JPH09110622A - Antibacterial resin containing phosphorus and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water soluble or water absorbing antibacterial resin containing phosphorus having an excellent antibacterial capability not substantially forming a pollution with bacteria by graft-polymerizing a polyvinyl alcohol with a specific monomer containing phosphorus and another specific monomer. SOLUTION: This antibacterial resin containing phosphorus is obtained by graft-copolymerizing a polyvinyl alcohol with an alkylvinylbenzylphosphonium halide of the formula (R<1> to R<3> are each a 1-14C alkyl; X is a halogen) and acrylamide. Further, it is preferable to perform a gelation of the copolymer by a heat-treatment or a cross-linking treatment. As the compound of the formula, e.g. triethylvinylbenzylphosphonium chloride is cited. The antibacterial resin containing phosphorus is obtained by blending 1 pts.wt. polyvinyl alcohol with 1-5 pts.wt. compound of the formula and 5-10 pts.wt. acrylamide. The phosphorus content is 0.1-5.0mmol/g resin as P. This antibacterial resin containing phosphorus manifests the antibacterial action in a short period, and is excellent in sustaining property, and further there is almost no elution of the antibacterial substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial phosphorus-containing resin and a method for producing the same. The present invention relates to a water-absorbing phosphorus-containing resin and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, water-absorbent resins have the characteristics of both high water-absorption and water retention, and therefore, for example, sanitary products, sanitary materials such as paper diapers, soil water retention agents for agricultural and horticultural use, seed coating agents, seedlings for raising seedlings. Sheet, food freshness keeping packaging,
It is used in a wide range of fields such as food and distribution drip absorbents, 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 as a sanitary material such as sanitary products and disposable diapers, the discharged matter is retained for a long time, bacteria are propagated, and odors become 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 used as a sealing material for civil engineering, due to underground burial for a long time, mold and bacteria propagate at the joint,
There is a problem that the sealing material is deteriorated.

On the other hand, a water-soluble resin represented by polyvinyl alcohol changes the viscosity of the aqueous solution, the surface tension, the protective colloidal property of the suspended particles, etc. in combination with the control of the degree of polymerization and the degree of saponification. A wide variety of applications are being developed such as fiber processing agents, pigment dispersants, sizing agents for paper materials, various adhesives, and films. However, it is easily affected by recurrence and mold, and its use is naturally limited when controlling this.

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

However, the water-absorbent resin proposed as described above contains an antibacterial agent, and is, for example,
There are problems such as discoloration due to light, decomposition of the antibacterial agent during heat processing of the resin, insufficient persistence of antibacterial activity, and further elution of the antibacterial agent. Further, organic antibacterial agents are difficult to use in foods, sanitary products, etc. due to their toxicity.

Further, in the case of a water-soluble resin typified by polyvinyl alcohol, when antibacterial properties are required, generally known antibacterial agents and bactericides are added and mixed. Therefore, the essential solution has not been reached.

In view of solving the above-mentioned conventional problems, the present invention takes advantage of polyvinyl alcohol and, as a function of the resin itself, shows an excellent antibacterial action by short-time contact and is excellent in durability. It is an object of the present invention to provide a water-soluble or water-absorbing phosphorus-containing resin having antibacterial activity with almost no elution of antibacterial substances.

[0008]

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 polyvinyl alcohol with the following general formula (1):

[0009]

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 grafted with alkylvinylbenzylphosphonium halide and acrylamide. The present invention provides an antibacterial phosphorus-containing resin, which is a copolymer obtained by polymerization.

The present invention also provides the above-mentioned antibacterial phosphorus-containing resin obtained by gelling a copolymer by heat treatment or crosslinking reaction treatment.

The present invention further provides that the alkylvinylbenzylphosphonium halide is a group consisting of triethylvinylbenzylphosphonium chloride, tripropylvinylbenzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride and trioctylvinylbenzylbenzylphosphonium chloride. The above-mentioned antibacterial phosphorus-containing resin is at least one selected from

Furthermore, the present invention provides the above-mentioned antibacterial phosphorus-containing resin which uses glutaraldehyde as a crosslinking agent in the crosslinking reaction treatment.

The present invention also provides the above-mentioned antibacterial phosphorus-containing resin in which 1 to 5 parts by weight of alkylvinylbenzylphosphonium halide and 5 to 10 parts by weight of acrylamide are used per 1 part by weight of polyvinyl alcohol. is there.

Further, in the present invention, the phosphorus content is P as 0.
The above-mentioned antibacterial phosphorus-containing resin having a range of 1 to 5.0 mmol / g resin is provided.

Furthermore, the present invention is characterized in that after adding the alkylvinylbenzylphosphonium halide represented by the general formula (1) and acrylamide to a polyvinyl alcohol solution, the above components are graft-polymerized in the presence of a catalyst. The present invention provides a method for producing an antibacterial phosphorus-containing resin.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As described above, the phosphorus-containing resin having antibacterial activity according to the present invention is largely a copolymer obtained by graft-polymerizing an alkylvinylbenzylphosphonium halide of the general formula (1) and acrylamide onto polyvinyl alcohol. It is a feature.

The type in which a monomer component is graft-polymerized to polyvinyl alcohol as disclosed in the present invention is originally water-soluble, but it is gelated by a heat treatment or a cross-linking reaction treatment, which will be described later, to form a highly water-absorbent resin. Can be Therefore, the antibacterial phosphorus-containing resin of the present invention may be hereinafter referred to as a water-soluble or highly water-absorbent resin.

(Polyvinyl alcohol) The polyvinyl alcohol usable in the present invention is not particularly limited and can be freely selected according to the purpose, and the degree of polymerization and the degree of saponification are not particularly limited.

(Alkylvinylbenzylphosphonium halide) In the alkylvinylbenzylphosphonium halide of the general formula (1), R ¹ , R ² and R ³ are methyl, ethyl, propyl, butyl, pentyl or hexyl. Group, heptyl group, octyl group, dodecyl group, octadecyl group, and other alkyl groups; phenyl group, tolyl group, xylyl group, and other aryl groups; benzyl group, phenylyl group, and other aralkyl groups; the alkyl groups, aryl groups, and aralkyl groups A group in which is substituted with a hydroxy group or an alkoxy group, and the like, among them, preferably hexyl,
An alkyl group such as octyl, an aryl group such as phenyl and tolyl, and more preferably an alkyl group.
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 a chlorine ion and a 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 affected by the length thereof, and the antibacterial effect tends to increase as the chain length increases, for example, with methyl, ethyl, butyl, and octyl.
However, since the water solubility or water absorption tends to decrease, it may be appropriately designed according to the purpose of use of the resin. Further, 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, bacterial cell membrane attack is high and antibacterial activity is high. The effect is high.

The alkylvinylbenzylphosphonium halide used in the present invention is not particularly limited as long as it has the general formula (1), but preferable examples thereof include triethylvinylbenzylphosphonium chloride and tripropyl. Examples thereof include vinylbenzylphosphonium chloride, tributylvinylbenzylphosphonium chloride, trihexylvinylbenzylphosphonium chloride, trioctylvinylbenzylphosphonium chloride and the like.

(Acrylamide) In the present invention, the term “acrylamide” refers to acrylamide and alkyl (methacryl) such as N-substituted alkyl (methacryl) amide such as methacrylamide, N-methylacrylamide, N-isopropylacrylamide and the like. It is meant to include a system monomer.

(Blending Ratio) In the antibacterial phosphorus-containing resin according to the present invention, the mixing ratio of the above-mentioned monomer components constituting the resin can be arbitrarily designed depending on the kind of the monomer and the use of the resin, but In the case of 1 part by weight of polyvinyl alcohol, 1 to 5 parts by weight of alkylvinylbenzylphosphonium halide, preferably 1 to 4 parts by weight, 5 to 10 parts by weight of acrylamide, preferably 6 to 9 parts by weight.
It is in the range of parts by weight. According to this blending ratio, in the antibacterial phosphorus-containing resin according to the present invention, the phosphorus content is generally in the range of 0.1 to 5.0 mmol / g as P, and especially 0.1.
It can be said that the range of 2-3 mmol / g is preferable.

When the amount of the alkyl vinyl benzyl phosphonium halide is less than 1 part by weight, 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. If it exceeds 5 parts by weight, it is not very economical.

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

(Graft Polymerization) In the graft polymerization of the present invention, as a polymerization catalyst, for example, hydrogen peroxide, benzoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2 is used.
-Peroxides such as ethylhexanate, t-butylperoxybivalate, t-butylperoxydiisobutyrate, t-butylperoxyisopropyl carbonate, lauroyl peroxide, azobisisobutyronitrile, azobisisovale Real acid, azo compounds such as azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) hydrochloride, and radical polymerization catalysts such as ammonium persulfate and persulfates such as potassium persulfate Alternatively, a redox-based initiator obtained by combining these with a reducing agent such as sodium hydrogen sulfite, ammonium sulfite, L-ascorbic acid, and ferrous salt can be used.

Examples of the polymerization solvent include 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 graft 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 to 30 hours. After completion of the polymerization, the antibacterial phosphorus-containing resin of the present invention can be obtained by purifying to remove unreacted components and solvent, followed by drying and pulverization.

The antibacterial phosphorus-containing resin thus obtained is water-soluble, but depending on the purpose, it can be gelled by the following two methods (crosslinking reaction) to be converted into a superabsorbent resin. That is, the water-soluble antibacterial phosphorus-containing resin can be made into a highly water-absorbent resin by heat treatment or by a crosslinking reaction treatment using a crosslinking agent.

The heat treatment can be carried out at 100 to 140 ° C., preferably around 120 ° C. for 4 to 12 hours, preferably 6 to 10 hours. In addition, the crosslinking reaction treatment using a crosslinking agent is carried out by adding a crosslinking agent such as glutaraldehyde, methylenebisacrylamide, methylenebismethacrylamide, methylenedimethacrylate, etc. to the liquid obtained by adding the antibacterial phosphorus-containing resin to the solvent as described above. For 0.
It is carried out by adding about 5 to 20% by weight, preferably about 1 to 10% by weight, and carrying out a crosslinking reaction at room temperature or with heating. Further, as another gelation method of the present invention, a crosslinking reaction treatment may be performed on the graft polymer. That is, a cross-linking agent such as methylenebisacrylamide is present when graft-copolymerizing two kinds of monomer components of alkyl vinyl benzyl phosphonium halide and acrylamide to polyvinyl alcohol, and directly gels in one step to obtain a water-absorbing resin. can do. Then, it can be desolvated by a known means, dried, and pulverized to obtain a product. Further, the copolymerized water-soluble resin that has not undergone the crosslinking reaction can be subjected to a purification treatment by forming a precipitate from the aqueous solution thereof, if necessary. Next, the obtained purified solution has a feature that it can be easily formed into a film or a fibrous shape, and then can be insolubilized (gelated).

The thus obtained antibacterial phosphorus-containing resin of the present invention exhibits effective antibacterial properties against various bacteria such as Escherichia coli, Staphylococcus aureus, fungi and algae. It also has extremely high stability to heat and solvents. On the other hand, the antibacterial phosphorus-containing resin of the present invention has an extremely good film-forming property because it is a graft copolymer of polyvinyl alcohol, and the superabsorbent resin obtained by gelling this resin is It has the ability to absorb and retain tens to hundreds of times its own weight of water without melting.

The anti-bacterial phosphorus-containing resin of the present invention having a high water absorption property is used to improve the water absorption rate as needed during or after the gelation treatment of the above water-soluble resin.
Attapulgite, kaolin, talc, diatomaceous earth can be added, and if necessary, various resin fillers such as organic materials such as pulp, wood powder, synthetic fiber, glass fiber, glass powder, fine silica and alumina. Inorganic substances such as apatite, zeolite, calcium silicate, 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.

Since the antibacterial phosphorus-containing resin of the present invention has a property of being water-soluble or highly water-absorbent, it may be in the form of amorphous powder, spherical granular powder, short fiber, long fiber, or It can be applied in various shapes such as non-woven fabric and film. Since the antibacterial phosphorus-containing resin of the present invention has excellent antibacterial properties, sanitary products, sanitary materials such as paper diapers, food freshness maintaining packaging materials, food / distribution drip absorbents, agricultural / horticultural soil water retention agents It can be used in a wide range of fields such as ship bottom antifouling paints, super absorbent fibers, anti-condensation materials, and highly permeable separation membranes. At the same time, antistatic property, flame retardancy, and antifouling property can be imparted.

[0036]

The basic skeleton of the antibacterial phosphorus-containing resin of the present invention is shown in FIG. In this example, X ⁻ is Cl ⁻ .

[0037]

The present invention will be described below with reference to examples. An example is shown in which the weight ratio of the monomer to the polyvinyl alcohol (PVA) having a synthetic polymerization degree of 2600 of the antibacterial phosphorus-containing resin is 1:10 and the graft polymerization is performed. That is, 0.30 g of PVA was dissolved by heating in 30 ml of dimethyl sulfoxide (DMSO). Furthermore, acrylamide (AAm) and four kinds of alkylvinylbenzylphosphonium halides (hereinafter T
RVB), that is, triethylvinylbenzylphosphonium chloride (hereinafter TEVB), tributylvinylbenzylphosphonium chloride (hereinafter TBVB), trihexylvinylbenzylphosphonium chloride (hereinafter THVB) and trioctylvinylbenzylphosphonium chloride (hereinafter referred to as THVB). TOVB) was precisely weighed at a predetermined charge weight ratio of 3.0 g and dissolved in the solution.

The solution was transferred to a polymerization test tube, 30 mg of potassium persulfate (KPS) was added as a graft polymerization initiator, and the atmosphere was replaced with nitrogen in a water bath for 1 hour. Then, after solidifying and sealing in a dry ice-methanol bath, the reaction temperature is 40 ° C.
Polymerization was performed while shaking at 20 ° C. for 20 hours. The obtained copolymer was precipitated in acetone and then dissolved in DMSO while heating. This operation was repeated twice and unreacted AA
m, DMSO etc. of the solvent are removed, and the copolymer is dried to
Various PVA-g-AAm-TRVB copolymers were obtained.
Various copolymers thus obtained are used in the following examples, and the compounding ratio of each component and the phosphorus content of the obtained copolymer are shown in Table 1.

Incidentally, 0.2 g of each of the copolymers obtained in the following examples was sampled, added to 30 ml of pure water, and stirred at room temperature. All were found to be completely water-soluble resins. Admitted.

[0040]

[Table 1]

Of the PVA-g-AAm-TRVB copolymer
Gelation (Part 1, heat treatment) The water-soluble antibacterial phosphorus-containing resin of the present invention obtained above was gelated by heat treatment (annealing), and its physical properties were examined as follows. That is: Of the monomer components, the water absorption amount of the resin when the above copolymer samples having different TRVB were heat treated at 120 ° C. for 8 hours (g of water absorbed in 1 g of the copolymer, and the results are shown in FIG. 2). The water absorption amount of the resin when the heat treatment time is kept constant at 10 hours for each copolymer sample and the heat treatment temperature is variously changed (the results are shown in FIGS. 3 to 8); The water absorption of the resin when the heating temperature was kept constant at 120 ° C. and the heating time was variously changed (results are shown in FIGS. 9 to 12); the heating temperature was changed for copolymer samples having various phosphonium groups. The amount of water absorbed by the resin when the temperature was 120 ° C. and the heat treatment time was constant at 8 hours (the results are shown in FIG.
~ 14)); for copolymer samples having various phosphonium groups and having various TRVB contents, the heat treatment temperature is 120 ° C.
And the water absorption of the resin when the heat treatment time was kept constant at 8 hours (the results are shown in FIG. 15); for the copolymer samples having various phosphonium groups and having various TRVB contents, the heat treatment temperature To 120 ° C
And deionized water of the resin and the water absorption amount of 0.09 wt% or 0.9 wt% sodium chloride aqueous solution when the heat treatment time was kept constant for 8 hours (the results are shown in FIGS.
Shown).

Of the PVA-g-AAm-TRVB copolymer
Gelation (Part 2, Treatment with Crosslinking Agent) The water-soluble antibacterial phosphorus-containing resin of the present invention obtained above is
Gelation was performed by treatment with a crosslinking agent, and its physical properties were examined.
First, samples of various water-soluble phosphorus-containing resins [PVA-g-
0.3 g of AAm-TBVB (1: 6: 4)] was immersed in 30 ml of an aqueous solution of glutaraldehyde (GA) having different concentrations,
A crosslinking reaction was performed at room temperature for 1 hour to form a gel. Then, various resins were obtained after purification by a conventional method.
The water absorption of this resin was measured. The results are shown in FIG.

Measurement of water absorption amount The above water absorption amount was measured as follows. The synthesized antibacterial phosphorus-containing resin (sample) of the present invention is placed in a non-woven bag and immersed in an excess of ion-exchanged water or sodium chloride aqueous solution with respect to the sample. 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 is sufficient for the water absorption amount to be saturated. This formula means g of liquid absorbed per g of resin.

[0044]

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

Next, the above experiment and the result thereof will be described in detail. Of the monomer components, the copolymer samples having different TRVB were heat-treated at 120 ° C. for 8 hours, and the water absorption amount of the resin was measured. It can be seen that it exhibited water absorption.

With respect to each copolymer sample, the water absorption amount of the resin was measured when the heat treatment time was kept constant at 10 hours and the heat treatment temperature was variously changed. It can be seen that under the heating condition of time, good water absorption is exhibited.

With respect to each copolymer sample, the water absorption amount of the resin was measured when the heat treatment temperature was kept constant at 120 ° C. and the heat treatment time was variously changed. As a result, the heat treatment time of about 6 to 10 hours was good. It turns out to bring results.

With respect to the copolymer samples having various phosphonium groups, the water absorption amount of the resin was measured when the heat treatment temperature was kept constant at 120 ° C. and the heat treatment time was kept at 8 hours. As a result, PVA-g-AAm- TRVB is 1:
It can be seen that at the compounding ratio of 6: 4, all the samples have good water absorption.

The results of measuring the water absorption of the resin for copolymer samples having various phosphonium groups and having various TRVB contents when the heat treatment temperature was 120 ° C. and the heat treatment time was constant at 8 hours It can be seen that, when the phosphorus content in the copolymer is 0.1 mmol or more, practically sufficient water absorption is exhibited.

For copolymer samples with different phosphonium groups and different TRVB contents, deionized water of the resin at constant heat treatment temperature of 120 ° C. and heat treatment time of 8 hours, and 0 As a result of measuring the water absorption amount of the 0.09% by weight or 0.9% by weight sodium chloride aqueous solution, water absorption to the sodium chloride aqueous solution was recognized in all the samples.

As a sample for measuring the antibacterial activity of the antibacterial phosphorus-containing resin, the PVA-g-A obtained in the above example was used.
Am-THVB water-soluble copolymer was added at 130 ° C for 2
What was heat-treated for 0 hours or what was cross-linked with glutaraldehyde as a cross-linking agent was used. As a representative of Gram-positive bacteria, S. aureus I
FO13276 was used in this test to prepare a bacterial suspension (ion-exchanged water and 0.9 wt% NaCl aqueous solution) having a predetermined number of bacteria (60 ml). A sample is added to this bacterial suspension to 0.0
5 g was added and shaken at 30 ° C. for 6 hours, and the number of remaining viable cells was examined. The number of remaining viable bacteria is 1 ml of bacterial suspension in 9 ml of sterile water.
, 10-fold dilution (if necessary, several steps dilution), 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 a colony The number was measured and calculated by the following formula.

[0052]

[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 FIGS. From these results, it was confirmed that the highly water-absorbent type antibacterial phosphorus-containing resin of the present invention clearly exhibits excellent antibacterial properties. This fact indicates that the non-gelling water-soluble type antibacterial phosphorus-containing polymer, which is its precursor, has a better antibacterial action than the fact that it is easy to contact with bacterial cells. it can.

[0054]

INDUSTRIAL APPLICABILITY The present invention provides an antibacterial phosphorus-containing resin having excellent antibacterial properties, water solubility or high water absorption, which is substantially free from bacterial contamination, and a method for producing the same.
Due to this high functionality, it can be expected to be used for various applications.

[Brief description of the drawings]

FIG. 1 is a view showing a basic skeleton of an antibacterial phosphorus-containing resin of the present invention.

FIG. 2 Among the monomer components, the above copolymer samples having different TRVB (PVA-g-AAm-TRVB (1: 6:
It is a figure which shows the water absorption amount time dependence of resin when 4) a copolymer) is heat-treated at 120 degreeC for 8 hours.

FIG. 3 is a diagram showing the water absorption amount of a PVA-g-AAm-TEVB copolymer that was heat-treated at various temperatures for 10 hours.

FIG. 4 is a diagram showing the water absorption of a PVA-g-AAm-TBVB copolymer that was heat-treated at various temperatures for 10 hours.

FIG. 5 is a diagram showing the water absorption amount of a PVA-g-AAm-THVB copolymer that was heat-treated at various temperatures for 10 hours.

FIG. 6 is a view showing the water absorption amount of a PVA-g-AAm-TOVB copolymer which was heat-treated at various temperatures for 10 hours.

FIG. 7 is a diagram showing the water absorption of a PVA-g-AAm-TRVB (1: 9: 1) copolymer that was heat-treated at various temperatures for 10 hours.

FIG. 8 is a diagram showing the water absorption amount of a PVA-g-AAm-TRVB copolymer that was heat-treated at various temperatures for 10 hours.

FIG. 9 is a diagram showing water absorption of PVA-g-AAm-TEVB copolymers obtained by keeping the temperature constant at 120 ° C. and changing the heat treatment time.

FIG. 10 is a diagram showing the amount of water absorption of a PVA-g-AAm-TBVB copolymer obtained by keeping the temperature constant at 120 ° C. and changing the heat treatment time.

FIG. 11 is a diagram showing the amount of water absorption of a PVA-g-AAm-THVB copolymer obtained by keeping the temperature constant at 120 ° C. and changing the heat treatment time.

FIG. 12 is a view showing a water absorption amount of a PVA-g-AAm-TOVB copolymer obtained by keeping the temperature constant at 120 ° C. and changing a heat treatment time.

FIG. 13: PVA obtained at a heat treatment temperature of 120 ° C.
It is a figure which shows the water absorption of the -g-AAm-TRVB (1: 9: 1) copolymer.

FIG. 14: PVA obtained at a heat treatment temperature of 120 ° C.
It is a figure which shows the water absorption of the -g-AAm-TRVB (1: 6: 4) copolymer.

FIG. 15: Heat-treated PVA-g-A with different TRVB contents
It is a figure which shows the water absorption of Am-TRVB (heat treatment temperature condition 120 degreeC, 8 hours).

FIG. 16: Heat-treated PVA-g-A with different TRVB contents
It is a figure which shows the water absorption amount in deionized water and sodium chloride aqueous solution of Am-TEVB (heat treatment temperature condition 120 degreeC, 8 hours).

FIG. 17: Heat-treated PVA-g-A with different TRVB contents
It is a figure which shows the water absorption amount in deionized water and sodium chloride aqueous solution of Am-TBVB (heat treatment temperature condition 120 degreeC, 8 hours).

FIG. 18: Heat-treated PVA-g-A with different TRVB contents
It is a figure which shows the water absorption amount in deionized water and sodium chloride aqueous solution of Am-THVB (heat treatment temperature condition 120 degreeC, 8 hours).

FIG. 19: Heat-treated PVA-g-A with different TRVB contents
It is a figure which shows the water absorption amount in deionized water and sodium chloride aqueous solution of Am-TOVB (heat treatment temperature condition 120 degreeC, 8 hours).

FIG. 20. PVA-g-AAm-TBVB cross-linked with various concentrations of glutaraldehyde aqueous solution (crosslinking agent).
It is a figure which shows the water absorption of a (1: 6: 4) copolymer.

FIG. 21: Heat treatment PVA-g-AAm-THVB (1:
It is a figure which shows the antibacterial activity of 9: 1).

FIG. 22: Crosslinking agent-treated PVA-g-AAm-THVB
It is a figure which shows the antibacterial activity of (1: 9: 1).

Claims (9)

[Claims] 1. Polyvinyl alcohol having 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 graft-polymerized with an alkylvinylbenzylphosphonium halide and acrylamide. An antibacterial phosphorus-containing resin, which is the obtained copolymer. 2. The antibacterial phosphorus-containing resin according to claim 1, wherein the copolymer is heat-treated or cross-linked to form a gel. 3. The alkyl vinyl benzyl phosphonium halide is selected from the group consisting of triethyl vinyl benzyl phosphonium chloride, tripropyl vinyl benzyl phosphonium chloride, tributyl vinyl benzyl phosphonium chloride, trihexyl vinyl benzyl phosphonium chloride and trioctyl vinyl benzyl phosphonium chloride. The antibacterial phosphorus-containing resin according to claim 1 or 2, which is at least one kind. 4. The antibacterial phosphorus-containing resin according to claim 2, wherein glutaraldehyde is used as a crosslinking agent in the crosslinking reaction treatment. 5. With respect to 1 part by weight of polyvinyl alcohol,
Alkyl vinyl benzyl phosphonium halide 1-5
The antibacterial phosphorus-containing resin according to claim 1 or 2, wherein 5 parts by weight and 5 to 10 parts by weight of acrylamide are used. 6. The antibacterial phosphorus-containing resin according to claim 1, wherein the phosphorus content is in the range of 0.1 to 5.0 mmol / g resin as P. 7. A polyvinyl alcohol solution having 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 after adding an alkylvinylbenzylphosphonium halide and acrylamide, A method for producing an antibacterial phosphorus-containing resin, which comprises graft-copolymerizing each of the above components in the presence of a catalyst. 8. The method for producing an antibacterial phosphorus-containing resin according to claim 7, wherein the antibacterial phosphorus-containing resin is further heat-treated or cross-linked to be gelled. 9. The method for producing an antibacterial phosphorus-containing resin according to claim 8, wherein the heat treatment temperature is in the range of 100 to 140 ° C.