamine and N, N, N ', N'-tetramethylpropane-1,3-diamine. No. Examples of the additive include a surfactant that affects the openness and independence of the polyurethane foam cell, a flame retardant that imparts flame retardancy to the foam, a filler that is convenient for recycling, a coloring agent, a plasticizer, and the like. When a filler is used in combination, it is advantageous for the production of a closed-cell non-aqueous foam. Examples of the surfactant include a polysiloxaneoxyalkylene copolymer containing an ethylene oxide unit, an ethylene oxide adduct of a non-polar phenol, and a sulfonated sodium ricinoleate.
Examples of the flame retardant include chloroalkyl phosphate, dibromoneopentyl glycol and the like. Fillers include silica, silica sand, carbon (powder), styrene beads, glass powder, bone powder, shell powder, plastic powder, rubber powder,
Fiber powder and the like.

In the present invention, as the ion exchange resin,
Known ion-exchangeable acidic groups (—COOH, —SO ₃
H), these metal bases (Au, Ag, Cu, Z
Resins having n, Fe, Al, Sn, Na, K salts or the like or basic groups (such as -NH ₂ , -N ⁺ R ₃ , where R is an alkyl group) (including newly manufactured products or activated products thereof). In addition to the above, cation or anion exchange resins which have already been used and recovered and regenerated can also be used. These resins are usually in the form of particles or powder. Even if the ion-exchange resin is already used and contaminated, its ion-exchange capacity is preferably 15% or more, especially 45% or more of the ion-exchange capacity of the original fresh ion-exchange resin. Can be. Particularly, the regenerated ion exchange resin obtained by pulverizing the ion exchange resin to 500 to 1 μm, preferably 300 to 5 μm is preferable because the ion exchange efficiency is high and the ion exchange resin itself can be recycled. In the regeneration treatment of the cation exchange resin, for example, the used and recovered ion exchange resin is repeatedly and successively passed through a diluted hydrochloric acid aqueous solution and a saline solution (in some cases, washed with methanol, MEK or the like, and then diluted hydrochloric acid aqueous solution and a saline solution). . The used and recovered anion exchange resin can be regenerated, for example, by successively and repeatedly passing a diluted aqueous sodium hydroxide solution, a diluted aqueous ammonium sulfate solution, and a diluted aqueous hydrochloric acid solution. It is preferable that each of these liquids is passed through a water washing step. After the regeneration treatment, when the ion-exchange resin is in the Na salt form, for example, it is sequentially passed through a dilute saline solution or diluted caustic soda aqueous solution. In this case, the metal salt of the ion-exchange resin can be obtained by passing the solution through an aqueous alkali solution or an aqueous solution of a Cu salt, an Ag salt, an Al salt, a Zn salt, or the like. The regeneration treatment of the ion exchange resin may be performed after producing the composite material of the present invention. When using a closed cell polyurethane foam as a base material, mixing an ion exchange resin with a binder and impregnating the polyurethane foam or applying it to the surface of the polyurethane foam, etc., pre-treat rather than post-treat. It is particularly preferable that the surface of the composite material is appropriately treated with methanol, ethanol, MEK, or the like as necessary after the production. The composite material of the present invention is most preferably produced by mixing an ion-exchange resin with a compounding raw material for producing a polyurethane-based foam, and producing and molding the mixture by a known polyurethane-based foam production method such as a batch method or a continuous method.

When activated carbon is used in combination in the present invention, the activated carbon is excellent in the ability to adsorb impurities and harmful substances, so that the adsorption function is further improved, and it is also useful for extending and promoting the filtration function and ion exchange function. . In the present invention, any known activated carbon can be used, but porous particles or powders are preferable.
Those having a specific surface area of 500 to 1500 m ² / g are more preferred.

In the composite material of the present invention, the ion exchange resin is used in an amount of 1/99 to 99/1, particularly 5 / It is preferable to use the composition in a weight ratio of 95 to 95/5. However, depending on the apparent density of the foam, the average cell diameter (number / 25 mm), the particle shape and the ion exchange capacity of the ion exchange resin, the application, etc. Are significantly different. Activated carbon also has an adsorbing function and promotes the function of the ion-exchange resin to extend its life.
Preferably, it is used in an amount of not more than% by weight.

[0013] The same procedure can be applied to the case where activated carbon is retained on a polyurethane foam together with an ion exchange resin. However, the activated carbon is mixed with the ion exchange resin or the like, and is impregnated into the polyurethane foam together or separately. May be.

The binder used in the present invention for fixing an ion exchange resin or activated carbon to a polyurethane foam is, for example, polyvinyl alcohol,
Starch, polyvinyl acetate, urea resin, melamine resin,
Examples thereof include a solution, suspension, and latex of a phenol resin and a polyurethane resin. These binders are preferably used in the range of 0.5 to 15% by weight based on the polyurethane foam. If the binder is used in a large excess, it will cover the surface of the ion exchange resin, and it will take time for the subsequent regeneration process, and in some cases, the ion exchange capacity of the ion exchange resin will be significantly reduced. It is important to do it. If the composite material of the present invention may be put into the mouth, an adhesive that is harmless to the human body is used.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. [Production of Polyurethane Foam Composite Material Retaining Ion Exchange Resin] Example 1 (1) Production of Flexible Polyurethane Foam 100 g of polyethertriol (hydroxyl value 56, manufactured by Sanyo Chemical Co., Ltd.), 3.9 g of pure water, silicone interface Activator L-520 (manufactured by Nihon Yunika Co., Ltd.) (1.1 g), catalyst TEDA (0.11 g) and tin octylate (0.25 g) were thoroughly mixed with stirring, and tolylene diisocyanate (TDI-80, Nippon Polyurethane Industry Co., Ltd.) was added to the mixture. 51)
g at room temperature and stirred and mixed.
Transfer of mm × 200 mm size of the polyethylene film on the inner surface of the plywood box in a box covered, by foaming, to give a soft open-cell polyurethane foam of apparent density 27 kg / m ^3. (2) Preparation of Binder Solution Containing Ion Exchange Resin Binder Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was diluted with 300 g of water in 1000 g of an emulsion.
R-W2-H Dry, Dowex SBR-PC-C
l Dry) or its (used) reclaimed and recovered products
Each 30 g was added, mixed and defoamed to prepare a binder solution. (3) The flexible open-cell polyurethane foam 100 mm × 100 mm × 10 mm was immersed in the binder solution, and the foam was compressed to remove bubbles.
%, And air-dried at 110 ° C. for 60 minutes to obtain an ion-exchange resin-impregnated and fixed flexible open-cell polyurethane foam composite material. Further, in the same manner, the length is 18.5 cm,
A cylindrical composite material having a diameter of 3.6 cm was produced. (4) Measurement of ion exchange capacity Measurement of cation exchange capacity After washing the sample with methanol and drying, put the weighed sample (1-2 g) in a chromatographic tube, add ion-exchanged water, and sample with a glass rod. Was completely purged, ion-exchanged water was flown using an AgNO ₃ aqueous solution until Cl ⁻ (in the case of hydrochloric acid regeneration) was no longer observed, and then 300 ml of a 4% NaCl aqueous solution was flowed for 90 minutes.
Make the total volume up to 500 ml with ion exchanged water,
The mixture was titrated with an N / 10 aqueous NaOH solution using a methylene blue mixed indicator. The ion exchange capacity (neutral salt decomposition capacity) was calculated by weight conversion. Measurement of anion exchange capacity After washing the sample with methanol and drying, put the weighed sample (1-2 g) in a chromatographic tube, add ion-exchanged water, and completely expel air contained in the sample with a glass rod. After that, ion-exchanged water was flowed until alkalinity was not recognized by phenolphthalein. Next, 300
A 4% aqueous solution of 4% NaCl was flowed for 90 minutes, the total volume was made up to 500 ml with ion-exchanged water, and the mixture was titrated with an aqueous N / 10 HCl solution using a mixed indicator of methyl red and methylene blue. The ion exchange capacity (neutral salt decomposition capacity) was calculated by weight conversion. The respective ion exchange capacities (ion exchange resin impregnation relative to the raw ion exchange resin and the ion exchange capacity ratio% of the fixed flexible open-cell polyurethane foam composite material) are summarized below. Sample No. 1: Dowex HCR-W2-H Dry
(Particle size: 200% or less 90%) / Polyurethane foam composite material (ion exchange capacity: 3.5 meq / g, ion exchange capacity ratio: 75%) 2: Recycled recycled Dowex HCR-W2-H
Sample No. Dry (particle size: 50% or less 95%) / polyurethane foam composite material (ion exchange capacity: 3.9 meq / g, ion exchange capacity ratio: 83%) 3: Dowex SBR-PC-Cl Dr
Sample No. y (particle size 200 μm or less 90%) / polyurethane foam composite material (ion exchange capacity 2.45 meq / g, ion exchange capacity ratio 61.3%) 4: Recycled Dowex SBR-PC-C
l Dry (particle size 50 μm or less 95%) / polyurethane foam composite material (ion exchange capacity 2.8 meq / g,
(Ion exchange capacity ratio 70%)

Example 2 In Example 1, 88 g of Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was replaced with 30 g of Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and score minformer. RF (Daiichi Kogyo Seiyaku Co., Ltd.) 8g
And Superflex VF (Daiichi Kogyo Seiyaku Co., Ltd.) 4
An ion exchange resin-containing binder solution was prepared in the same manner except that g was used. This is Stork's FP11C
The foam obtained by foaming with Foam was placed on the surface of the flexible open-cell polyurethane foam having a size of 100 mm × 100 mm × 10 mm obtained in Example 1 by about 1 μm.
After being applied to a thickness of 1 mm, it was air-dried at 110 ° C. for 40 minutes to produce the following ion-exchange resin-coated and fixed flexible open-cell polyurethane foam composite material. Then, the ion exchange capacity of these composite materials was measured. Sample No. 5: Dowex HCR-W2-H Dry
(Particle size: 200% or less 90%) / polyurethane foam composite material (ion exchange capacity 3.3 meq / g, ion exchange capacity ratio 70%) 6: Recycled Dowex HCR-W2-H
Sample (Dry (particle size 50 μm or less 95%) / polyurethane foam composite material (ion exchange capacity 3.1 meq / g, ion exchange capacity ratio 66%) 7: Dowex HCR-W2-Cu Dr
y (particle size 200 μ or less 90%) / polyurethane foam composite material (ion exchange capacity 4.1 meq / g, ion exchange capacity ratio 87%)

Example 3 An ion-exchange resin was added to and mixed with an all-MDI flexible foam system HM-101A (manufactured by Nippon Polyurethane Industry Co., Ltd.), and HM-101B (NCO content 2
7.6%, manufactured by Nippon Polyurethane Industry Co., Ltd.)
500mm x 500m
The resultant was placed in a container having a size of mx 300 mm, foamed, and molded to produce the following ion-exchange resin-containing soft open-cell polyurethane foam composite material. Further, similarly, a cylindrical composite material having a length of 18.5 cm and a diameter of 3.6 cm was produced. Sample No. 8: Dowex HCR-W2-H Dry
(Particle size 200 μ or less 90%) / polyurethane foam = 40: 60 (weight ratio) composite material (apparent density 85 kg /
m ³ ) Sample No. 9: Dowex HCR-W2-H Dry
(Particle size: 45% or less 90%) / polyurethane foam =
40:60 (weight ratio) composite material (apparent density 103 kg /
m ³ ) Sample No. 10: Recycled Dowex HCR-W2-
H Dry (particle size 50 μ or less 95%) / polyurethane foam = 40: 60 (weight ratio) composite material (apparent density 7
5 kg / m ³ ) Sample No. 11: Recycled Dowex HCR-W2-
Sample No. Cu Dry (particle size 50 μm or less 95%) / polyurethane foam = 40: 60 (weight ratio) composite material (apparent density 81 kg / m ³ ) 12: Recycled Dowex HCR-W2-
Ag Dry (particle size of 50% or less 95%) / polyurethane foam = 40: 60 (weight ratio) composite material (apparent density 78 kg / m ³ ) 13: Dowex SBR-PC-Cl D
ry (particle size 50 μ or less 95%) / polyurethane foam = 40: 60 (weight ratio) composite material (apparent density 75 kg
/ M ³ ) Sample No. 14: Dowex HCR-W2-H Dr
y (particle size 200 μ or less 90%) / polyurethane foam = 50: 50 (weight ratio) composite material (apparent density 125 k
g / m ³ ) Sample No. 15: Dowex HCR-W2-H Dr
y (particle size 45 μ or less 90%) / polyurethane foam = 50: 50 (weight ratio) composite material (apparent density 140 kg
/ M ³ ) Sample No. 16: Recycled Dowex HCR-W2-
H Dry (particle size 50 μ or less 95%) / polyurethane foam = 50: 50 (weight ratio) composite material (apparent density 1
00 kg / m ³ ) Sample No. 17: Recycled Dowex HCR-W2-
Sample No. Cu Dry (particle size of 50% or less 95%) / polyurethane foam = 20: 80 (weight ratio) composite material (apparent density 73 kg / m ³ ) 18: Recycled Dowex HCR-W2-
Ag Dry (particle size of 50% or less 95%) / polyurethane foam = 20: 80 (weight ratio) composite material (apparent density 70 kg / m ³ ) 19: Dowex SBR-PC-Cl D
ry (particle size 50 μ or less 95%) / polyurethane foam = 20: 80 (weight ratio) composite material (apparent density 75 kg
/ M ³ )

Example 4 Polyol RX300 (manufactured by Sanyo Chemical Co., Ltd.) 656.5
g of a fluorocarbon blowing agent R-11 (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.), 850 g of an ion-exchange resin was added thereto, followed by stirring and mixing. 3.3 g of 1 (made by Kao Corporation) and 1 water
3.1 g, 9.8 g of silicone surfactant SH190 (manufactured by Toray Dow Corning Co., Ltd.), and CFC-based blowing agent R-1
1 (Mitsui DuPont Fluorochemical Co., Ltd.) 11
7.2 g was added and mixed by stirring. This polyol-based mixture and Polymeric MDI (MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) were added at a weight ratio of 185: 100 and mixed, and 350 g of the mixture was placed on an aluminum plate to form a frame having a thickness of 20 mm. Material and 50cm x 50cm kraft paper (made by Achilles Co., Ltd.) are immediately poured into a container (50 ° C) installed on the upper and lower surfaces, and an aluminum plate on the top and a kraft paper lid on the bottom. Clamped and foamed. After leaving for 20 minutes, the clamp was removed, and a board (a rigid closed-cell type polyurethane foam composite material containing an ion exchange resin) having kraft paper on both surfaces was manufactured. Sample No. 21: Dowex HCR-W2-H Dr
y (particle size 200 μ or less 90%) / polyurethane foam composite material Sample No. 22: Dowex HCR-W2-H Dr
y (particle size 45 μ or less 90%) / polyurethane foam composite material Sample No. 23: Recycle and Recycle Dowex HCR-W2-
H Dry (particle size 50 μm or less 90%) / polyurethane foam composite material Sample No. 24: Dowex HCR-W2-Cu D
ry (particle size 50 μm or less 90%) / polyurethane foam composite material Sample No. 25: Recycled Dowex HCR-W2-
Ag Dry (particle size: 55μ or less 95%) / polyurethane foam composite material

Example 5 30 g of a shrink, amine-based polyether polyol
Ion exchange resin 1 in a mixture of 70 g of ethylenediamine-based polyether polyol and 30 g of CFC-based blowing agent R-11 (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.)
Then, the silicone surfactant SH190 (manufactured by Toray Dow Corning Co., Ltd.) is further added thereto.
2.0g, amine catalyst TEDA 1.25g and flame retardant T
10.0 g of CEP and 10 g of CFC-based foaming agent R-11 (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.) were added and mixed with stirring. Polymeric MDI is added to this polyol mixture.
(MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.)
The mixture was added and mixed at a weight ratio of 60: 100, and the mixture was blown and foamed with an SP-56 type air spray manufactured by Viking Co., Ltd. to form a hard independent resin containing an ion exchange resin having a thickness of about 1 mx 0.8 mx and below. A cellular polyurethane-based sprayed foam composite was obtained. The sample No. In the case of 26,
In the polyol mixture containing no ion-exchange resin, Polymeric MDI (MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added at a weight ratio of 100: 100, mixed, and sprayed and foamed in the same manner as described above.
A rigid closed cell polyurethane-based sprayed foam of about 1 mx 0.8 mx about 18 mm containing no ion exchange resin was obtained. Sample No. Sample No. 26: Control spraying (foam thickness about 18 mm) 27: Dowex HCR-W2-H Dr
Sample No. y (particle size 200 μ or less 90%) / polyurethane foam composite material (foam thickness about 18.5 mm) 28: Dowex SBR-PC-Cl D
ry (particle size 200 μ or less 90%) / polyurethane foam composite material (foam thickness about 17 mm) 29: Dowex HCR-W2-H Dr
Sample No. y (particle size: 50% or less 90%) / polyurethane foam composite material (foam thickness: about 19 mm) 30: Dowex HCR-W2-Cu D
ry (particle size 45μ or less 95%) / polyurethane foam composite material (foam thickness about 16mm)

Example 6 An ion-exchange resin and activated carbon were added to and mixed with an all-MDI flexible foam system HM-101A (manufactured by Nippon Polyurethane Industry Co., Ltd.), and HM-101B (NCO
Content 27.6%, manufactured by Nippon Polyurethane Industry Co., Ltd.)
Add with COindex 100 and mix to 500mm x 5
It was placed in a 00 mm × 300 mm container and foamed to produce the following ion-exchange resin-containing soft open-cell polyurethane foam composite material. Sample No. 31: Dowex HCR-W2-H Dr
y (particle size 200μ or less 90%) / activated carbon (particle size 200μ
Below 100%) / polyurethane foam = 20/20
/ 60 (weight ratio) composite material (apparent density 122 kg / m
³ )

Example 7 [Purification of River Water] A flexible open-cell polyurethane foam composite material having a length of 18.5 c and having an ion-exchange resin obtained in Examples 1 and 3
m, a cylindrical molded product having a diameter of 3.6 cm) is packed without compression into a glass tube having a length of 20 cm, well water (collected in Yanagimachi, Shinjuku-ku) is poured from the upper portion at a rate of 75 ml / min, and filtered water is dropped from the lower portion. Obtained. For comparison, the soft open-cell polyurethane foam obtained in Example 1 (without holding an ion-exchange resin) or the soft open-cell polyurethane foam produced in the same manner as in Example 3 without using the ion-exchange resin. Filtered water was obtained in the same manner as described above, using only the polyurethane-based foam. The transparency and odor of the obtained filtered water were measured.
Shown in

[0022]

[Table 1]

Example 8 [Antibacterial and antifungal] (1) Sensitive desk medium-N containing bacteria of Staphylococcus epidermidis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa or Bacillus subtilis
(Nissui) plate (10 ⁶ bacteria), ion-exchange resin-supported polyurethane foam composite material (10 mm × 10 mm × 10 mm) sample N wetted with 0.5% agar
o. 1 to 30 (however, sample Nos. 5 to 7 are put from the application part), and incubated at 5 ° C.
After culturing at 18 ° C. for 18 hours, the size of the halo was measured. (2) A polyurethane foam composite material (10 mm × 10 mm ×) which was wetted with 0.5% agar on a plate of Sabouraud agar medium (Eiken) containing fungi such as athlete's foot, black mold, or Candida fungi. 10mm x 10mm) Sample N
o. 1 to 30 (however, sample Nos. 5 to 7 are put from the application part), and incubated at 5 ° C.
After culturing at 72 ° C. for 72 hours, the size of the halo was measured. Table 2 summarizes these results. In Table 2, the sample No. Reference numeral 20 denotes a control board (a rigid polyurethane foam not holding an ion exchange resin, manufactured by Achilles Corporation) having kraft paper on both surfaces. In Table 2, ++ indicates that the halo has a diameter of 20 mm or more,
+ Indicates that the halo has a diameter of 11 mm or more and less than 20 mm, and-
Indicates that no halo is observed.

[0024]

[Table 2] When a polyurethane-based foam which does not hold an ion-exchange resin was used, it was-for all bacteria and fungi. In particular, it has been found that the closed-cell polyurethane foam composite material has remarkable antibacterial and antifungal properties.

Example 9 [Adsorption of Gas Substance] (1) Sample No. 1-4, 8-10, 13-16, 19
Alternatively, a predetermined amount of 31 is cut out and weighed, and this is
The suspension was suspended at the center of a desiccator having a volume of 0 cm and a volume of 2.7 liters, and 1.0 mg (50 μl) of triethylamine or 0.18 mg (20 μl) of isovaleric acid was injected into a glass Petri dish provided on the bottom surface of the desiccator and immediately sealed. . Leave the desiccator at 40 ° C. for 30 minutes, then at room temperature (2
(5 ° C.) for 30 minutes, and the gas in the desiccator was removed from a gas detector tube No. 180 (for measuring triethylamine) or No. 180 The gas concentration was measured with 81 L (for measuring isovaleric acid). In the same manner, the control gas concentration when only the polyurethane foam not holding the ion exchange resin was put was measured. The results for triethylamine are summarized in Table 3, and the results for isovaleric acid are summarized in Table 4. In addition, the gas concentration and the gas adsorption rate were calculated by the following equations. Gas concentration (ppm) = measured value × detected substance conversion coefficient × temperature coefficient (the conversion coefficient of triethylamine is 0.9, the temperature coefficient is 0.95, the conversion coefficient of isovaleric acid is 1.5, The temperature coefficient is 0.9.) Gas adsorption rate (%) = (concentration of control gas−gas concentration during adsorption) × 100 ÷ control gas concentration

[0026]

[Table 3]

[0027]

[Table 4] From the results shown in Tables 3 and 4, those holding a cation exchange resin are effective for adsorption of amines and other alkali neutral salts, and those for holding acid and acidic neutral salts are anion exchange resins. Was excellent.

Example 10 [Adsorption of Body Odor] A small piece (size of about 18 mm × 36 mm × 5 m) of a polyurethane foam composite material holding an ion exchange resin shown in Table 5
m) is affixed to the right and left armpits and the upper thigh crotch side of a 31-year-old man and a 27-year-old woman, respectively, and the surface is covered and fixed with medical adhesive tape. The residual body odor of the small piece was examined by a sensory test by a tester a) and a 22-year-old woman (a sensory tester b). Also, a small piece (about 18 mm × 36 mm × 6 mm) of the ion-exchange resin-holding polyurethane foam composite material shown in Table 6 was attached to the shoe insole, and the surface was covered and fixed with medical adhesive tape. 36 hours after the 27-year-old woman was put on, she was detached, and the residual body odor of the small piece was examined by a sensory test by a 25-year-old man (sensory tester a) and a 22-year-old woman (sensory tester b). For comparison, the residual body odor was examined in the same manner as described above, using the flexible open-cell polyurethane foam not holding the ion exchange resin obtained in Example 1. Table 5 summarizes the measurement results of the residual body odor on the right axilla and upper thigh crotch side, and Table 6 summarizes the measurement results of the residual body odor of the shoe insole. In Tables 5 and 6, the degree of residual body odor was 0 (none) <1 (weak) <2 (substantially strong).
<3 (strong).

[0029]

[Table 5]

[0030]

[Table 6]

Example 11 [Anti-pollinosis as a mask] An ion-exchange resin-supported polyurethane foam composite material (size: 45 mm x 60 mm x 5 mm) shown in Table 7 was set between the outer gauze layers of a commercially available sanitary mask. A 45-year-old man who complains of nasal discharge by going out and has a change in voice due to cedar pollinosis,
18 year old man, 15 year old man, 33 year old woman, 17 year old woman 5
With the mask worn on the name (excluding desorption during meals), between February 25 and March 20, 1996,
Shinjuku Gyoen is in the park for about 40 to 50 minutes, and is passed through twice.
After hours, they were interviewed for symptoms. For comparison, a commercially available sanitary mask set with a soft open-cell polyurethane foam manufactured in the same manner as in Example 3 without using an ion-exchange resin was worn, and the symptoms were heard in the same manner as above. Investigated. Table 7 summarizes these results. In Table 7, 0 (no hay fever symptoms) <1 (almost no) <2 (voice change) <3 (voice change nasal discharge).

[0032]

[Table 7] From the results in Table 7, it was confirmed that the mask incorporating the ion-exchange resin-holding polyurethane foam composite material of the present invention reduced pollinosis.

Example 12 [Adsorption of smoke and scent as a mask] Polyurethane foam composite material (size: 45 mm x 65 mm x 5 mm) having an ion exchange resin shown in Table 8 and 18
A 24-year-old male (sensory tester a) and a 25-year-old female (sensory tester b) wearing the multi-layered gauze into a commercially available sanitary mask and wearing them at a business office in the Nihonbashi Building, Tokyo, A sensory test was conducted on the aroma (odor) of cigarette smoke and audio colon. For comparison, a flexible open-cell polyurethane foam produced in the same manner as in Example 3 without using an ion-exchange resin and 1
A sensory test was carried out in the same manner as described above while wearing a commercially available sanitary mask incorporating eight-layer gauze. Table 8 summarizes these results. In Table 8, the scent (smell) of cigarette smoke and audio colon was 0: disappeared.
1: Significantly weakened, 2: Slightly weakened, 3: No change.

[0034]

[Table 8]

[0035]

As described above, according to the present invention, various ionic substances present in liquids and gases, harmful substances, harmful substances, irrespective of large facilities and equipment, and in any place. It has become possible to provide a composite material which can be easily used to remove malodorous substances or fine powders by filtration, ion exchange, or further adsorption, and furthermore, provide a deodorant, antibacterial or antifungal material. . That is, specifically, (1) The composite material of the present invention is a polyurethane-based elastic material, which is an antibacterial, antifungal, and odor-adsorbing cushion, mattress, scourer, cleaner, packaging material, carpet packing material, It can be used as a doll, a toy, a flower insertion substrate, a sheet, a medical material, a rehabilitation material, and the like. (2) The composite material of the present invention is a non-open cell type polyurethane foam, for example, a rigid foam, which is obtained by spraying or pouring in addition to boards, panels, siding materials, slab foam trim materials, pulp materials and the like. Bacteria and molds can be suppressed by using on-site foams, and the generation of odors associated with them can be suppressed.
It can be used as a heat insulator. (3) Since the composite material of the present invention is antibacterial, antifungal, and odor-adsorbing, it can be widely applied to automobile interior materials such as seat cushions, seat backs, floor mats, bed rests, instrument panels, steering wheels, and the like. It is possible to significantly contribute to the countermeasures against car hogging. (4) Since the composite material of the present invention has an ion exchange function, it can be widely used as various polyurethane conductive materials. (5) By putting the composite material of the present invention in a portable container and passing it through polluted water or hard water,
Since these can be watered, sterilized, softened, or purified, they can be used as a simple small-sized water treatment device for securing drinking water or the like even in normal or emergency situations. (6) Since the composite material of the present invention has a high deodorizing effect on organic compounds such as ammonia, triethylamine, and isovaleric acid, it can be used for breasts, underarms, crotch, or socks of human body underwear.
It can be used as shoe floors, menstrual pads, etc. (7) The composite material of the present invention has a large antibacterial and antifungal activity against bacteria and angi group, and as an antibacterial material and an antifungal material, coating materials such as wall materials, flooring materials, measuring instruments or interior materials, and paper for foods. It can be used for containers (paper packs), artificial breeding floors for vegetable plants, and packaging materials for fish, meat, fruits, vegetables, and the like. (8) Since the composite material of the present invention can filter pollen of cedar and cypress and suppress pollinosis, it can be used as a mask material. (9) When bath water that has been bathed is passed through the composite material of the present invention, it is possible to regenerate and reuse bath water. Further, in the composite material of the present invention using activated carbon in addition to the activated carbon, an adsorption function is added, and a filtration function and an ion exchange function are promoted and the life thereof can be extended.

Claims (3)

[Claims] 1. A composite material having filtration and ion exchange functions, comprising a polyurethane foam holding an ion exchange resin. 2. An adsorbent, comprising a polyurethane foam holding an ion exchange resin and activated carbon.
A composite material having filtration and ion exchange functions. 3. A deodorant, antibacterial or antifungal material comprising the composite material according to claim 1.