JP2002263483A - Water absorption body and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water absorption body that is light in weight and small in volume when carried but absorbs water for use to show sufficient function of weight, volume and shape follow-up property of the outline, that can be repeatedly used by drying, that has shape stability and that removes unnecessary water, or to provide a water absorption body having a function as a sandbag, and to provide a water absorption body having higher water absorptivity and having a faster absorption rate than a conventional material, and moreover, to contribute to global environment by manufacturing products with high added value using polymer wastes such as a resin or inorganic solid wastes such as metals and ceramics, which are regarded difficult to treat as wastes. SOLUTION: The water absorption body contains a modified polymer compound, a surfactant and a supporting body in a water-transmitting bag body. The modified polymer compound is prepared by introducing acidic groups into a polymer compound preferably obtained from a waste material and containing (a) acrylonitrile and (b) at least one kind of styrene and/or conjugated dienes.

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 used for removing unnecessary water remaining due to water leakage or flooding, and a sandbag used for preventing or repairing the embankment of a river due to flooding or the like. The present invention relates to a water absorbing body having the function of

[0002]

2. Description of the Related Art As a water absorber used for removing unnecessary water remaining due to water leakage or flooding, a fibrous material such as cloth has been used. However, when a large amount of water needs to be removed, such as a rupture of a water pipe due to a disaster such as an earthquake, a large-scale flooding of water over a wide area due to flood damage, or a leak from a tank in a factory, the water absorption capacity of such conventional water absorbers Was not enough. The water-absorbing body having the function of a sandbag is a civil engineering material for preventing flooding of rivers and lakes due to a flood or the like. Conventionally, for example, a hemp bag filled with soil has been used. Such a conventional water absorber has been produced near a disaster site because it is difficult to transport because of its large weight and volume.
In the event of a disaster, it is necessary to immediately apply a water absorber having the function of a sandbag to the necessary places when necessary.
In the case of the conventional water absorber, its production often cannot keep up with the required amount. In addition, when carrying the water absorbing body from a distance, the water absorbing body must be carried using a vehicle or the like, and labor for loading and unloading the water absorbing body is required. Furthermore, vehicles may not be able to pass to the disaster site due to road collapse. Under such circumstances, more human life property was lost due to floods.

[0003]

As described above, a conventional water absorber or a water absorber having the function of a sandbag used for removing unnecessary water remaining in water or flooding is large in both weight and volume, and is transportable. It takes labor. Therefore, there is a demand for a water absorber that is small in both weight and volume and easy to carry. According to the present invention, both the weight and the volume are small during transportation, and the water absorbing body having the function of a water absorbing body for removing unnecessary water or a sandbag, which absorbs water during use and sufficiently satisfies the function of following the shape of the weight, volume and external shape. The purpose is to provide. Another object of the present invention is to provide a water absorbent that can be repeatedly used by drying and has shape stability. Further, the present invention provides a water absorber having a higher water absorption than a conventional water absorber or a water absorber having a function of a sandbag used for removing unnecessary water remaining in water or flooding, and has a high water absorption rate. With the goal. Furthermore, the present invention uses a polymer waste material such as a resin or an inorganic solid waste material such as a metal or a ceramic, for example, which has been difficult to treat as a waste, and provides a higher value-added product to the global environment. The purpose is to contribute.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a polymer compound containing acrylonitrile and styrene and / or a conjugated diene in which an acidic group has been introduced is modified. It has been unexpectedly obtained that the above-mentioned object can be achieved at once by using a molecular compound. That is, such compounds have water absorption,
Since it takes on a gel shape due to water absorption, both weight and volume are small during transportation, and it absorbs water during use and has high functionality that sufficiently satisfies the function of following the shape of weight, volume and external shape. A water-absorbing body having the function of a body or a sandbag can be provided. The water-absorbent body using such a modified polymer compound as a water-absorbing material has an excellent utility of being able to cope with urgency in use since the water-absorbing speed is higher than that of a conventional sandbag. In addition, the water-absorbing body is troubled as a waste, for example, polymer waste materials such as resin,
Alternatively, there is also an advantage that it is possible to contribute to the global environment by recycling inorganic solid waste materials such as metals and ceramics. Furthermore, the present inventors have studied the improvement of the water absorption and the water absorption rate of the water absorbent, and as a result of including a surfactant together with the modified polymer compound, the wettability of the water absorbent can be improved. As a result, an unexpected finding that the water absorption rate can be improved was obtained.

That is, the present invention relates to a modified polymer in which an acidic group is introduced into a polymer containing (1) (a) acrylonitrile and (b) at least one of styrene and / or conjugated diene. And a surfactant and a support are contained in a water-permeable bag-like body, and (2) the support is a flexible reticulate body as described in (1) above. (3) wherein the modified polymer compound is supported by a support; and (4) the surfactant is an anionic surfactant and / or Or (5) the water absorber according to the above (1), which is a nonionic surfactant.
Furthermore, the water-absorbing body according to the above (1), wherein a solid having a specific gravity of 1 or more is contained in the water-permeable bag.
(6) The water-absorbing body according to (5), wherein the solid having a specific gravity of 1 or more is made of a natural mineral, and (7) the solid being a waste having a solid having a specific gravity of 1 or more. (5) The water absorber according to (5), (8) the water absorber according to (5), wherein the solid material has a specific gravity of 1 or more formed by binding waste. (5) wherein the solid material comprises magnetic waste.
3. The water absorbent according to item 1.

Further, according to the present invention, an acidic group is introduced into a polymer compound containing (a) acrylonitrile obtained from waste material and (b) at least one kind of styrene and / or conjugated diene. The modified polymer compound, the surfactant, and the support are contained in a water-permeable bag-like body, and (11) the support is a flexible net-like body, The water absorbent according to 10),
(12) The water absorbent according to (10), wherein the modified polymer compound is supported by a support.
3) The surfactant according to the above (10), wherein the surfactant is an anionic surfactant and / or a nonionic surfactant, and (14) a solid having a specific gravity of 1 or more. (15) The water-absorbent material according to (10), wherein the solid material having a specific gravity of 1 or more is made of a natural mineral. (16) The water absorbent according to (14), wherein the solid having a specific gravity of 1 or more binds the waste. (18) The water absorbing material according to (14), wherein the solid material having a specific gravity of 1 or more is made of magnetic waste. About the body

Further, the present invention provides a modified polymer compound in which an acidic group is introduced into a polymer compound containing (19) (a) acrylonitrile and (b) at least one of styrene and / or conjugated diene. And a surfactant and a support are filled in a water-permeable bag-like body. (20) The method according to (19), wherein the support is a flexible network. (21) The method for producing a water absorbent according to (19), wherein the modified polymer compound is supported by a support.
2) The method for producing a water absorbent according to the above (19), wherein the surfactant is an anionic surfactant and / or a nonionic surfactant.
The method for producing a water absorbent according to the above (19), wherein a solid having a specific gravity of 1 or more is filled in a water-permeable bag.
(24) The method for producing a water absorbent according to (23), wherein the solid having a specific gravity of 1 or more is made of a natural mineral.
(25) The method for producing a water absorbent according to (23), wherein the solid having a specific gravity of 1 or more comprises waste.
6) The method for producing a water-absorbing body according to the above item (23), wherein the solid having a specific gravity of 1 or more is formed by binding wastes. (27) The solid having a specific gravity of 1 or more has magnetism. The present invention relates to the method for producing a water absorbent according to the above (23), which is made of waste.

Further, the present invention relates to (28) acrylonitrile obtained from waste material and (b) styrene and / or
Alternatively, a modified polymer compound in which an acidic group is introduced into a polymer compound containing at least one or more conjugated dienes, a surfactant, and a support are filled in a water-permeable bag. (29) a method for producing a water absorbing body,
The water absorbent according to the above (28), wherein the support is a flexible network, and the modified polymer compound (30) is supported by the support. (31) The method for producing a water absorbent according to (28), wherein the surfactant is an anionic surfactant and / or a nonionic surfactant.
2) The method for producing a water-absorbent body according to the above (28), wherein a solid having a specific gravity of 1 or more is filled in a water-permeable bag-like body. (34) The method for producing a water-absorbent body according to (32), wherein the solid-material having a specific gravity of 1 or more is made of waste. (35) The method for producing a water-absorbing body according to the above (32), wherein the solid substance having a specific gravity of 1 or more is formed by binding and forming waste. (36) The solid substance having a specific gravity of 1 or more. Is made of magnetic waste.
2) A method for producing a water absorbent according to the above.

[0009]

Embodiments of the present invention will be described below in detail with reference to the drawings. Hereinafter, a water absorber 1 as shown in FIGS. 1 to 4 will be described as a water absorber to which the present invention is applied and which has a function of a water absorber or sandbag for removing unnecessary water. The water absorbing body 1 having the function of a water absorbing body or sandbag for removing unnecessary water according to the present invention,
A water-permeable bag-like body 2, a modified polymer compound in which an acidic group is introduced into a polymer compound containing acrylonitrile, styrene and / or conjugated diene, which is included in the water-permeable bag-like body 2, A water-absorbing material containing a surfactant and a support are provided. More specifically, the water-absorbing body 1 according to the present invention, which functions as a water-absorbing body for removing unnecessary water or a sandbag, in a dry state, as shown in the cross-sectional view of FIG. In a water-absorbing and swollen state, as shown in the sectional view of FIG. 2, a water-absorbing material 3b containing the modified polymer compound and a surfactant, and a support 4 And 4. FIG. 3 is a cross-sectional view in a dry state of the water-absorbing body 1 according to the present invention in which a solid 5 having a specific gravity of 1 or more is contained, and FIG. 4 is a cross-sectional view in a water-absorbing swelling state.

The polymer compound containing (a) acrylonitrile and (b) at least one kind of styrene and / or conjugated diene used in the present invention includes:
The compound preferably contains about 5 to 80 mol%, preferably about 10 to 60 mol%, more preferably about 20 to 50 mol% of acrylonitrile units in the compound. In order for the resulting modified polymer compound to function effectively as a water-absorbing polymer compound without substantially exhibiting water solubility when the polymer compound is treated with an acid, the content is about 5 mol%. The above is preferable. Further, the polymer compound is prevented from being hardened, and it is easy to pulverize the polymer compound into small pieces in the process of producing the water absorbent according to the present invention, while styrene and / or conjugated in the polymer compound are reduced. The content is preferably about 80 mol% or less in order to prevent the diene unit content from decreasing and the rate of introduction of acidic groups from decreasing, and to exhibit water absorption, particularly water absorption in an aqueous electrolyte solution. .

As the polymer compound used in the present invention, at least one of styrene and / or a conjugated diene (for example, butadiene or isoprene) as a constitutional unit other than acrylonitrile is contained in an amount of about 20 to 95 mol%, preferably about 20 to 95 mol%. Is about 40-85 mol%
And more preferably about 50 to 80 mol%. These styrene and / or conjugated diene constituent units are where the ionic acidic group is introduced into the compound by subjecting the polymer compound to acid treatment, and the water absorption of the absorbent polymer compound to be purified, particularly This is necessary to improve the water absorption of the electrolyte aqueous solution.

The polymer compound used in the present invention may further contain another constituent unit as long as the acrylonitrile and styrene and / or conjugated diene are contained in predetermined amounts. These other constituent units are not particularly limited, but include, for example, maleic anhydride, itaconic anhydride, α-methylstyrene, acrylamide, methacrylamide, acrylic acid or acrylate, methacrylic acid or methacrylic acid ester, acetic acid Examples thereof include vinyl, vinyl chloride, ethylene, propylene, butylene, vinylpyrrolidone, and vinylpyridine. The acrylate and methacrylate preferably have about 1 to 10 carbon atoms, and may be saturated or unsaturated.

The weight average molecular weight (Mw) of the polymer compound used in the present invention is generally about 1,000 to 20,
About 1,000,000, preferably about 10,000 to 1.0
It is about 00,000. In order for the resulting modified polymer compound to effectively function as a water-absorbing polymer compound without substantially exhibiting water solubility when the polymer compound is treated with an acid, the weight average molecular weight (Mw) is about It is preferable that it is about 1,000 or more. In addition, the weight-average molecular weight (Mw) is about 2 to promote the acid treatment reaction for introducing an acidic group into the copolymer efficiently and to shorten the reaction time.
It is preferable that it is about 0,000,000 or less.

As the polymer compound used in the present invention, specifically, for example, ABS (acrylonitrile-
Butadiene-styrene) resin, SAN (styrene-acrylonitrile) resin, ASA (acrylonitrile-styrene-acrylamide) resin, ACS (acrylonitrile-chlorinated polyethylene-styrene) resin, AAS (acrylonitrile-acrylate-styrene) resin, NB
It is preferable to use a polymer material such as R (acrylonitrile-butadiene) rubber. These materials may be newly produced unused resin granules (virgin pellets), or may be used resins or waste materials molded for specific applications. As waste materials,
For example, there are waste products (semi-finished products) in the production process of resin raw materials and molded products, housings and various parts materials already used for electric appliances and automobiles, or tubes, hoses, various cushioning materials, and the like. The used resin refers to a resin recovered from the above waste materials. Waste materials in the present invention may be any waste materials from factories, stores, homes, etc., but rather than general waste from homes, etc., collected from factories, stores, etc. Waste materials are more preferable because many of them have relatively uniform compositions.

The polymer compound used in the present invention may be an alloy of the polymer material and another resin, for example, a face dye, a stabilizer, a flame retardant, a plasticizer, a filler, and other auxiliary materials. A used resin or a waste material containing a known additive such as an agent may be used. Further, a mixture of used resin or waste material and unused material (virgin material) may be used. As the other resin that can be mixed with the polymer material in the alloy, a resin known per se may be used, but a resin that does not inhibit the acid treatment of the present invention is preferable. Specific examples of such a resin include polyphenylene ether, polycarbonate, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, polyamide, and polyester. The mixing amount of these resins is approximately 60 to the above-mentioned polymer material in order to smoothly carry out the acid treatment.
It is preferable that the content is not more than about weight%.

The polymer compound used in the present invention is preferably made into small pieces for convenience in acid treatment for introducing an acidic group. The method for forming the small pieces is not particularly limited, but the following methods can be mentioned. For example, there is a method of sieving after crushing by a crusher. In particular, when the polymer compound contains a rubber component, it is preferable to pulverize after freezing. Further, there is also a method of heating and melting to pelletize (granulate) into fine beads. The size of the small piece of the polymer compound is preferably about 3.5 mesh or less. The surface area of the reactant increases to facilitate the acid treatment reaction, shorten the reaction time, and increase the acid group density in the formation of acidic groups by the acid treatment to improve water absorption (performance as a water-absorbing polymer compound). The above range is preferable for this purpose.

When the polymer compound of the present invention further contains an inorganic substance, an acid treatment for introducing an acidic group is promoted (the periphery of the inorganic pigment is easily treated with an acid, that is, the inorganic compound is not reacted during the reaction. Since the pigment is detached from the polymer compound and the acid easily penetrates into the surface of the polymer compound), the acid group density increases in the formation of the acid group by the acid treatment,
Water absorption is improved. Therefore, in the present invention, it is preferable that the polymer compound contains an inorganic substance.

As the inorganic substance, carbon black and / or titanium oxide is preferable. These carbon blacks and titanium oxides may be, for example, those generally used as a coloring agent, a reinforcing agent, or an electrical conductivity imparting agent for plastics. Specifically, as the carbon black, for example, those manufactured by any of the channel method, the furnace method, and the thermal method may be used, each may be used alone, or a plurality of them may be used in combination. . The average particle size is usually about 0.005 to 100.
It is about μm, preferably about 0.01 to 10 μm. The titanium oxide may be, for example, any of rutile-type, anatase-type, and ultrafine-particle titanium, each of which may be used alone, or two or more of them may be used in combination. The average particle size is usually about 0.01 to 50 μm.
m, preferably about 0.05 to 10 μm.
The content of the carbon black and titanium oxide contained in the polymer compound is about 0.01 to 20% by weight, preferably about 0.05% by weight, based on the dry weight of the polymer compound.
About 10% by weight.

The water-absorbent material of the present invention comprises, as one of its constituents, a modified polymer compound in which an acidic group is introduced into the above-mentioned polymer compound. Examples of the method for introducing an acidic group into the polymer compound include a method of treating the polymer compound with an acid. By converting the polymer compound to an acid, conversion to a water-absorbing polymer compound is performed. More specifically, part of acrylonitrile in the polymer compound becomes an amide or a carboxyl group or a salt thereof, while
An acidic group is introduced into styrene or a conjugated diene.

As the acid used in the acid treatment of the present invention, an inorganic acid capable of introducing an acidic group into styrene or a conjugated diene is preferable. Specific examples of the inorganic acid include sulfonating agents such as concentrated sulfuric acid, sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid, and nitric acid, fuming nitric acid, phosphoric acid, phosphorus chloride, and phosphorus oxide. Among these, concentrated sulfuric acid,
Sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid are preferred, and concentrated sulfuric acid of about 70% by weight or more is more preferred. These 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, by first treating the above-mentioned polymer compound with concentrated sulfuric acid and then adding sulfuric anhydride, it is possible to obtain a water-absorbing polymer compound which is water-based and stable in shape. This is because the nitrile portion in the polymer compound is primarily subjected to a hydrolysis reaction by the treatment with concentrated sulfuric acid, and then the styrene or conjugated diene portion is forcibly sulfone-crosslinked by treatment with sulfuric anhydride. This is because a water-absorbing polymer compound having a high degree of crosslinking can be obtained. Therefore, the above acid treatment is one of the preferred embodiments of the acid treatment in the present invention.

The amount (prepared amount) of the inorganic acid used in the reaction is about 1 to 500 times, preferably about 10 to 200 times the weight of the above-mentioned polymer compound. By increasing the rate of introduction of an acidic group into styrene or a conjugated diene or the rate of hydrolysis of an acrylonitrile group, the production of an acidic group is promoted, and in order to impart water absorption, the amount of the inorganic acid charged is controlled by the above-mentioned polymer. About 1 or more times the weight of the compound is preferred. From the viewpoint of economy and workability, the amount of the inorganic acid to be charged is preferably about 500 times or less based on the weight of the polymer compound.

The acid treatment in the present invention may be performed in an inorganic acid, or may be performed in a system using an organic solvent. Examples of the organic solvent that can be used in the acid treatment include aliphatic halogenated hydrocarbons having about 1 to 2 carbon atoms (preferably 1,2-dichloroethane, chloroform, dichloromethane, 1,1-dichloroethane, and the like), and aliphatic cyclic hydrocarbons. Hydrocarbons (preferably cyclohexane, methylcyclohexane, cyclopentane, etc.), nitromethane, nitrobenzene, sulfur dioxide, paraffinic hydrocarbons (preferably having about 1 to 7 carbon atoms), acetonitrile, carbon disulfide, tetrahydrofuran, tetrahydrofuran Pyran, 1,
2-dimethoxyethane, acetone, methyl ethyl ketone, thiophene and the like. Preferably, it has 1 carbon atom
About 2 aliphatic halogenated hydrocarbons, aliphatic cyclic hydrocarbons, nitromethane, nitrobenzene and sulfur dioxide. These solvents may be used alone or in combination of two or more. In the mixed solvent, the mixing ratio is not particularly limited. The amount of these organic solvents is preferably less than about 200 times the weight of the polymer compound. The above range is preferable from the viewpoint of increasing the reaction rate of the acid treatment and from the economical viewpoint.

In the above acid treatment, a Lewis base may be used if desired. Examples of the Lewis base include alkyl phosphates (eg, triethyl phosphate or trimethyl phosphate), dioxane, acetic anhydride, ethyl acetate, ethyl palmitate, and the like.
Examples include diethyl ether and thioxane. In addition,
The inorganic acid or organic solvent once used in the acid treatment may be recovered and used as it is after the reaction, or may be recovered by a method such as extraction or distillation and used again for the reaction.

In the present invention, an acid group is introduced into the styrene and / or conjugated diene unit by subjecting the above polymer compound to the above-mentioned acid treatment, while a nitrile group is introduced into the acrylonitrile unit by a hydrolysis reaction. By being converted into an amide group or a carboxyl group, it is converted into a modified polymer compound having water absorption (water-absorbing polymer compound).

By the above acid treatment, styrene or conjugated die
As an acidic group (ionic group) introduced into the unit
Is, for example, the formula -SO₃M (where M is a hydrogen atom or
For example, cations such as metals such as sodium and potassium
Represent. A) a sulfo group which may form a salt represented by the formula:
-PO (OM₁) (OM₂) Or the formula -CH₂PO
(OM₁) (OM₂) (Where M₁And M₂Are the same
One or different, as defined for M above. Formed salt) represented
An optional substituent, -NO₂To mention
it can. In addition, the formula -OSO₃M (where M is the aforementioned
A sulfate group which may form a salt represented by
Formula -OPO (OM₁) (OM₂) (Where M ₁And M₂Is
The same or different, and is the same as M above. )
A phospho group which may form a salt of the formula
₃(Where M₃Is equivalent to M. ) To form a salt represented by
An optionally substituted hydroxyl group, formula -COOM₄(Where M₄Is M
And the same meaning. Carbo which may form a salt represented by)
Xyl groups and the like. Among these acidic groups,
A ruho group or a salt thereof is preferred. One of these acidic groups
May be introduced into the polymer compound, or two
Or more may be introduced into the polymer compound.

However, in order to satisfy the performance as a water-absorbing polymer compound, the amount of the acidic group contained in the modified polymer compound should be about 5 to 95 mol% based on all monomer units.
About 10 mol%, preferably about 10 to 70 mol%. In order that the modified polymer compound does not substantially exhibit water solubility and effectively exhibits water absorption, the amount of the acidic group is preferably about 95 mol% or less based on all monomer units. Further, in order to effectively maintain the effect of water absorption, the amount of the acidic group,
About 5 mol% or more based on all monomer units is preferred.

When the acidic group in the modified polymer compound is a sulfo group, the copolymer is directly combined with the aforementioned sulfonating agent such as concentrated sulfuric acid, sulfuric anhydride, fuming sulfuric acid and chlorosulfonic acid. The sulfo group is introduced by reacting or reacting the polymer compound with a sulfonating agent in a state of being dissolved or dispersed in an organic solvent, and subsequently the sulfo group is converted into a basic substance (for example, sodium hydroxide or Neutralization with potassium hydroxide or the like allows conversion to a sulfonate. Further, when the acidic group in the modified polymer compound is a —PO (OH) ₂ group, phosphorus trioxide is added to a solvent, and the resultant is further hydrolyzed to first form a —PO (OH) ₂ group. After being introduced, the salt can be obtained by reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide).
The acid groups of the modified polymer compound is _-CH 2 PO (O
H) In the case of _two groups or a salt thereof, the acidic group can be introduced into the polymer compound by a method known per se. The acidic group in the modified polymer compound is -N
When the compound is an O ₂ group, the acidic group of the polymer compound can be introduced by reacting the mixed solution of sulfuric acid and nitric acid with the polymer compound.

As a method for introducing a sulfate group which may form a salt, preferably, the above-mentioned polymer compound having an unsaturated bond is reacted with a high-temperature sulfuric acid aqueous solution to first introduce a sulfate group, By reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide). As a method for introducing a carboxyl group which may form a salt, preferably, n-butyllithium is added to the polymer compound having an aromatic ring, and then the carboxyl group is first reacted with dry ice to form a carboxyl group. It becomes possible to introduce a group, and then a carboxylate can be obtained by reacting with a basic compound (for example, sodium hydroxide or potassium hydroxide).

--OPO (OH) _{2 which} may form a salt
As a method for introducing a group, preferably, -OPO (OH) ₂ group is first introduced by adding phosphorus trioxide to the above-mentioned polymer compound having an unsaturated bond, followed by hydrolysis, and thereafter, a basic compound ( (E.g., sodium hydroxide or potassium hydroxide) to form the same salt. As a method for introducing a hydroxyl group which may form a salt, preferably, the above-described polymer compound having an unsaturated bond is reacted with an aqueous sulfuric acid solution to firstly introduce a hydroxyl group, and thereafter, a basic compound ( (E.g., sodium hydroxide or potassium hydroxide) to form the same salt.

The acid treatment reaction in the present invention is preferably carried out under the following conditions in order to introduce the above-mentioned predetermined amount of acidic group into the copolymer. The reaction temperature varies greatly depending on whether or not an organic solvent is used.
The temperature is about 200 ° C, preferably about 30 to 120 ° C. To increase the reaction rate to some extent from the viewpoint of practicality, and to obtain a modified polymer compound as a water-absorbing polymer compound having good performance, the reaction temperature is about 0 ° C.
Preferably, it is at least about. The reaction temperature is preferably about 200 ° C. or less in order to prevent the molecular chain of the polymer compound from being broken by thermal decomposition and the modified polymer compound from being dissolved in water.
The reaction time of the acid treatment varies greatly depending on the reaction temperature and cannot be unconditionally determined, but is generally about 1 minute to 40 hours, preferably about 5 minutes to 2 hours. The above range is preferable in order to allow the reaction to proceed sufficiently and increase production efficiency.

In the present invention, the reaction product obtained as described above may be subjected to a post-treatment known per se. Specifically, it is preferable to wash the reactants. As a method for washing the reaction product, the reaction solution is directly added to a large amount of water or a basic aqueous solution, or the reaction product is first filtered from the same reaction system with a filter or the like, and the reaction product is added with a large amount of water or a basic solution. For example, a method of pouring into an aqueous solution may be mentioned. At this time,
The nitrile group in the polymer compound is converted into an amide group or a carboxyl group and / or a salt thereof. Incidentally, as the basic substance used in the basic aqueous solution,
Examples thereof include compounds such as oxides, hydroxides, carbonates, acetates, sulfates, and phosphates of alkali metals (such as sodium, lithium, and potassium) and alkaline earth metals (such as magnesium and calcium). However, in order to improve the absorption effect (particularly the absorption effect on an aqueous electrolyte solution) of the modified polymer compound exhibiting water absorption and the deodorizing effect of ammonia gas and the like, it is desirable to perform only water washing without neutralization.

The reaction product obtained as described above is in the form of a gel, and thereafter, it is dried by heating, heating, depressurizing, centrifuging, pressing or the like to obtain the desired water-absorbing polymer compound. By the treatment method described above, a nitrile group and the same hydrolyzate (amide group or carboxyl group and / or a salt thereof) and a water-absorbing polymer compound having an acidic group can be obtained. It has an unreacted nitrile group to improve water insolubility and gel strength, and has a higher water absorption (particularly with respect to the aqueous electrolyte solution) due to a hydrolyzate of the nitrile group and an acidic group. Will be done.

In the present invention, the above-mentioned modified polymer compound is an essential requirement, and a material having a simple water absorbing function can be used in combination. Known water absorbing materials can be used for these materials. Examples of these materials include gel cross-linked products such as polyacrylate, polyvinyl alcohol, polyacrylamide, polyoxyethylene, polyamino acid, and poly (N-alkylvinylacetamide), or gel cross-linked copolymers mainly composed of the units. And modified products obtained by cross-linking and grafting with hydrophilic polymers including polysaccharides such as starch and cellulose. Among them, a polymer compound containing acrylonitrile and styrene or a conjugated diene, which is one of the objects of the present invention, or a used resin or waste material is used for the purpose of effectively using it as a material having higher added value. Are preferred.

In the present invention, as the water absorbing material 3,
It is characterized in that a surfactant is contained in addition to the modified polymer compound. As described above, by allowing the surfactant to coexist with the modified polymer compound, it is possible to improve the wetting of the water absorber, and as a result, there is an advantage that the water absorption speed of the water absorber increases.

The surfactant used in the present invention includes:
Anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used as appropriate. Examples of anionic surfactants include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amides, fatty alcohol phosphates, and sulfonates of dibasic fatty acid esters. , Fatty acid amide sulfonate, formalin condensed naphthalene sulfonate, and the like. Examples of the cationic surfactant include an aliphatic amine salt, a quaternary ammonium salt, and an alkylpyridinium salt. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, and polyoxyethylene sorbitan alkyl ester. In the surfactant used in the present invention, an anionic surfactant and / or a nonionic surfactant are preferably used. This is because a salt with the acidic group contained in the modified polymer compound is not formed, and as a result, a decrease in the water absorption of the modified polymer compound can be further prevented.

As a material of the water-permeable bag 2 of the present invention, a cloth of natural fibers or synthetic fibers is used. Examples of the natural fiber include cotton, hemp, and silk.
Examples of the synthetic fiber include polyamide, polyimide, polyester, polyethylene, and polypropylene. It is preferable that these fibers are singly or mixed and knitted or woven into a cloth. However, in some cases, it may be a nonwoven fabric. Further, depending on the case, it may be one in which pores penetrating the front and back of the film-like body are formed.

The support 4 of the present invention is not particularly limited in its shape or material as long as it can support the modified polymer compound. Here, “support” means the water-permeable bag-like body 2
In order to prevent the modified polymer compound from tilting extremely in the above, the modified polymer compound may be attached or impregnated. As the support, specifically, a flexible network is preferable. As the flexible net 4, a cloth of natural fibers or synthetic fibers is used. As the material, the same material as the material of the water-permeable bag 2 can be used. That is, examples of the natural fiber include cotton, hemp, and silk. Examples of the synthetic fiber include polyamide, polyimide, polyester, polyethylene, and polypropylene. It is preferable that these fibers are singly or mixed and knitted or woven into a cloth. However, in some cases, nonwoven fabric or paper may be used. Further, depending on the case, it may be one in which pores penetrating the front and back of the film-like body are formed.

In this case, it is preferable that the occupation ratio of the through holes in the support 4, preferably the flexible network, is higher than that of the water-permeable bag 2, whereby the water absorption is improved. By adhering or impregnating the support with a water-soluble modified polymer compound, the water-absorbing modified polymer compound can be fixed to the support. Thereby, even if the water-absorbing body according to the present invention is used repeatedly by absorbing water, drying after use, and then reusing it, the water-absorbing modified polymer compound becomes out of shape such as being biased inside the water-absorbing body. Can be prevented, and the number of times of repeated use can be increased.

The method of fixing the support of the present invention by adhering or impregnating the water-absorbing modified polymer compound with the support may be performed by dispersing the water-absorbing modified polymer compound in a water-absorbing and swelling state on the support. The method of coating and drying the system can be mentioned. In addition, as the method, a method in which a dispersion of the water-absorbing modified polymer in a non-swelling state in an organic liquid is applied to the support and dried. As a result, the operation of coating and drying can be simplified and the energy used can be reduced, so that it is suitably used in the present invention. Further, as the method, a method in which water or an organic liquid is contained in the support, and the water-absorbing modified polymer compound in a dry state is adhered to the support and dried. The sheet-like body fixed by adhering or impregnating the above-mentioned water-absorbing modified polymer compound to the support by the method as described above can be obtained by performing a compression operation using a static pressure press or a roller. In this case, the heating can be performed at room temperature, but it is more effective to perform the heating at room temperature or higher.

In the present invention, a solid having a specific gravity of 1 or more can be present in the water-permeable bag. In this way, when the water-absorbing body of the present invention is used as a sandbag, there is an advantage that the water-absorbing body is less likely to be washed away by water or the like, particularly in an initial stage of installation. Examples of the solid having a specific gravity of 1 or more according to the present invention include those formed of natural minerals, those formed of waste, and those formed by binding waste. Examples of these materials include metals, ceramics, glass, and materials in which these are bonded to each other. For such binding, a polymer material having a specific gravity of 1 or less can be used. The polymer material used for the binding is not particularly limited, for example, polystyrene, styrene-propylene copolymer,
Styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-
Acrylic ester copolymer, styrene-methacrylic ester copolymer, polyester resin, polyvinyl alcohol, water-soluble resin such as casein or sodium polyacrylate, alcohol-soluble resin such as copolymerized nylon or methoxymethylated nylon, polyurethane,
Curable resins that form a three-dimensional network structure, such as melamine resin or epoxy resin, and the like can be given.

In the present invention, a magnetic substance having a specific gravity of 1 or more may be used. Due to this magnetism, there is an advantage that the water-absorbing body according to the present invention can be magnetically sucked, and can be transported by a crane or the like. In addition, there is an advantage that the sandbag can be identified by the magnetism. Those having magnetism include those having ferrimagnetism, ferromagnetism, or parasitic magnetism. More specifically, as the ferromagnetic material, iron, nickel, cobalt or an alloy thereof,
Alternatively, alloys containing these, further, transition metals or alloys thereof, and alloys containing rare earth elements can be given. Furthermore, as a ferrimagnetic material,
Examples include magnetite, maghemite, hematite, manganese zinc ferrite, manganese nickel ferrite, barium ferrite, or strontium ferrite. These may be those made of natural minerals, those made of waste, and those formed by binding waste. These materials can increase the weight of the water absorbing body in comparison with a general inorganic material, and have an effect of relatively increasing the weight of the water absorbing body in a water absorbing state. In addition, since these materials can be obtained from inductor elements of used electric devices, deflection yokes of speakers and televisions, and are difficult to process in disassembly processing of electronic devices, they are also useful from the viewpoint of effective utilization. is there.

[0042]

EXAMPLES Here, a sample was actually prepared as an example of a water-absorbing material according to the present invention, and a comparative sample and an evaluation thereof were performed. However, the present invention is not limited to this.

Example (Preparation of water-absorbing polymer compound) Concentrated sulfuric acid (96% by weight) 3
0 parts by weight, 1 part by weight of ABS resin waste material was added, and 80 ° C.
For 20 minutes. In addition, as ABS resin waste material,
Used for the black part of an 8 mm cassette tape guard panel, containing 52 mol% of styrene, 28 mol% of acrylonitrile, 20 mol% of butadiene, and 2 wt% of carbon black. The resin was pulverized with a frozen shredder to 16-32
A mesh classifier was used. After completion of the reaction, the solid matter in the system was filtered with a glass filter, washed with water, neutralized with 50 parts by weight of 1N sodium hydroxide solution, further washed with sufficient water, and the pH of the filtrate was adjusted to 8 or less. When it was no longer, it was taken out and dried in a circulating drier at 105 ° C. for 2 hours. By this operation, a black solid was obtained. From the elemental analysis result of sulfur, it was confirmed that the sulfo group in this solid was 33 mol% in all monomer units. Further, the content of sodium is almost equimolar to the sulfo group (1.1)
Met.

(Preparation of Water Absorbent Body) The above black solid was pulverized, and the average particle diameter of the pulverized substance was 0.8 mm.
The pulverized product was dispersed in cyclohexane, dip-coated on gauze, dried, and adhered or impregnated with a water-absorbing modified polymer to a flexible network. The dried sheet was pressed at 100 ° C. An aqueous solution of sodium lauryl sulfate was sprayed and dried on both sides of the sheet. This sheet was cut into sheet-like pieces, which were laminated and sealed in a bag made of a thick cotton cloth impregnated with sodium lauryl sulfate. The content of sodium lauryl sulfate is from 1% to 0.1% of the dry weight of the water absorbent.
%.

Comparative Example A water absorbent was produced in the same manner as in the example except that only the surfactant, sodium lauryl sulfate, was used.

The water-absorbent bodies of the same shape obtained in the examples and comparative examples were placed on a uniform water surface having a depth of 1 cm, and the water-absorbing swelling rate was estimated from the change in the thickness of the absorber. Before immersion, the thickness was almost the same, but the thickness after 1 minute was 2.1 cm in the example and 1.6 cm in the comparative example, and it is clear that the use of a surfactant increases the water absorption rate. became.

[0047]

The water absorbent according to the present invention has a higher water absorption and a higher water absorption rate than a conventional water absorbent or a water absorbent having the function of a sandbag, which is used for removing unnecessary water remaining in water or flooding. It can sufficiently cope with a case where a large amount of water needs to be absorbed or a case where the water must be quickly absorbed. It can be applied not only to pure water, but also to water containing electrolytes such as seawater, sewage, and muddy water. it can. Further, the present invention provides a water absorbing body which is small in weight and volume during transportation and sufficiently satisfies the function of following the shape of weight, volume and external shape by absorbing water during use, and particularly useful as a sandbag. Further, the water absorbent according to the present invention has an advantage that it can be used repeatedly.

The water-absorbing material according to the present invention can be produced by using a used resin or a waste material. Also, a solid material having a specific gravity of 1 or more which is hardly treated in a dismantling treatment of an electronic device can be used. It can be made by
It also has the advantage that it can contribute to the global environment.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a water absorbent according to the present invention when it is dried.

FIG. 2 is a cross-sectional view of the water-absorbent body according to the present invention when it swells by water absorption.

FIG. 3 is a cross-sectional view of the water absorbent according to the present invention containing a solid having a specific gravity of 1 or more, when the absorbent is dried.

FIG. 4 is a cross-sectional view of the water-absorbent body according to the present invention containing a solid having a specific gravity of 1 or more, when the water-absorbent body swells.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Water-absorbing body 2 Water-permeable bag-like body 3 Water-absorbing material 4 Support 5 Solid matter with specific gravity of 1 or more

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tsutomu Noguchi 6-7-35 Kita Shinagawa, Shinagawa-ku, Tokyo F-term in Sony Corporation (reference) 2D018 AA06 4G066 AC13A AC13B AC14A AC14B AC17A AC17B AE01D AE05B AE06B BA12 CA43 EA20 FA11 4J002 AC071 BC061 BG101 BN151 CH022 EG016 EH046 EN016 EN136 EU046 EV186 EV256 FD010 FD312 FD316 GL00 4J100 AB02Q AL03R AM02P AM15R AS02Q AS02R BA01H BA17H BA41H BA56H BA64H CA04 CA05 CA31 HB44 JA67

Claims (20)

[Claims] 1. A modified polymer compound in which an acidic group is introduced into a polymer compound containing (a) acrylonitrile and (b) at least one of styrene and / or conjugated diene, a surfactant, A water absorber, wherein the support is contained in a water-permeable bag. 2. The method according to claim 1, wherein the support is a flexible network.
The water absorbent according to the above. 3. The water absorbent according to claim 1, wherein the modified polymer compound is supported by a support. 4. The polymer compound according to claim 1, wherein the polymer compound contains (a) acrylonitrile obtained from waste material and (b) at least one of styrene and / or conjugated diene. The water absorbent according to the above. 5. The water absorbent according to claim 1, wherein the surfactant is an anionic surfactant and / or a nonionic surfactant. 6. The water-absorbing material according to claim 1, wherein a solid having a specific gravity of 1 or more is contained in the water-permeable bag. 7. The water absorbent according to claim 6, wherein the solid having a specific gravity of 1 or more is made of a natural mineral. 8. The water absorbent according to claim 6, wherein the solid having a specific gravity of 1 or more is made of waste. 9. The water absorbing body according to claim 6, wherein the solid having a specific gravity of 1 or more is formed by binding waste. 10. The water absorbent according to claim 6, wherein the solid having a specific gravity of 1 or more is made of magnetic waste. 11. A modified polymer compound in which an acidic group is introduced into a polymer compound containing (a) acrylonitrile and (b) at least one of styrene and / or conjugated diene, a surfactant, A method for producing a water-absorbent body, comprising filling a support with a water-permeable bag. 12. The water absorbing body according to claim 11, wherein the support is a flexible network. 13. The method according to claim 11, wherein the modified polymer compound is supported on a support. 14. The polymer compound according to claim 11, wherein the polymer compound contains (a) acrylonitrile obtained from waste material and (b) at least one of styrene and / or conjugated diene. The method for producing a water absorbent according to the above. 15. The method for producing a water absorbent according to claim 11, wherein the surfactant is an anionic surfactant and / or a nonionic surfactant. 16. The method for producing a water absorbent according to claim 11, further comprising filling a solid having a specific gravity of 1 or more into the water-permeable bag. 17. The method according to claim 16, wherein the solid having a specific gravity of 1 or more is made of a natural mineral. 18. The method according to claim 16, wherein the solid having a specific gravity of 1 or more is waste. 19. The method for producing a water absorbent according to claim 16, wherein the solid having a specific gravity of 1 or more is formed by binding waste. 20. The method according to claim 16, wherein the solid having a specific gravity of 1 or more is made of magnetic waste.