JPH0912643A - Antibacterial super absorbent resin and method for producing the same - Google Patents

Abstract

(57) [Summary] [Structure] For example, an antibacterial superabsorbent resin obtained by cross-linking polymerization of triethylvinylbenzylphosphonium chloride and acrylamide in the presence of a cross-linking agent, and a method for producing the same. [Effect] According to the present invention, as a function of the resin itself, an antibacterial superabsorbent resin that exhibits an excellent antibacterial action upon contact for a short time and hardly elutes an antibacterial substance is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly water-absorbent resin having excellent antibacterial properties which is substantially free from bacterial contamination and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, since water-absorbent resins have both properties of high water-absorption and water-retention, sanitary products, sanitary materials such as paper diapers, soil water-retaining agents for agricultural and horticultural use, seed coating agents, and nursery sheets. It is used in a wide range of fields such as food freshness retention packaging materials, food / distribution drip absorbent materials, gel fragrances, disposable body warmers, sealing materials, and concrete curing / modifying agents. However, for example, a water-absorbent sheet manufactured using a water-absorbent resin has a drawback in that when the water-absorbent resin absorbs water, the surface material of the water-absorbent sheet also becomes in a water-containing state, and thus molds and bacteria are likely to propagate on the surface. For example, when the water-absorbent sheet is used for sanitary items, sanitary materials such as disposable diapers, in order to retain the discharged material for a long time,
Bacteria propagate and odor becomes a problem. Further, when it is used as a drip sheet for food, microorganisms are easily propagated in water produced from fresh fish and meat, and bacteria are propagated on the surface of the sheet, which deteriorates the freshness of food. When it is used as a sealing material for civil engineering, it has a problem that mold and bacteria propagate at the joint due to long-time underground burying and the sealing material deteriorates.

Therefore, in order to solve such a problem, for example, a method in which a zeolite having silver ions having an antibacterial action and a super absorbent resin are sandwiched between two membranes to form a water absorbent sheet (Japanese Patent Laid-Open No. 63-63). No. 156540) or a method of imparting an antibacterial effect by uniformly mixing a water-soluble glass containing silver with a super absorbent resin (JP-A-1-153748).
Alternatively, a method of further mixing a zinc 2-pyridinethiol-1-oxide antibacterial agent into a mixed system of a polyolefin resin and a superabsorbent resin (JP-A-5-9344).
For example, so-called addition type antibacterial water-absorbent resin in which an inorganic or organic antibacterial agent is added to the resin has been proposed.

[0004]

However, the antibacterial water-absorbent resin proposed as described above contains an antibacterial agent, and is, for example, discolored by light or the like, or antibacterial during heat treatment of the resin. There are problems that the agent decomposes, the antibacterial activity is insufficiently maintained, and the antibacterial agent elutes. Further, organic antibacterial agents are difficult to use in foods, sanitary products, etc. due to their toxicity. In view of solving the conventional problems as described above, the present invention, as a function of the resin itself, shows an excellent antibacterial action by a short time contact,
Further, it is an object to provide an antibacterial superabsorbent resin in which an antibacterial substance is hardly eluted.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides the following general formula (1)

[0006]

Embedded image

(Wherein R ¹ , R ² and R ³ represent the same or different alkyl groups having 1 to 14 carbon atoms, and X ⁻ represents a halogen atom), and an alkylvinylbenzylphosphonium halide and acrylamide. The present invention provides an antibacterial highly water-absorbent resin obtained by cross-linking and polymerizing in the presence of a cross-linking agent.

The present invention also provides that the alkylbenzylphosphonium halide is selected from the group consisting of triethylvinylbenzylphosphonium chloride, tripropylvinylbenzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride and trioctylvinylbenzylphosphonium chloride. At least one selected
The above-mentioned antibacterial highly water-absorbent resin, which is a seed, is provided.

Further, the present invention provides the above-mentioned antibacterial superabsorbent resin, wherein the crosslinking agent is methylenebisacrylamide or methylenebismethacrylamide.

Furthermore, in the present invention, the compounding ratio (mol%) of alkylvinylbenzylphosphonium halide: acrylamide: crosslinking agent is 0.5 to 10:90 to respectively.
The above-mentioned antibacterial superabsorbent resin having a range of 98: 1 to 5 is provided.

In the present invention, the cross-linked polymer has a phosphorus content of P
The antibacterial superabsorbent resin is provided in the range of 0.1 to 1.0 mmol / g.

Further, the present invention is characterized in that the alkylvinylbenzylphosphonium halide represented by the above general formula (1) and acrylamide are used as monomer components, and the monomer components are copolymerized in a solvent in the presence of a crosslinking agent and a catalyst. The present invention provides a method for producing an antibacterial superabsorbent resin.

Hereinafter, the present invention will be described in more detail. As described above, the antibacterial superabsorbent resin according to the present invention is characterized by being a copolymer in which the alkylvinylbenzylphosphonium halide of the general formula (1) and acrylamide are crosslinked. (Alkylbenzylphosphonium halide) In the alkylbenzylphosphonium halide of the general formula (1), R ¹ , R ² and R ³ are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Alkyl groups such as heptyl group, octyl group, dodecyl group, octadecyl group; aryl groups such as phenyl group, tolyl group, xylyl group; aralkyl groups such as benzyl group, phenylyl group; and the above alkyl groups, aryl groups, aralkyl groups Examples thereof include groups substituted with a group or an alkoxy group, of which alkyl groups such as heptyl and octyl are preferred, aryl groups such as phenyl and tolyl are more preferred, and alkyl groups are more preferred. In addition, R ¹ , R ² and R ³ may or may not be the same group.

Examples of the halogen atom of X include a halogen atom of fluorine, chlorine, bromine or iodine (I ⁻ , I ₃ ⁻ ), among which chlorine ion and bromine ion are preferable.

When R ^{1 to} R ³ are lower alkyl groups such as methyl group and ethyl group, they are water-soluble and also soluble in organic solvents such as alcohol. Conversely, R ¹
Solubility in water tends to decrease as R ³ becomes a higher alkyl group such as a pentyl group, a hexyl group or an octyl group. In the case of an alkyl group, the antibacterial effect is influenced by the length of the alkyl group, and the antibacterial effect tends to increase with, for example, methyl, ethyl, butyl, and octyl. However, since the water absorption tends to decrease, it may be appropriately designed according to the purpose of use of the resin. When only one of R ^{1 to} R ³ is a higher alkyl group such as octadecyl (C18) and the other two are lower alkyl groups such as a methyl group, cell membrane attack is high and the antibacterial effect is low. high.

The alkylbenzylphosphonium halide used in the present invention is not particularly limited as long as it is represented by the general formula (1), but preferable examples thereof include triethylvinylbenzylphosphonium chloride and tripropylvinyl. Examples thereof include benzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride, trioctylvinylbenzylphosphonium chloride and the like.

(Acrylamide) In the present invention, “acrylamide” is meant to include acrylamide as well as N-alkylamides such as methacrylamide and N-methylacrylamide. In addition, other water-soluble vinyl compounds may be used in combination if necessary.

(Crosslinking Agent) The crosslinking agent used in the present invention is not particularly limited, but for example, methylenebisacrylamide, methylenebismethacrylamide and ethylene glycol dimethacrylate are preferably used.

(Blending Ratio) In the antibacterial superabsorbent resin according to the present invention, the mixing ratio of the above-mentioned monomer components constituting the resin varies depending on the type of the monomer and the use of the resin and can be arbitrarily designed. Alkyl vinylbenzyl phosphonium halide based on the proportion of 0.5 to 10 mol%, acrylamide 90 to 98 mol% and crosslinking agent 1 to 5 mol%, preferably alkyl vinyl benzyl phosphonium halide 1 to 5 mol%, acrylamide A range of 92 to 96 mol% and a crosslinker 2 to 5 mol% is preferred. According to this blending ratio, in the antibacterial superabsorbent resin according to the present invention, the phosphorus content is 0.1 to 1.1 as P.
It can be said that the range of 0 mmol / g is preferable.

When the content of alkyl vinyl benzyl phosphonium halide is less than 0.5 mol%, the antibacterial property of the resin becomes insufficient, and conversely, when the content of the alkyl vinyl benzyl phosphonium halide increases, the water absorption amount and the antibacterial property also increase. However, if it exceeds 10 mol%, it is not very economical. When the cross-linking agent is less than 1 mol%, the resin tends to be water-soluble and the physical properties of the water-absorbent gel tend to be poor.
On the other hand, if it exceeds 5 mol%, the water absorption will be deteriorated and the physical properties of the resin will be deteriorated in any case.

If necessary, other vinyl monomer,
For example, acrylic acid, methacrylic acid and their alkyl esters can be used in appropriate amounts.

(Polymerization of Alkylbenzylphosphonium Halide with Acrylamide) In the present invention, the polymerization of alkylbenzylphosphonium halide with acrylamide is carried out in the presence of a crosslinking agent.

For the above-mentioned polymerization, a radical polymerization catalyst may be used. As the radical polymerization catalyst, hydrogen peroxide,
Benzoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethyl hexanate, t-butyl peroxy vivarate, t-butyl peroxy diisobutyrate,
Peroxides such as t-butylperoxyisopropyl carbonate, lauroyl peroxide, azobisisobutyronitrile, azobisisovalerial acid, azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Amid compounds such as amidinopropane) hydrochloride, radical polymerization catalysts such as persulfate such as ammonium persulfate and potassium persulfate, and sodium bisulfite, ammonium sulfite, L-ascorbic acid, ferrous salt, etc. A redox type initiator in combination with the reducing agent is used.

The polymerization solvent is, for example, methanol,
Examples thereof include ethanol, acetone, N, N-dimethylformamide, dimethylsulfoxide, n-hexane and cyclohexane, and these can be used alone or in combination of two or more.

In the present invention, the polymerization conditions vary depending on various raw materials, but the polymerization temperature is room temperature to 100 ° C., preferably 10 to 80 ° C., and the polymerization time is 3 to 48 hours, preferably 5
~ 30 hours. After the completion of the polymerization, if necessary, hydrolysis, purification, drying, and pulverization treatment are carried out to obtain the antibacterial and highly water-absorbent resin of the present invention.

The thus obtained antibacterial superabsorbent resin of the present invention contains various bacteria such as Escherichia coli and Staphylococcus aureus.
It shows effective antibacterial properties against fungi and algae. It also has extremely high stability to heat and solvents. In addition, the antibacterial superabsorbent resin of the present invention does not dissolve in water and has a weight of several tens of weight.
It has the ability to absorb and retain hundreds of times more water.

In the antibacterial superabsorbent resin of the present invention, at the time of or after the copolymerization, attapulgite, kaolin, talc, diatomaceous earth may be added to improve the water absorption rate, if necessary. Further, if necessary, various resin fillers such as organic materials such as pulp, wood powder, synthetic fiber, glass fiber, glass powder, finely divided silica, alumina, apatite, zeolite, calcium silicate,
Inorganic substances such as mica and shirasu can be added. Further, a small amount of a foaming agent, an antifoaming agent, an antiaging agent, a heat stabilizer, an antioxidant, a dyeing agent, a pigment, a coloring agent and the like can be added. In addition, an emulsion of a thermoplastic resin, a latex of synthetic rubber, and a water-soluble polymer can be mixed for the purpose of improving viscosity and strength.

The antibacterial superabsorbent resin of the present invention has an amorphous powder form, a spherical granular powder form, a short fibrous form, depending on the purpose of use.
It can be formed into various shapes such as long fiber shape, non-woven shape, and film shape. The antibacterial superabsorbent resin of the present invention has excellent antibacterial properties, and therefore, sanitary products, sanitary materials such as paper diapers, food freshness-keeping packaging materials, food / distribution drip absorbents, agricultural / horticultural soil water retention. It can be used in a wide range of fields such as chemicals, antifouling paints for ship bottoms, highly water-absorbent fibers, anti-condensation materials, and highly permeable separation membranes. At the same time, antistatic property, flame retardancy, and antifouling property can be imparted.

[0029]

The basic skeleton of the antibacterial superabsorbent resin of the present invention is shown below. Incidentally, X ^- as Cl ^- and N as a crosslinking agent,
This is an example using N'-methylenebisacrylamide.

[0030]

Embedded image

[0031]

The present invention will be described below with reference to examples. Synthesis of antibacterial super absorbent resin Three alkylbenzylphosphonium halides (hereinafter T
RVB), that is, tributylvinylbenzylphosphonium chloride (hereinafter TBVB), trihexylvinylbenzylphosphonium chloride (hereinafter THVB) and trioctylvinylbenzylphosphonium chloride (hereinafter TOVB), acrylamide (hereinafter AAm) and N, N-methylenebisacrylamide (hereinafter M
BAA) is dissolved in 20 ml of dimethylsulfoxide (hereinafter referred to as DMSO) at a prescribed mol% and azobisisobutyronitrile is used as a polymerization initiator in a predetermined mol%.
In addition, it was placed in a polymerization test tube. After substituting nitrogen for 60 minutes in a water bath and sealing, the mixture was polymerized while shaking at 50 ° C. to synthesize a copolymer. The resulting copolymer is subjected to repeated swelling-shrinkage with DMSO, ion-exchanged water and acetone to remove unreacted monomers and the like, purified, and then finely ground,
After air drying, it was dried in a vacuum dryer for 24 hours, and the dried copolymer was further sieved to 14 to 32 mesh and 32 to 60 mesh to obtain an antibacterial superabsorbent resin.

The compounding ratios of TRVB, AAm and MBAA are shown in Table 1 below.

[0033]

[Table 1]

Three types of TRVB were used in the experiment as described above, and the phosphorus content of the resin obtained by the above mixing ratio is shown in Table 2 below.

[0035]

[Table 2]

Measurement of Water Absorption The synthesized antibacterial superabsorbent resin of the present invention (sample) was
Place in a non-woven bag and soak the sample in excess ion-exchanged water or sodium chloride solution. After a predetermined time,
The bag is taken out from the liquid, water on the sample surface and the bag surface is wiped off, and the weight (A) is measured. The water absorption weight (B) of the bag itself and the dry weight (C) of the sample are also measured in advance. The water absorption amount (W) is defined by the following equation. Also, in the following experiment, the immersion time in the liquid is
Basically, it was set to 48 hours, which was sufficient for the water absorption amount to be saturated. This formula means g of liquid absorbed per g of resin.

[0037]

## EQU1 ## W = (A-B-C) / C

Experiments were conducted on the relationship between various factors and the water absorption of the resin. The outline is as follows: Relationship between various temperatures and water absorption of resin (Fig. 1); Relationship between content of cross-linking agent and water absorption of resin (Figs. 2 and 3); Content of various alkylbenzylphosphonium halides and water absorption Relationship with amount (Fig. 4); Relationship between various concentrations of sodium chloride aqueous solution and water absorption of crosslinker and resin (Figs. 5, 6 and 7); and various concentrations of sodium chloride aqueous solution and alkylbenzylphosphonium It is the relationship between the halide and the water absorption of the resin (FIGS. 8, 9 and 10);

Next, the above experiment and the result thereof will be described in detail. Relationship between various temperatures and water absorption of resin As a sample, TBVB: AAm: MBAA = 2: 9
5: 3 (mol%), THVB: AAm: MBAA = 2:
94: 4 (mol%) and TOVB: AAm: MBAA
= 2: 93: 5 (mol%), the water absorption of ion-exchanged water at a temperature of 20 to 35 ° C was examined. The result is shown in FIG. From Figure 1, even if the temperature changes, the water absorption does not change,
It turns out that it is stable.

Relationship between Content of Crosslinking Agent and Water Absorption of Resin First, alkylbenzylphosphonium halide (TRV
As B), TBVB having a fixed mixing ratio is used,
The blending ratio of BAA was changed in the range of 2 mol% to 5 mol%, and the water absorption of the ion-exchanged water at the room temperature and the immersion time of 0 to 48 hours was examined. The result is shown in FIG. From FIG. 2, when the mixing ratio of the cross-linking agent is in the range of 3 to 5 mol%, the immersion time is about 6
It is understood that the water absorption amount is saturated from the time, but the water absorption amount increases with the lapse of the immersion time when the crosslinking agent is 2 mol%. This means that the amount of the crosslinking agent is greatly influenced by the water absorption rate and the water absorption amount. Next, as alkylbenzylphosphonium halide (TRVB), in addition to TBVB, THVB and TOVB are
The blending ratio of the cross-linking agent MBAA was changed in the range of 2 mol% to 5 mol%, and the water absorption amounts of ion-exchanged water and 0.9 wt% NaCl aqueous solution at room temperature for 48 hours were examined. The result is shown in FIG. As a control, TR
An experiment was also conducted by using one without VB. From FIG. 3, it can be seen that these resins containing TRVB show high water absorption in ion-exchanged water, and resins containing TBVB and THVB show a relatively high water absorption even though the water absorption decreases in NaCl solution. understood. Also,
It can be seen that the water absorption amount greatly changes depending on the mixing ratio of the cross-linking agent MBAA. The control sample showed almost the same water absorption in the ion-exchanged water and the NaCl solution.

Various alkylbenzylphosphonium
Relationship between Halide Content and Water Absorption As alkylbenzylphosphonium halide (TRVB), the compounding ratio of TBVB, THVB and TOVB was changed in the range of 1 to 5 mol% and the ion-exchanged water was immersed at room temperature for 48 hours for 48 hours. The water absorption was examined. The result is shown in Figure 4.
Shown in From FIG. 4, it can be seen that the amount of water absorption increases with an increase in the blending ratio of TRVB, TBVB, THVB,
It can be seen that the order is the resin containing TOVB.

Aqueous solutions of sodium chloride having various concentrations
And the relationship between the cross- linking agent and the water absorption amount of the resin In the case where the cross-linking agent MBAA is 2 to 5 mol%, in the case of ion-exchanged water, 0.009 wt%, 0.09 wt% and 0.9 wt% NaCl aqueous solution. The change in water absorption at 48 hours at room temperature was examined. The result is shown in FIG.
7 to FIG. Alkylbenzylphosphonium halides (TRVB) include TBVB (Fig. 5) and THVB
(FIG. 6) and TOVB (FIG. 7) were used. 5 to 7
From the results, the water absorption decreased with the increase of the blending ratio of the cross-linking agent MBAA, and the water absorption was the highest for ion-exchanged water, followed by 0.009% by weight, 0.09% by weight,
It can be seen that the order is 0.9% by weight NaCl aqueous solution.

Aqueous solutions of sodium chloride having various concentrations
And absorption of alkylbenzylphosphonium halide and resin
Relationship with water amount As alkylbenzylphosphonium halide (TRVB), TBVB (FIG. 8), THVB (FIG. 9) and TO
Absorption of 0.009% by weight, 0.09% by weight and 0.9% by weight NaCl aqueous solution at room temperature for 48 hours by varying the blending ratio of VB (FIG. 10) within the range of 1 to 5 mol%. The change in quantity was investigated. The results are shown in FIGS. From FIGS. 8 to 10, except for TOVB, the water absorption amount is 0.
009 wt% NaCl aqueous solution is the highest, then 0.09
It can be seen that the order is the weight% and the 0.9 weight% NaCl aqueous solution.

As a sample for measuring the antibacterial activity of the antibacterial superabsorbent resin, an antibacterial superabsorbent resin having a TOVB content of 1 to 5 mol% and a superabsorbent resin having a TOVB content of 0 mol% were used as controls. . As a representative of Gram-negative bacteria, Escherichia coli IFO3301 was used in this test to prepare a bacterial suspension (ion-exchanged water and 0.9 wt% NaCl aqueous solution) of a predetermined number of bacteria (60 m
l). Add 0.025g of sample to this bacterial suspension,
The mixture was shaken at 6 ° C for 6 hours, and the number of remaining viable cells was examined. The remaining viable cell count was obtained by inoculating 9 ml of sterile water with 1 ml of bacterial suspension and diluting 10-fold (if necessary, diluting in several steps), adding a neutralizing agent to inactivate the activity of the resin, and 0.1 ml of the bacterial suspension was spread on a flat medium, placed in an incubator and grown at 30 ° C. for 15 to 24 hours, then the number of colonies was counted and calculated by the following formula.

[0045]

[Number 2] viable cell count = M × in 10 ^x /0.1 formula, M is the number of colonies, x is a dilution number.

The results of the experiment are shown in FIG. From FIG.
In the case of ion-exchanged water, it can be seen that the antibacterial activity also increases as the blending ratio of TOVB increases. In addition, NaCl
The antibacterial activity in solution was not as high as in ion-exchanged water.

A microbial cell removal coefficient was calculated from the results of this experiment. The cell removal coefficient is calculated by the following formula.

[0048]

[Formula 3] Cell removal coefficient D (ml / g · h) = (V / Wt ·
t) log (No / Nt) where V is the volume of the bacterial suspension (ml), Wt is the dry weight of the resin (g), t is the contact time (h), and No is the initial viable cell count (cel).
l / ml) and Nt are the viable cell counts (cel
l / ml) respectively.

The results are shown in Table 3 below.

[0050]

[Table 3] Table 3 TOVB mol% Cell removal coefficient D (ml / g · h) 0.9% by weight ion-exchanged water NaCl aqueous solution ━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━ 1 572 92 2 380 50 3 1384 884 4 1508 96 5 2368 111

From the results shown in Table 3, the resin containing TOVB was
It can be seen that the antibacterial property increases with the content thereof, and that the tendency is particularly great in ion-exchanged water.

Next, as a sample, TOVB: AAm:
MBAA = 5: 92: 3 mol% dry resin and swelling resin were used, and the contact time between the sample and the bacterial suspension was 0-2.
The above experiment was repeated except that the time was set to 4 hours, and the antibacterial activity was examined (ion-exchanged water). As a control, TOV
B0 mol% was used. FIG. 12 shows the result. FIG.
From 2, it can be seen that the antibacterial superabsorbent resin of the present invention has excellent antibacterial activity even if the dry resin is added to the bacterial suspension as it is or the resin once swollen with water is added, but both are excellent. It is found that it has antibacterial activity.

[0053]

According to the present invention, as a function of the resin itself, an antibacterial and highly water-absorbent resin which exhibits an excellent antibacterial action when contacted for a short time and hardly elutes an antibacterial substance is provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between various temperatures and a water absorption amount of a resin.

FIG. 2 is a diagram showing a relationship between a content of a cross-linking agent and a water absorption amount of a resin.

FIG. 3 is a diagram showing a relationship between a content of a cross-linking agent and a water absorption amount of a resin.

FIG. 4 is a diagram showing the relationship between the content of various alkylbenzylphosphonium halides and the amount of water absorption.

FIG. 5 is a graph showing the relationship between various concentrations of aqueous sodium chloride solutions and cross-linking agents, and water absorption of resin.

FIG. 6 is a diagram showing the relationship between various concentrations of aqueous sodium chloride solutions and cross-linking agents, and the water absorption of resin.

FIG. 7 is a graph showing the relationship between various concentrations of aqueous sodium chloride solutions and cross-linking agents, and the water absorption of resin.

FIG. 8 is a graph showing the relationship between various concentrations of aqueous sodium chloride solutions and alkylbenzylphosphonium halides and water absorption of resin.

FIG. 9 is a graph showing the relationship between various concentrations of aqueous sodium chloride solutions and alkylbenzylphosphonium halides and the water absorption of the resin.

FIG. 10 is a diagram showing the relationship between various concentrations of aqueous sodium chloride solutions and alkylbenzylphosphonium halides and the water absorption of the resin.

FIG. 11 is a graph showing the antibacterial activity of the antibacterial superabsorbent resin of the present invention.

FIG. 12 is a view showing the antibacterial activity of the antibacterial superabsorbent resin of the present invention.

Claims (10)

[Claims] 1. The following general formula (1): (In the formula, R ¹ , R ² and R ³ represent the same or different alkyl groups having 1 to 14 carbon atoms, and X represents a halogen atom), and an alkylvinylbenzylphosphonium halide and acrylamide are crosslinked with each other. An antibacterial highly water-absorbent resin obtained by cross-linking and polymerizing in the presence of. 2. The alkylbenzylphosphonium halide is selected from the group consisting of triethylvinylbenzylphosphonium chloride, tripropylvinylbenzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride and trioctylvinylbenzylphosphonium chloride. The antibacterial highly water-absorbent resin according to claim 1, which is at least one kind. 3. The antibacterial superabsorbent resin according to claim 1, wherein the crosslinking agent is methylenebisacrylamide or methylenebismethacrylamide. 4. A compounding ratio (mol%) of alkylvinylbenzylphosphonium halide: acrylamide: crosslinking agent.
Are in the range of 0.5 to 10:90 to 98: 1 to 5, respectively, and the antibacterial superabsorbent resin according to any one of claims 1 to 3. 5. The phosphorus content of the crosslinked polymer is 0.1 as P.
The antibacterial highly water-absorbent resin according to claim 4, which is in the range of ~ 1.0 mmol / g. 6. The following general formula (1): (In the formula, R ¹ , R ² and R ³ represent the same or different alkyl groups having 1 to 14 carbon atoms, and X represents a halogen atom), and alkyl vinylbenzyl phosphonium halide and acrylamide as a monomer component, A method for producing an antibacterial highly water-absorbent resin, which comprises copolymerizing the monomer component in a solvent in the presence of a crosslinking agent and a catalyst. 7. The alkylbenzylphosphonium halide is selected from the group consisting of triethylvinylbenzylphosphonium chloride, tripropylvinylbenzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride and trioctylvinylbenzylphosphonium chloride. The manufacturing method according to claim 6, which is at least one kind. 8. The method according to claim 6, wherein the crosslinking agent is methylenebisacrylamide or methylenebismethacrylamide. 9. A blending ratio (mol%) of alkylvinylbenzylphosphonium halide: acrylamide: crosslinking agent.
Are in the range of 0.5 to 10:90 to 98: 1 to 5 respectively, and the production method according to any one of claims 6 to 8. 10. The phosphorus content of the crosslinked polymer is 0.1 as P.
The production method according to claim 9, wherein the amount is in the range of 1 to 1.0 mmol / g.