JP2001293370A - Absorbing member and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an absorbing member having excellent water absorbability, absorbing water to develop excellent antibacterial properties, having a light weight and a small volume at the time of transport, increased in its weight and volume at the time of water absorption, having high shape followability and capable of being used as soil. SOLUTION: The water absorbing member absorbs and removes water stagnated on a floor surface by leak of water or flooding and is obtained by filling a water permeable bag made of a cotton fabric with an antibacterial water absorbent 14 comprising a modified polymeric compound. The water absorbing member absorbs water to swell. Since the water absorbing member is filled with the antibacterial water absorbent, it does not become an insanitary state such that microorganisms or the like are generated even if it absorbs water. When the water absorbing member is dried, it again restores water absorbability and can be used as the water absorbing member. The antibacterial water absorbent (modified polymeric compound) is manufactured by applying acid treatment or metal salt forming treatment to a general organic resin waste material comprising an ABS resin or the like and has a hydrolysate of a nitrile group and a metal salt of an acid group added as a substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water absorbing body for absorbing and removing water remaining on a floor surface or the like that has leaked or flooded, and a dike when a water level of a river or the like rises due to a flood or the like. The most suitable water absorber as a sandbag used to prevent the break of the embankment by raising the embankment, or to repair the breach of the embankment when the embankment is broken, and the manufacturing method thereof. The present invention relates to a water-absorbing body having excellent antibacterial properties in a state of absorbing water and a method for producing the same.

[0002]

2. Description of the Related Art When water remaining on a leaked or submerged floor surface or ground is absorbed and removed, water is often absorbed and removed using a water-absorbing body. BACKGROUND ART Conventionally, a water absorbing body is made of a fibrous material such as a cloth having a water absorbing property, such as absorbent cotton or a mop. In addition, in order to prevent flooding of rivers and lakes in the event of a flood, etc., a water absorber having a function of a sandbag has attracted attention as a substitute for the sandbag.

[0003] Conventionally, sandbags have been made by putting a filler such as earth and sand in a strong bag such as a hemp bag, and are used to raise a dike in the event of a flood or the like to prevent flooding of rivers, lakes and marshes. It is used to close the breach of a dyke. Also, at the digging site where a hole is dug in the soil layer,
It is also used for earth retaining, etc. The sandbag requires a certain bulk and weight in order to prevent it from moving against water pressure or the like from the viewpoint of its function, so that the sandbag is large in volume and heavy.

By the way, sandbags are heavy and bulky, so that they must be manufactured as sandbag products in a remote place and transported to a use site using a vehicle or the like. In addition, labor is required for transportation and unloading. In other words, the material is unsuitable for transportation. In addition, in the event of a landslide, it is necessary to promptly supply people's life assets to the places where they are needed, when necessary, to protect them from flooding. So far, sandbags have been important civil engineering materials needed in the event of a disaster, but when disasters occur, handmade sandbags filled with sand and sand are used as needed near the disaster occurrence site as needed. Have been.

[0005]

However, the above-mentioned conventional water absorber has the following points to be improved. The first problem is that conventional water-absorbing bodies, including those having the function of sandbags, have poor antibacterial properties when they are in a state of absorbing water, and when left in the state of absorbing water, microorganisms proliferate. Is unsanitary. The second problem is that the conventional water absorbent using a fibrous material to absorb and remove leaked water and the like has a low water absorption, so that a small amount of water is absorbed. The problem is that a large amount of water absorber is required.

[0006] The third problem is that, when a water-absorbing body is used as a sandbag, the sandbag is heavy and bulky as described above. It is a problem that it is manufactured in. In this case, there is a problem that the production efficiency is extremely low, and the necessary number of sandbags cannot be satisfied in the event of a disaster. That is,
Sandbags are materials necessary to protect the lives and properties of residents in an emergency such as a flood, and it is important that the sandbags are easy to produce and can be quickly applied. Therefore, instead of a handmade sandbag, a sandbag that is small in weight and volume and easy to transport, and that increases in weight and volume when used, is required so that it can be used quickly in an emergency. Have been.

[0007] A fourth problem is that it is difficult to reuse the conventional water-absorbing body even if the water-absorbing body is once dried. The fifth problem is that conventional water absorbers, particularly water absorbers using fibrous materials, do not utilize waste resources and are not recycled products, and thus do not effectively utilize earth resources.

Therefore, the present invention has excellent water absorption and excellent antibacterial properties in a state of absorbing water, and furthermore, when transported,
It is an object of the present invention to provide a water absorber that is small in weight and volume, increases in weight and volume by absorbing water during use, and has a high shape-following external shape, and further, can be used as a sandbag. . Furthermore, the present invention, by drying the water-absorbing body that has absorbed water, a water-absorbing body that can be used repeatedly, and further, by utilizing organic polymer waste materials and inorganic solid waste materials recovered from wastes that are in trouble for treatment, It aims to provide a water absorber that can contribute to the maintenance of the global environment.

[0009]

In order to achieve the above object, a water absorber according to the present invention is made of an organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene as a raw material. A water absorbent having an antibacterial water absorbent made of a modified polymer compound in a water-permeable bag-like body,
The modified polymer compound has a metal salt of an acid group added as a substituent.

The method for producing a water-absorbing material according to the present invention is characterized in that an antibacterial water-absorbing agent comprising a modified polymer compound starting from an organic polymer material containing acrylonitrile and at least one styrene and / or conjugated diene is used. A method for producing a water-absorbent body having a water-permeable bag-like body, comprising: an acid treatment step of reacting an organic polymer material with an acid to add an acid group as a substituent to the organic polymer material; and A metal treatment step of forming a metal salt of an acid group by reacting the passed organic polymer material with a metal salt.

In the present invention, when the modified polymer compound has an unreacted nitrile group, the insolubility in water and the gel strength are increased when water is absorbed.
In addition, water absorption is improved by a nitrile group hydrolysis reaction forming group, and excellent antibacterial properties and water absorption are provided by an acid group metal salt added as a substituent to styrene and / or conjugated diene.

In the present invention, an antibacterial water-absorbing agent, that is, an antibacterial modified polymer compound is required, but it is possible to use a combination of an antibacterial modified polymer compound and another water-absorbing agent having only water absorbency. it can. As another water-absorbing agent, a known water-absorbing material can be used.However, in order to effectively use the waste material of the organic polymer material which is one of the objects of the present invention, acrylonitrile, styrene and acrylonitrile recovered from the waste material are used. It is preferable to use an organic polymer material containing at least one of a conjugated diene and / or another water absorbing agent having an ionic group added as a substituent by acid treatment.

According to the present invention, with the above construction, the weight and the volume are small during transportation, the weight and the volume are significantly increased by absorbing water during use, and the water absorbing body has excellent external shape followability, or A water absorber that can be used as a sandbag is realized. In addition, since an antibacterial water-absorbing agent is used, it is possible to prevent infestation of microorganisms in a state where water is absorbed. Therefore, it is possible to prevent the odor of decay, the occurrence of bacteria, the coloration due to propagation, the occurrence of unsanitary conditions such as the occurrence of "sliminess" by the bacteria, and the deterioration of the surface and inside of the water absorbing body. Can be prevented. Also, since the water absorbing body does not change,
By drying the water-absorbing body, the water can be repeatedly used. Furthermore, by recycling the waste of the organic polymer compound and the waste of the inorganic solid matter, which are difficult to treat, it is possible to contribute to the maintenance of the global environment.

[0014] The starting materials of the modified polymer compound constituting the starting material antimicrobial water absorbing agent of the antibacterial water absorbing agent is an organic polymer material containing acrylonitrile and one or more styrene and / or conjugated diene. The organic polymer material has an acrylonitrile unit content of 5 mol% or more and 80 mol% or more.
Molar% or less, preferably 10 to 60% by mole, more preferably 20 to 50% by mole. When the content of the acrylonitrile unit is less than 5 mol%, it becomes water-soluble upon acid treatment, and it becomes difficult to form an antibacterial water-absorbing agent having insolubility in water. Conversely, if it exceeds 80 mol%, the organic polymer material becomes hard and difficult to pulverize into small pieces, or the content of at least one of styrene and conjugated diene in the organic polymer material decreases, Since the introduction rate of the group (acid group) also decreases, it becomes difficult to impart excellent antibacterial properties.

Conversely, according to the present invention, the structural unit other than acrylonitrile of the organic polymer material is subjected to an acid treatment to introduce an ionic acid group as a substituent into the organic polymer material. At least one of styrene and / or conjugated diene is required. The acid group serves as a site for improving the water absorption of the modified polymer compound, particularly for the aqueous electrolyte solution, and for supporting a metal ion imparting antibacterial properties. The content of at least one type of styrene and / or conjugated diene is in the range of 20 mol% to 95 mol%, preferably 40 mol% to 85 mol%, more preferably 50 mol% to 80 mol%. It is desirable to include one. The conjugated diene is, for example, butadiene, isoprene and the like.

If acrylonitrile and styrene and / or conjugated diene are contained in predetermined amounts, another constituent unit may be contained in the organic polymer material or the waste material of the organic polymer material. Is also good. These other structural units include maleic anhydride, itaconic anhydride, α-methylstyrene, acrylamide, methacrylamide, acrylic acid, and acrylate (carbon number: 1 to 10
The following saturated and unsaturated hydrocarbons), methacrylic acid and methacrylic acid esters (saturated and unsaturated hydrocarbons having 1 to 10 carbon atoms), vinyl acetate, vinyl chloride, ethylene, propylene, butylene, vinylpyrrolidone, Vinyl pyridine and the like can be mentioned.

The molecular weight of the organic polymer material, which is the starting material of the modified polymer compound, is expressed as a weight average molecular weight (Mw) of 1,0.
Not less than 00 and not more than 20,000,000, further not more than 10,000
The range is generally from 00 to 1,000,000. When the weight-average molecular weight is less than 1,000, it becomes water-soluble at the time of acid treatment, and it becomes impossible to obtain a water-absorbing agent insoluble in water. Conversely, if the weight average molecular weight is higher than 20,000,000, the reaction rate at the time of acid treatment becomes slow, so that the economic efficiency is inferior and it is not practical.

As an organic polymer material containing acrylonitrile and at least one of styrene and conjugated diene, ABS resin (acrylonitrile-butadiene-styrene resin), SAN resin (styrene-acrylonitrile resin), ASA resin (acrylonitrile-styrene- Resin-based polymer materials such as acrylate resin) and ACS resin (acrylonitrile-chlorinated polyethylene-styrene resin) can be suitably used. Further, a rubber-based polymer material such as NBR (acrylonitrile-butadiene rubber) can be suitably used.

The organic polymer material may be a newly manufactured virgin pellet, a discharged product (semi-product) generated in a resin production process or a molding process of a molded product, or a specific product. It may be a used waste material formed and used. The used waste material refers to, for example, a waste material such as a housing, various parts, a tube, a hose, and various cushioning materials used for an electric product, an automobile, or the like. Emission sources may be any factories, stores, households, etc., but those collected from factories, stores, etc., have relatively more composition than general waste from households, etc. More desirable.

The organic polymer material may be an alloy with another resin, and may include a coloring pigment, a coloring paint, a stabilizer, a flame retardant, a plasticizer, a filler, and other auxiliary agents. Waste material containing the agent may be used. Further, a mixture of used waste material and virgin material may be used.

The other resin which can be mixed with the organic polymer material and the alloy is desirably a resin which does not inhibit the acid treatment. Examples thereof include polyphenylene ether, polycarbonate, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, and the like. Examples thereof include polyamide (nylon) and polyester. The mixing resin is desirably mixed at a content of 60% by weight or less based on the organic polymer material. That is, when the content of these resins increases,
This is because the reaction during the acid treatment is inhibited.

Pretreatment of Organic Polymer Before the acid treatment of the organic polymer, it is desirable to first crush the organic polymer into small pieces of 3.5 mesh or less. When the size is larger than 3.5 mesh, the surface area per unit volume of the organic polymer material which participates in the acid treatment reaction becomes small, and the acid treatment becomes difficult, so that the reaction time becomes long and is not practical. Also, the water absorption of the antibacterial water-absorbing agent is significantly reduced. There are the following methods for crushing into small pieces. The first crushing method is a method of crushing using a crusher and then sieving. When the organic polymer material contains a rubber component, it is preferable to pulverize using this method after the freezing treatment. Second
Is a method of melting by heating and then pelletizing into fine beads.

Inorganic Additives of Organic Polymer Materials When carbon black or titanium oxide is contained as an inorganic additive in the organic polymer material, acid treatment is promoted, so that the antibacterial effect and the water absorbing effect of the water absorbing agent are promoted. Is improved. The reason is that during the reaction of the acid treatment, the periphery of the inorganic pigment is acid-treated and the inorganic pigment easily comes off the organic polymer material, so that the surface of the organic polymer material becomes a porous surface, and the acid becomes highly organic. This is because it easily permeates into the molecular material.

Carbon black and titanium oxide are originally
It may be contained in an organic polymer material,
Alternatively, they may be separately added to and mixed with the organic polymer material.
In addition, in terms of improving the antibacterial properties and water absorption performance of the water-absorbing organic polymer resin obtained by converting the organic polymer material into a modified polymer resin, an organic polymer material containing carbon black and titanium oxide was originally used. It is preferable to use carbon black and titanium oxide because they are uniformly and uniformly dispersed. Carbon black and titanium oxide are plastic colorants, reinforcing agents,
What is generally used as an electrical conductivity imparting agent may be used. The content of the inorganic substance such as carbon black and titanium oxide contained in the organic polymer material is 0.01% by weight or more and 20% by weight or less, preferably 0.05% by weight, based on the dry weight of the organic polymer material. It is in the range of 10% by weight or less.

The carbon black may be produced by any of a channel method, a furnace method, and a thermal method, and may be produced by using each alone or in combination of a plurality of methods. The average particle size of the carbon black is from 0.005 μm to 100 μm, preferably from 0.01 μm to 10 μm.

Titanium oxide is a rutile type, an anatase type,
Any type of ultrafine titanium particles may be used, and each may be used alone or in combination. The average particle diameter of titanium oxide is 0.01 μm or more and 50 μm or less,
Preferably, it is in the range of 0.05 μm or more and 10 μm or less.

[0027] In process step the present invention production process, the organic polymer material is acid treatment, followed by the formation reaction of the salt to it, the organic polymer material can be converted to the antibacterial water absorbing agent. That is, by the acid treatment, a part of acrylonitrile in the organic polymer material generates a reaction product group by a hydrolysis reaction, while an acid group is introduced into styrene or conjugated diene. Next, by performing a salt-forming treatment by contacting with an aqueous solution of a metal salt or the like, the introduced acid group can be converted into a metal salt mainly composed of, for example, silver, copper, or zinc.

Acid Treatment of Organic Polymer Material The acid used in the acid treatment step of the present invention is preferably an inorganic acid. The amount of the inorganic acid charged is in the range of 1 to 500 times, preferably 10 to 200 times the weight of the organic polymer material to be subjected to the acid treatment. If the addition amount of the inorganic acid is less than one time, the introduction ratio of ionic groups of styrene and conjugated diene and the hydrolysis reaction ratio of acrylonitrile groups decrease. As a result, the generation rate of acid groups that are sites for supporting metals such as silver, copper, and zinc that impart antibacterial properties is reduced,
The formation of these salts is inhibited. Conversely, if the addition amount of the inorganic acid is more than 500 times, it is necessary to neutralize an excess amount of the inorganic acid, which is disadvantageous both economically and operation time.

Examples of the inorganic acid used in an inorganic acid acid treatment to be used in the acid treatment, sulfuric acid, sulfuric anhydride,
Fuming sulfuric acid, a sulfonating agent such as chlorosulfonic acid, and
Nitric acid, fuming nitric acid, phosphoric acid, phosphorus chloride, phosphorus oxide and the like. Among these, concentrated sulfuric acid, sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid are preferred, and concentrated sulfuric acid having a concentration of 70% by weight or more is particularly preferred.

The inorganic acids may be used alone or in combination of two or more. When used in combination, they may be mixed or added sequentially. For example, an organic polymer material is first treated with concentrated sulfuric acid, and then sulfuric anhydride is added to complete the reaction, so that in an aqueous system, shape stability is high, excellent antibacterial properties, and high water absorption. A modified polymer compound having properties, that is, a water absorbing agent can be obtained. This is because the nitrile portion in the organic polymer material mainly generates a hydrolysis reaction group by a hydrolysis reaction by the treatment with concentrated sulfuric acid, and then the styrene or conjugated diene is forcibly treated by the treatment with sulfuric anhydride. This is because a gel having a high degree of cross-linking can be obtained because of sulfone cross-linking.

Acid treatment using an organic solvent The acid treatment may be performed in an inorganic acid, or may be performed in a reaction system using an organic solvent. Examples of the organic solvent usable as the reaction system include C ₁ or C ₂ aliphatic halogenated hydrocarbons (preferably 1,2-dichloroethane, chloroform, dichloromethane, 1,1-dichloroethane) or aliphatic cyclic hydrocarbons. (Preferably, cyclohexane, methylcyclohexane, and cyclopentane) are used.
Also, nitromethane, nitrobenzene, sulfur dioxide,
Examples thereof include a paraffinic hydrocarbon having 1 to 7 carbon atoms, acetonitrile, carbon disulfide, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, acetone, methyl ethyl ketone, and thiophene. Preferably, aliphatic halogenated hydrocarbons C ₁ or C _2, alicyclic hydrocarbons, nitromethane, nitrobenzene, and sulfur dioxide.

These solvents may be used alone or as a mixture of a plurality of types. In the mixing between the above-mentioned solvents, the mixing ratio is not particularly limited. The amount of these organic solvents is preferably less than 200 times the weight of the organic polymer material. When the addition amount of the organic solvent is 200 times or more, the reaction rate of the acid treatment decreases, and the cost of the organic solvent increases, which is economically disadvantageous.

In the acid treatment, a Lewis base may be used if necessary. Examples of the Lewis base include alkyl phosphates such as triethyl phosphate and trimethyl phosphate, dioxane, acetic anhydride, ethyl acetate, ethyl palmitate, diethyl ether, dioxane and the like.

The acid group introduced into the styrene or conjugated diene unit by the acid treatment includes sulfonic acid, —PO (OH) ₂ ,
—CH ₂ PO (OH) ₂ is a preferred example. In addition, among these acid groups, a sulfonic acid group is preferable. When a sulfonic acid group is introduced as an acid group, the organic polymer material and a sulfuric acid such as concentrated sulfuric acid, sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid are reacted as they are or in an organic solvent. You can do it. In addition, the introduction of -PO (OH) ₂ group can be achieved by adding phosphorus trioxide to an organic solvent and further subjecting it to a hydrolysis reaction. These acid groups may be used alone or in combination of two or more.

In order to satisfy the antibacterial and water-absorbing properties of the antibacterial water-absorbing agent, the amount of the ionic group (acid group) contained in the organic polymer material should be 5 mol% or more and 95 mol% or more with respect to all units. Mol% or less, preferably 10 mol% or more and 70 mol%
It is as follows. When the introduction ratio of the acid group is more than 95 mol%, the acid-treated product of the organic polymer material exhibits water solubility, and it is difficult to produce an antibacterial water-absorbing agent having high shape stability.
Conversely, when the introduction ratio of the acid group is less than 5 mol%,
The water absorption (particularly with respect to the aqueous electrolyte solution) decreases, and the subsequent salt formation, for example, ion exchange treatment of silver, copper, and zinc does not proceed, and it is difficult to exhibit excellent antibacterial properties.

By carrying out the acid treatment under the following reaction temperature and reaction time conditions, the above-mentioned predetermined amount of ionic groups (acid groups) can be introduced into the organic polymer material. The reaction temperature of the acid treatment varies greatly depending on whether or not an organic solvent is used, but is generally from 0 ° C to 200 ° C, preferably from 30 ° C to 120 ° C.
It is as follows. If the reaction temperature is lower than 0 ° C., the reaction rate becomes slow and impractical, and a water absorbing agent having good water permeability and water absorption cannot be obtained. Also, 200
When the temperature is too high, the molecular chains of the organic polymer material are easily broken by thermal decomposition, and the insolubility in water decreases. The reaction time varies greatly depending on the reaction temperature, but is generally from 1 minute to 40 hours, preferably from 5 minutes to 2 hours. If the reaction time is too short, the reaction does not proceed sufficiently. Conversely, if the reaction time is too long, the production efficiency will deteriorate.

The inorganic acid or organic solvent once used in the above-mentioned acid treatment may be recovered after the completion of the reaction and recovered as it is, or may be recovered by a method such as extraction or distillation and used again in the reaction.

In the present invention, by subjecting the organic polymer material to the above-described acid treatment, an acid group is introduced as a substituent into the styrene and / or conjugated diene unit, while the acrylonitrile unit undergoes a hydrolysis reaction. A generated group is generated, amidated, and modified into a hydrophilic polymer compound.

Salt formation treatment Next, in the present invention, the acid group introduced as a substituent into the styrene and / or conjugated diene unit is replaced with, for example, silver,
The organic polymer material can be converted into an antibacterial water-absorbing agent by neutralizing with a cation mainly composed of copper and zinc to form a salt. When forming a metal salt of an acid group, first, a reaction product of the acid treatment reaction system is filtered with a filter or the like, washed with a large amount of water, and then a metal salt of silver, copper, or zinc is added. However, a method in which an acid treatment reaction system is directly added to an aqueous solution of a metal salt of silver, copper, or zinc may be used. In addition, organic or inorganic salts other than the above-mentioned metal salts of silver, copper, and zinc, and further, hydroxides can be used in combination. These salts or hydroxides include ammonium, sodium, lithium,
Alkali metals such as potassium, alkaline earth metals such as magnesium and calcium, hydroxides, carbonates, acetates, sulfates, phosphates and organic acid salts of metals such as aluminum, titanium, germanium, tin and iron Compounds of the following are mentioned as examples.

The reaction product obtained through the above steps is
It is a gel-like substance, which is then sun dried, heat dried,
Drying under reduced pressure, or centrifugal dehydration, press dehydration, etc.,
The desired antibacterial water-absorbing agent can be obtained.

By the treatment method described above, an antimicrobial material having a nitrile group, a group formed by the same hydrolysis reaction, and a salted acid group can be obtained. This product has an unreacted nitrile group to improve water solubility and gel strength, and furthermore, the water absorption is increased by a hydrolysis reaction group of the nitrile group and an acid group that has been converted into a salt, and Will gel.

Water Absorbent Mixed with Antibacterial Water Absorbent It is essential that the water-absorbing body of the present invention has an antibacterial modified polymer (antibacterial water absorbent). An agent and a water-absorbing agent having only water absorption can be used in combination. As the water-absorbing agent having only water-absorbing property, a known water-absorbing material can be used. Preferably, acrylonitrile and an organic polymer material containing styrene and / or a conjugated diene, or the used waste material is used. It is desirable to realize the effective use of the earth resources which is one of the objects of the present invention.

In order to produce a water-absorbing agent having only water absorption using an organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene, or the used waste material, the acid treatment described above is used. A water-absorbing agent obtained by subjecting an organic polymer material to an acid treatment under the same conditions as described above may be used. Further, a salt other than silver, copper, and zinc may be formed in the subsequent salt forming step.

Other antibacterial agents to be mixed with the antibacterial water-absorbing agent, and known antibacterial materials such as inorganic antibacterial materials, organic natural product extracted antibacterial materials, and organic synthetic antibacterial materials can be appropriately used in combination. As these inorganic antibacterial materials,
Chlorine compounds such as sodium hypochlorite, peroxides such as hydrogen peroxide, boric acid, boric acid compounds such as sodium borate, copper compounds such as copper sulfate, zinc sulfate, and zinc chloride. Zinc compounds, sulfur, lime polysulfide, sulfur compounds represented by hydrated sulfur, calcium compounds represented by calcium oxide, silver thiosulfite complex salts, silver compounds represented by silver nitrate, iodine, silicon fluoride And sodium.

Examples of the organic natural product-extracting antibacterial material include hinokitiol, Moso bamboo extract, and creosote oil.

Examples of the organic aliphatic compound antibacterial material include an organic tin compound represented by tributyltin oxide, a cyclopentane derivative represented by copper naphthenate, a halogen compound represented by methyl bromide, ethyl alcohol, isopropyl alcohol A dihydric alcohol compound represented by 2-bromo-2-nitro-1,3-propanediol, a formaldehyde, a saturated aldehyde represented by glutaraldehyde,
There are carboxylic acid compounds represented by sorbic acid and potassium sorbate.

Further, ether compounds represented by ethylene oxide and propion oxide, lactone compounds represented by beta-oxypropiolactone, quaternary ammonium salt compounds represented by 3-trimethoxysilylpropyldimethyloctadecyl ammonium chloride,
There are amino acid derivatives represented by di (octylaminoethyl) glycine hydrochloride, sulfonic acid compounds represented by sodium lauryl sulfate, and hydroxamic acid compounds represented by bisdecalinium acetate.

Further, cyanuric acid compounds typified by chlorinated isocyanuric acid, cyanic acid compounds typified by methyl isocyanate, sulfone compounds typified by bis (trichloromethyl) sulfone, and polyhexamethylene biguanidine hydrochloride. Representative guanidine compounds, 1,3
A hydantoin compound represented by -dichloro-5,5-dimethylhydantoin; a dithiol compound represented by 5-oxy-3,4-dichloro-1,2-dithiol;
Examples include arsine compounds represented by iron methylarsinate, phosphoric acid ester compounds represented by aluminum tris (ethyl phosphate), and thiocarbamide compounds.

As the organic aromatic compound antibacterial material, carbonate compounds represented by bis (4-nitrophenyl) carbonate, quaternary ammonium salt compounds represented by benzalkonium chloride and benzethonium chloride,
Monoamine compounds represented by 2,6-dichloro-4-nitroaniline; diamine compounds represented by nitroethylbenzylethylenediamine potassium; hydroxylamine compounds represented by N-nitroso-N-cyclohexylhydroxylamine aluminum; dihydromethyloxa Anilide compounds represented by tincarboxanilide dioxide, imidazole compounds represented by 2- (4-thiazolyl) benzimidazole, 5-methyl-
There is a benzothiazole compound represented by 1,2,4-triazolo-3,4-benzothiazole.

Further, triazine compounds represented by 2,4-dichloro-6-chloroanilino-1,3,5-triazine, guanidine compounds represented by chlorhexidine hydrochloride, chlorhexidine gluconate, and pyridine represented by cetylpyridinium chloride Compounds, pyrimidine compounds represented by dimethylpyrazolylhydroxyphenylpyrimidine, 2,2L-methylenebis-3,4,
Halogenobenzene compounds represented by 6-trichlorophenol, benzenesulfonic acid compounds represented by copper hydroxynonylbenzenesulfonate, benzenecarboxylic acid compounds represented by benzoic acid, mercaptocarboxylic acid compounds represented by thimerosal, oxybenzoic acid There are hydroxycarboxylic acid compounds represented by ethyl acid.

Further, monohydric phenol compounds represented by phenol and cresol, dihydric phenol compounds represented by resorcinol, phenoxy ether compounds represented by phenoxyethanol, and phenol ester compounds represented by pentachlorophenyl laurate A phenyl compound represented by triphenyltin oxide, a biphenyl compound represented by diphenyl,
There are monovalent naphthol represented by beta naphthol, naphthalene compound represented by monochloronaphthalene, and isoquinoline compound represented by dodecylisoquinolinium bromide.

Other examples include nitrile compounds, isothiazole compounds, thiadiazole compounds, halogenophenol compounds, pyrrole compounds, quinone compounds, quinoline compounds, and organic phosphate compounds.

Water-permeable bag-like body of water-absorbing body The water-permeable bag-like body used in the water-absorbing body according to the present invention is not limited in its type and form as long as it is water-permeable. For example, natural fiber or synthetic fiber cloth can be used. Examples of natural fibers include cotton, hemp, silk and the like. As synthetic fibers, polyamide, polyimide,
Examples include polyester, polyethylene, and polypropylene. It is preferable that these fibers are used alone or as a mixture and woven into a cloth. In addition, a nonwoven fabric may be used. Further, it may be formed of a film-shaped body whose front and back are penetrated by pores.

With the above-described structure, a water absorber having an antibacterial water-absorbing agent and a non-antibacterial water-absorbing agent that is small in weight and volume during drying and easy to use is realized. In addition, at the time of water absorption, since the weight and volume increase due to water absorption and the external shape has high followability, the water absorbing body according to the present invention also functions as a sandbag. Further, by recycling polymer waste materials or inorganic solid waste materials that have been troubled as wastes, it is possible to contribute to the maintenance of the global environment.

Solids in Water Absorbent Used as Sandbag In the water absorbent of a preferred embodiment of the present invention, in addition to the water absorbing agent, a solid having a particle size of 0.01 mm or more and 100 mm or less and a specific gravity of 1 or more is added to a water-permeable bag. It may be mixed in the shape. The solid content is preferably 1% by weight or more and 99% by weight or less of the dry weight of the water absorbing agent.

In the water-absorbing material according to the present invention, solids that can be mixed with the water-absorbing agent are collected or mined from the natural world, such as gravel, pebbles,
Minerals including sand and the like, wastes, and those formed by binding wastes are also included. Further, the solid matter may be magnetic waste. Examples of the solid material include metal, ceramics, glass, and those obtained by binding these to each other. As the binder at the time of binding, a binder made of a polymer material, for example, an epoxy resin-based adhesive can be used.

Further, in the water absorbent according to the present invention, a magnetic substance can be used as a solid. Those having magnetism include those having ferrimagnetism, ferromagnetism, and parasitic magnetism. Due to the magnetic properties of the solids, the water-absorbing bodies attract each other due to the magnetic force during mobile transportation, so that handling with a crane or the like becomes easy. In addition, the magnetism makes it possible to identify the water absorbing body. When a ferromagnetic material is used as a solid having magnetism, for example, iron, nickel, cobalt, alloys containing these or alloys containing these, further, transition metals and alloys thereof, further containing rare earth elements Alloys can be mentioned. Furthermore, examples of ferrimagnetic materials include magnetite, maghemite, manganese zinc ferrite, manganese nickel ferrite, barium ferrite, and strontium ferrite.

Since these magnetic materials have a higher specific gravity than ordinary inorganic materials, the weight of the water absorbent when used as sandbags can be increased. In addition, these magnetic materials
It is a waste material that is difficult to dispose in the dismantling process of electronic equipment, and is useful from the viewpoint of effective utilization.

[0059]

Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. Embodiment 1 of Water Absorbent Body This embodiment is an example of an embodiment of a water absorbing body according to the present invention, and FIG. 1A is a cross-sectional view and a diagram showing a configuration of a water absorbing body of this embodiment. FIG. 1B is a cross-sectional view showing the water-absorbing body of the present embodiment in a state of swelling by absorbing water. The water absorber 10 of the present embodiment is a water absorber that absorbs and removes water that has leaked or flooded and that has accumulated on a floor surface or the like, and is shown in FIG.
As shown in FIG. 5, an antibacterial water-absorbing agent 14 composed of the above-mentioned modified polymer compound is filled in a water-permeable bag-like body 12 made of cotton cloth. When the water absorbing body 10 absorbs water,
Swell as shown in (b). Since the water-absorbing body 10 is filled with the antibacterial water-absorbing agent 14, even if it absorbs water, there is no possibility that microorganisms and the like are generated and the state becomes unsanitary.
Therefore, when the water absorber 10 is dried, it recovers water absorbability again and can be used as a water absorber. Also, as long as the antibacterial water absorbing agent is filled in at least 5 parts by weight, even a water absorbent mixed with a non-antibacterial water absorbing agent shows antibacterial properties.

Second Embodiment of Water Absorbent Body This embodiment is an example of an embodiment in which the water absorbent body according to the present invention is applied to a sandbag, and FIG. 2A shows the structure of the water absorbent body of this embodiment. FIG. 2B is a cross-sectional view illustrating the water-absorbing body of the present embodiment in a state of being swollen by absorbing water. The water absorbing body 20 of the present embodiment is a water absorbing body used as a sandbag, and as shown in FIG. 2A, a water-permeable bag 22 made of linen cloth contains the above-described modified polymer compound. And a solid substance 26 having a specific gravity of 1 or more. The solid 26 has a particle size of 2 mm or more and 10 mm or more.
mm or less is a manganese nickel ferrite-based granular solid.

The water absorbing body 20 of the present embodiment, during transportation,
As shown in FIG. 2A, the antibacterial water-absorbing agent 24 is lightweight and not bulky, and when used, as shown in FIG. 2B.
Swells due to water absorption and increases in weight and volume, thus performing the function of a sandbag. Further, the water absorbing body 20 includes an antibacterial water absorbing agent 24.
Since it is filled with water, even if water is absorbed, there is no possibility that microorganisms and the like are generated and the state becomes unsanitary. Therefore, when the water absorbing body 20 is dried, the water absorbing property is restored, and the water absorbing body 20 can be used as a water absorbing body. In addition, during mobile transportation, the water absorbing body 20
Are attracted to each other by the magnetic force of the manganese nickel ferrite solid 26, so that handling by a crane or the like becomes easy. In addition, the magnetism makes it possible to identify the water absorbing body.

Experimental Examples Here, in order to evaluate the water absorbent according to the present invention, water absorbents were actually produced as an experimental sample and a comparative sample, respectively, and an evaluation test was performed while comparing them with each other. However, the present invention is not limited by the following experimental examples. Experimental Example 1 In this experimental example, first, as described below, an antibacterial water absorbing agent and a non-antibacterial water absorbing agent were manufactured as the water absorbing agent of the water absorbing body. On the other hand, a thick cotton bag was prepared as a water-permeable bag filled with a water absorbing agent. Next, 95 parts by weight of the non-antibacterial water-absorbing agent and 5 parts by weight of the antibacterial water-absorbing agent were put in a bag to obtain a water-absorbing body of the sample of Experimental Example 1. In addition, 100 parts by weight of the non-antibacterial water-absorbing agent was put in a bag to obtain a water-absorbing body of Comparative Example 1 sample. Subsequently, the water-absorbing body of the sample of Experimental Example 1 and the water-absorbing body of the sample of Comparative Example 1 were immersed in pool water on the building roof. Both of them absorbed water of 15000 parts by weight or more of the water absorbing agent in the water absorbing body and swelled. By leaving both water absorbers as it is under sunny weather, they are dried almost equally,
The volume was reduced. By leaving it on the roof of the building as it is, the phenomenon of swelling by absorbing rainwater falling on rain and the phenomenon of reducing the volume by natural drying were repeated.

As a result, green lower plants were generated or adhered to the entire surface of the water-absorbent material of the comparative example 1 sample, and release of odor was confirmed. No such phenomenon was observed.

Antibacterial Water Absorbing Agent of Experimental Example 1 In Experimental Example 1, SAN recovered from a transparent portion of an 8 mm cassette tape guard panel was used as a raw material of the antibacterial water absorbing agent.
Using the resin waste material, it was pulverized with a shredder and pulverized into a class of 16 mesh to 32 mesh. SAN
The composition of the resin waste material was 60 mol% of styrene and 40 mol% of acrylonitrile.

Then, 1 part by weight of the SAN resin waste material was added to 30 parts by weight of concentrated sulfuric acid having a concentration of 96% by weight, and the temperature was 80 ° C.
For 20 minutes to effect an acid treatment reaction. After the completion of the reaction, the reaction system was filtered with a glass filter, and solids in the reaction system were separated and washed with water. Next, the mixture was neutralized with 50 parts by weight of a 1N sodium hydroxide solution, and further washed with a sufficient amount of water. The filter cake obtained by filtration was dispersed in 1000 parts by weight of pure water, and 10 parts by weight of a 1.0 M aqueous solution of copper sulfate pentahydrate was added. After sufficiently stirring, the mixture was washed with water, filtered, and solid I got something. The obtained solid was dried in a circulating drier at a temperature of 100 ° C. for 3 hours. By the above treatment, a brown solid was obtained as an antibacterial water-absorbing agent. The sulfonic acid groups in this solid were 36 mol% of the total monomer units.
Further, the content of copper is 0.1 mol in a molar ratio with the sulfonic acid group.
91.

Non-antibacterial water-absorbing agent of Experimental Example 1 In Experimental Example 1, as a raw material of the non-antibacterial water-absorbing agent, A was recovered from a black portion of an 8 mm cassette tape guard panel.
First, using the BS resin waste material, it was pulverized by a frozen shredder and pulverized into a classified material of 16 mesh to 32 mesh. The ABS resin waste was 52 mole% styrene, 28 mole% acrylonitrile, 20 mole% butadiene, and contained 2% carbon black by weight.

Then, 1 part by weight of the ABS resin waste material was added to 30 parts by weight of concentrated sulfuric acid having a concentration of 96% by weight, and the temperature was 80 ° C.
For 20 minutes to effect an acid treatment reaction. After the completion of the reaction, the reaction system was filtered with a glass filter, and solids in the reaction system were separated and washed with water. Next, the mixture was neutralized with 50 parts by weight of a 1N sodium hydroxide solution, and further washed with a sufficient amount of water. Then, when the pH of the filtrate became 8 or less, the solid matter was filtered and separated, and the obtained solid matter was heated to a temperature of 1 in a circulating drier.
Drying was performed at 05 ° C. for 2 hours.

By the above treatment, a black solid was obtained as a non-bacterial water-absorbing agent. From the elemental analysis result of sulfur, it was confirmed that the sulfonic acid group in the water absorbing agent was 33 mol% in all the monomer units. The sodium content was almost equimolar to the sulfonic acid group (1.1).

Experimental Example 2 In this experimental example, an antibacterial water-absorbing agent was first manufactured as described below as a water-absorbing agent for a water-absorbing body. A thick cotton bag was prepared as a water-permeable bag filled with a water absorbing agent. Next, 100 parts by weight of the antibacterial water-absorbing agent was placed in a bag as a water-absorbing agent for the water-absorbing body, to obtain a sample of Experimental Example 1. Further, Comparative Example 1 of Experimental Example 1 was used as a sample of Comparative Example 2.
A sample water absorber was used. Then, the water absorbent of the sample of Experimental Example 2 and the water absorbent of the sample of Comparative Example 2 were immersed in pool water on the building roof. Both swelled by absorbing more than 15,000 parts by weight of water absorbing material. By leaving both water absorbers in the clear and sunny weather, they were almost equally dried and reduced in volume. By leaving it on the roof of the building as it is, the phenomenon of swelling by absorbing rainwater falling on rain and the phenomenon of reducing the volume by natural drying were repeated.

As a result, green lower plants were generated or adhered to the entire surface of the water-absorbent material of the comparative example 2 sample, and release of odor was confirmed. No such phenomenon was observed.

The antibacterial water-absorbing agent of Experimental Example 2 To 70 parts by weight of cyclohexane, 3 parts by weight of the ABS resin waste used as a raw material in Experimental Example 1 were added, and 4.2 parts by weight while maintaining the temperature at 30 ° C. Was added dropwise. Then, the mixture was kept at a temperature of 30 ± 2 ° C. for 2 hours to carry out an acid treatment reaction, and the reaction system was filtered to separate a solid substance and washed with water. Subsequently, the obtained solid was dispersed in 2,000 parts by weight of pure water, and 50% of a 1.0 M aqueous solution of zinc sulfate heptahydrate was added thereto.
After the addition of 30 parts by weight of a 1.0 M aqueous solution of copper sulfate pentahydrate and sufficient stirring, the solid was separated by filtration and washed with water. The obtained solid was dried in a dryer for 2 hours.

The solid obtained by the above treatment was used as the antibacterial water-absorbing agent of Experimental Example 2. The sulfonic acid group in the antibacterial water-absorbing agent of Experimental Example 2 was 25 mol% in all the monomer units. The content of zinc was 0.42 in molar ratio to sulfonic acid groups, and the content of copper was 0.36 in molar ratio to sulfonic acid groups.

[0073]

As described above, the present invention has a metal salt of an acid group added as a substituent,
An organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene, that is, a water absorbent having both excellent antibacterial properties and water absorbency, using a very common organic raw material as a raw material. I have. Therefore, by applying the present invention, a water absorber used in the case of water leakage, submergence, or the like, or a lighter body that is lightweight and non-bulky during transportation, and that increases in weight and volume during water absorption and can be used as a sandbag. Has been realized. In addition, the water-absorbing body according to the present invention is filled with an antibacterial water-absorbing agent, so even if it absorbs water, microorganisms and the like are generated, and it does not become unsanitary, so it is hygienic, And, when dried, the water absorption is restored again, and it can be used as a water absorbent. In addition, the water absorber according to the present invention can be manufactured as a raw material using a used organic polymer material, and thus has an advantage that earth resources can be effectively used.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view illustrating a configuration of a water absorber according to a first embodiment, and FIG. 1B is a cross-sectional view illustrating the water absorber according to the first embodiment in a state where water is swollen and swollen. is there.

FIG. 2A is a cross-sectional view illustrating a configuration of a water absorbing body (sandbag) according to a second embodiment, and FIG. 2B is a water absorbing body (sandbag) according to the second embodiment in a state of absorbing water and swelling. FIG.

[Explanation of symbols]

10... The water absorbent of the first embodiment, 12... Cotton bag, 14.
... Antimicrobial water-absorbing agent, 20...
... hemp bag, 24 ... antibacterial water-absorbing agent, 26 ... solid matter.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 212/10 C08F 212/10 4J100 236/12 236/12 C08J 11/04 ZAB C08J 11/04 ZAB C08K 3 / 00 C08K 3/00 9/08 9/08 C08L 9/02 C08L 9/02 25/12 25/12 E02B 3/04 301 E02B 3/04 301 F term (reference) 2D018 AA06 4D004 AA18 AA19 AA43 BA02 CA45 CC17 4F301 AA11 AA21 BA21 CA09 CA23 CA34 CA36 CA53 4G066 AA11D AA13D AA47D AA75A AB03A AB09A AC12B AC14B AC17B AC39A AE20D CA43 DA08 EA20 FA21 4J002 AC07W AC07X BC06W BC06X BC10W BG11W BG11X BN10W BN10X BN12W BN12X BN14W BN14X BN15W BN15X DA066 DA086 DC006 DL006 FB276 FD016 GL00 4J100 AB02Q AB07Q AC01R AL01R AM02P AS01Q AS01R AS02Q AS02R AS03Q AS03R AS06Q BA56H BA56Q BA56R CA04 CA05 CA31 HA61 HB52 JA19

Claims (13)

[Claims] 1. A water absorbent having an antibacterial water absorbing agent comprising a modified polymer compound made of an organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene in a water-permeable bag. A water absorbent, wherein the modified polymer compound has a metal salt of an acid group added as a substituent. 2. An organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene as a raw material, and another water-absorbing agent having an ionic group added as a substituent by acid treatment is used as water. The water-absorbing body according to claim 1, wherein the water-absorbing body is provided in a permeable bag. 3. The water absorber according to claim 1, wherein the metal salt is a salt of one or more of zinc, copper and silver. 4. The modified polymer compound according to claim 1, wherein the modified polymer compound contains acrylonitrile and at least one of styrene and / or conjugated diene, and the starting material is an organic polymer material recovered from waste materials. Item 3. The water absorbent according to Item 1 or 2. 5. The water-absorbing material according to claim 1, wherein the water-permeable bag has a solid having a specific gravity of 1 or more in addition to the modified polymer compound. 6. The water absorber according to claim 5, wherein the solid is at least one of a natural mineral and a solid waste. 7. The water absorbent according to claim 5, wherein the solid substance is formed by binding solid waste. 8. The water absorbent according to claim 5, wherein the solid is magnetic waste. 9. Water absorption having an antibacterial water absorbing agent comprising a modified polymer compound made of an organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene in a water-permeable bag. An acid treatment step of reacting an organic polymer material with an acid to add an acid group as a substituent to the organic polymer material, and an organic polymer material and a metal salt that have undergone the acid treatment step. And a metal treatment step of forming a metal salt of an acid group. 10. The method for producing a water absorbent according to claim 9, wherein an inorganic acid is used as the acid in the acid treatment step. 11. The method for producing a water absorbent according to claim 10, wherein concentrated sulfuric acid having a concentration of 70% by weight or more is used as the inorganic acid. 12. The method according to claim 9, wherein in the metal treatment step, a metal salt of one or more of zinc, copper, and silver is formed. 13. A starting material for a modified polymer compound,
The method for producing a water absorbent according to claim 9, wherein an organic polymer material containing acrylonitrile and at least one of styrene and / or conjugated diene and recovered from waste materials is used.