JPH0717808A - Antimicrobial high polymer and its production and antimicrobial material using antimicrobial high polymer and its production - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial high polymer having excellent microorganism absorbing ability and antimicrobial performance and soluble in solvents though it is insoluble or sparingly soluble in water. CONSTITUTION:An antimicrobial high polymer consisting of a vinyl-based copolymer of the formula (R is H or 1-3C alkyl; Y is H, 1-3C alkyl, benzyl, ether, carboxyl, carboxylic acid ester or aryl; X is halogen). The copolymer is obtained by copolymerizing a vinylpyridine monomer with a monovinyl monomer and then quaternizing a pyridine group of the resultant copolymer with hydrogen halide and a ratio of the both monomers in copolymerization, i.e., a ratio of (n) to (m) in the formula is preferably (10-90) to (90-10), especially (10:90) to (50:50) and the polymerization degree is preferably >=300. The antimicrobial high polymer is applied to a substrate in form of a solvent solution or a dispersion and the coated substrate is dried to produce the objective antimicrobial material. As the substrate, a porous body having large surface area or nonwoven fabric is preferably used.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an antibacterial polymer having excellent microbial adsorption performance and antibacterial performance, which is insoluble or sparingly soluble in water, but soluble in a solvent, and a method for producing the same, and The present invention relates to an antibacterial material using an antibacterial polymer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a polymer having a microorganism adsorbing performance, there is a microorganism adsorbing resin proposed by the present applicant in JP-A-3-47536. This microbial adsorption resin has the general formula

[Chemical 5] (Wherein R ¹ is a benzyl group, a C ^{4 to} C ¹⁶ alkyl group, or a pentafluorophenylmethyl group, R ² is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, and Y is hydrogen. Atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group or an aryl group).

Further, Japanese Patent Laid-Open No. 3-174419 proposes a microbial adsorbent using the above-mentioned microbial adsorbent resin and adhering this resin to a porous body.

These JP-A-3-47536 and JP-A-3-47536
The microbial adsorption resin proposed in No. 174419 is
It has excellent microbial adsorption performance, and although it is insoluble or sparingly soluble in water, it has a unique property of being soluble in a solvent, so it can be attached to a porous body such as a nonwoven fabric for processing.
It has an advantage that the adsorbed area per unit weight can be increased and a microbial adsorbent having high microbial adsorption performance can be obtained. Further, since the microorganism adsorbing resin can adsorb microorganisms in a living state, it was extremely effective in the fields of bioreactors, biosensors and the like.

In order to remove the microorganisms adsorbed by using the microorganism adsorbent disclosed in JP-A-3-174419, the microorganism adsorbent is washed with water or air.
Remove the microorganisms on the adsorbent to the outside of the microbial adsorbent, or
Alternatively, it is necessary to attach a bactericidal agent to a microbial adsorbent as disclosed in JP-A-4-9304 and take measures to sterilize the adsorbed microorganism by the action of the bactericidal agent.

However, in the case of the method of removing the microorganisms on the adsorbent from the system of the microorganism adsorbent by washing the adsorbent with water or air, it takes time and the microorganisms on the adsorbent are completely removed. There was a problem that I could not do it. Further, in the microbial adsorbent having a bactericidal agent attached together with the microbial adsorbent resin of JP-A-4-9304, although it has the advantage that it can adsorb microorganisms on the adsorbent and sterilize it, For its production, a disinfectant attachment process had to be carried out separately from the process for producing the microorganism adsorbent. Further, in the disinfecting agent adhesion processing, it is difficult to match the adhering portion of the microbial adsorbent resin and the adhering portion of the bactericide, and the portion exhibiting the microbial adsorbing performance and the portion sterilizing the microorganisms are separated from each other. In some cases, adsorption and sterilization effects could not be obtained.

The present invention has been made in view of the above problems, and has excellent microbial adsorption performance and antibacterial performance, and is insoluble or poorly soluble in water but soluble in a solvent. It is an object of the present invention to provide a functional polymer, a method for producing the same, an antibacterial material using the antibacterial polymer, and a method for producing the same.

[0008]

In order to achieve the above object, the invention according to claim 1 has the general formula

[Chemical 6] (Wherein R is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic ester The main point is an antibacterial polymer composed of a vinyl-based copolymer (hereinafter referred to simply as a vinyl-based copolymer) represented by a group or an aryl group).

According to the invention of claim 2, n: m in the general formula
The gist is an antibacterial polymer characterized by a ratio of 10:90 to 90:10.

According to a third aspect of the invention, after copolymerization using a vinylpyridine monomer and a monovinyl monomer,
The gist is a method for producing an antibacterial polymer characterized by quaternizing a pyridine group with hydrohalic acid.

The fourth aspect of the invention has as its gist an antibacterial material characterized in that an antibacterial polymer composed of a vinyl-type copolymer is attached to a substrate.

The invention of claim 5 has as its gist an antibacterial material characterized in that an antibacterial polymer is attached to a porous substrate.

The invention of claim 6 has as its gist an antibacterial material characterized in that an antibacterial polymer is attached to a nonwoven fabric.

The present invention has as its gist a method for producing an antibacterial material, which comprises applying an antibacterial polymer to a substrate in the form of a solvent solution and drying the substrate.

The gist of the invention of claim 8 is to provide a method for producing an antibacterial material, which comprises applying an antibacterial polymer in the form of a dispersion to a substrate and then drying.

The antibacterial polymer of the present invention comprises a vinyl-based copolymer obtained by copolymerizing 4-vinylpyridine with a monovinyl monomer and then reacting with a hydrohalic acid such as hydrochloric acid or hydrobromic acid. It will be. This vinyl-based copolymer is a conventionally known crosslinked polyvinylpyridinium halide (described in Japanese Patent Publication No. 62-41641).
It has the same excellent microbial adsorption performance as, and also has excellent antibacterial performance. Therefore, microorganisms can be efficiently adsorbed and sterilized without being used in combination with an antibacterial agent. The vinyl copolymer is a random copolymer or a block copolymer.

Examples of monovinyl monomers used for copolymerization include monoolefins such as ethylene, propylene and butene, styrene, vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, aliphatic vinyl ester, acrylonitrile and these. However, the present invention is not limited to this, and various compounds can be used alone or in combination. However, the use of a monovinyl monomer having a highly hydrophilic functional group is not desirable because the resulting copolymer becomes water-soluble depending on the degree of polymerization.

The ratio of 4-vinylpyridine to monovinyl monomer, that is, the ratio of n: m, varies depending on the type of monovinyl monomer used and the degree of polymerization, but is generally 10:90 to 90:10, More preferably 1
It is preferably in the range of 0:90 to 50:50. Because, if the proportion of 4-vinylpyridine is less than this range, sufficient microbial adsorption performance and antibacterial performance cannot be obtained,
This is because the water-insolubility becomes high, and if it exceeds this range, the vinyl-based copolymer obtained has high microbial adsorption performance and antibacterial performance, but high water solubility. The vinyl-based copolymer preferably has a degree of polymerization of at least 300 or more. When the degree of polymerization is lower than this, the obtained copolymer has high water solubility.

A copolymer of a monovinyl monomer and 4-vinylpyridine is reacted with a hydrohalic acid such as hydrochloric acid or hydrobromic acid to quaternize the pyridine group in the copolymer and represented by the following formula. To form a pyridinium group.

[0020]

[Chemical 7] It is considered that this pyridinium group mainly serves to adsorb microorganisms. Although this mechanism is not clear, since this pyridinium group is positively charged and the cell surface of microorganisms is generally negatively charged, electrostatic interaction is presumed to be one of the important factors. It Further, it is considered that the antibacterial performance of the antibacterial polymer is also due to the pyridinium group of the vinyl copolymer. The reason is that cations are generally known to adversely affect the growth of microorganisms, and it is considered that the microorganisms are killed or their growth is suppressed by the influence of the pyridinium group, which has a strong cation power.

Since this antibacterial polymer is insoluble or sparingly soluble in water and soluble in a solvent, it is applied to a substrate in the form of a solvent solution or dispersion and dried to obtain an antibacterial material. Can be obtained. In this case, compared to using the antibacterial polymer in the form of beads, blocks, or plates and using the polymer itself as an antibacterial material having microbial adsorption performance, the action area of the polymer is dramatically increased. It is possible to obtain an antibacterial material that can be expanded and has high microbial adsorption performance and antibacterial performance.

Next, an antibacterial material using the above antibacterial polymer will be described. This antibacterial material can be obtained by applying an antibacterial polymer to a substrate in the form of a solvent solution or dispersion as described above and drying. The application of the antibacterial polymer in the form of a solvent solution means that the vinyl-based copolymer constituting the antibacterial polymer is substantially insoluble or hardly soluble in water, such as dimethylformamide (DMF). Utilizing the property of being soluble in a solvent, it means that the above-mentioned antibacterial polymer is dissolved in a solvent to form a solution, and this solution is applied to a substrate by means such as impregnation or coating. In addition, the application of the antibacterial polymer in the form of a dispersion means that the antibacterial polymer made of a vinyl copolymer that is insoluble or sparingly soluble in water is dispersed in a liquid such as water or alcohol. This is to prepare a dispersion liquid and apply the dispersion liquid to a substrate by means such as impregnation or coating. By applying the antibacterial polymer to the substrate in this manner and drying it, the solvent or dispersion medium was removed, and the antibacterial polymer consisting of the vinyl copolymer was thinly and uniformly attached to the substrate. It is possible to obtain an antibacterial material.

As the base material to which the antibacterial polymer is attached,
A porous material such as a non-woven fabric, a woven material, a knitted material, a paper, a foam, a ceramics sintered body, or a particulate material of organic, inorganic, or metal, a honeycomb, a structure such as a multi-stage plate can be used. Among them, since the porous body has a large surface area, a large amount of antibacterial polymer can be attached by that amount, and an antibacterial material having high microbial adsorption performance and antibacterial performance can be obtained, which is preferable. Among them, the nonwoven fabric is desirable in that it has a three-dimensional structure, has a large surface area, and has a low pressure loss. In addition, when the antibacterial polymer is dissolved in an organic solvent and applied, the antibacterial polymer is thinly applied to the surface of the constituent fibers of the nonwoven fabric,
An antibacterial material that can be evenly attached, dramatically increases the surface area per unit weight of the antibacterial polymer, and increases the active area of the antibacterial polymer, and has higher microbial adsorption performance and antibacterial performance. Can be obtained. When a nonwoven fabric is used as the base material, the density of the nonwoven fabric is controlled even when a large amount of microorganisms are adsorbed, so that voids can be secured and a structure that does not cause clogging can be obtained.

The amount of the antibacterial polymer adhered to the substrate is not particularly limited, but the amount adhered is 0.01 to 30 with respect to the substrate.
Those in the range of wt% have high microbial adsorption performance and antibacterial performance, and are economical. When a large amount of the antibacterial polymer exceeding 30 wt% is attached, the effect is not improved even if the amount of the antibacterial polymer used is increased, which is uneconomical.

The microorganism in the present invention refers to bacteria, fungi, algae, viruses and the like.

[0026]

EXAMPLES The present invention will be described in detail below with reference to examples. Example Using 4-vinylpyridine and styrene monomers distilled under reduced pressure, 4-vinylpyridine and styrene were mixed at a ratio of 4-vinylpyridine / styrene = 1 / 2.75 mol, and a radical polymerization initiator was added thereto. Azobis-isobutyronitrile (AIBN) is added as AIBN / (4-vinylpyridine + styrene) = 0.2 mol%, and alcohol is further added to 4-vinylpyridine + styrene = 54 wt%.
The resulting alcoholic solution was subjected to copolymerization at 80 ° C. for 6 hours in a nitrogen atmosphere, and then a hydroquinone polymerization inhibitor equimolar to AIBN was added to terminate the polymerization.

Then, a commercially available 36% hydrochloric acid aqueous solution was added to this copolymer solution at a ratio of 4-vinylpyridine / hydrochloric acid = 1/1, and quaternization treatment was carried out at 80 ° C. for 6 hours. The concentration of the obtained vinyl-based copolymer is 25% by weight.
The mixture was diluted with alcohol until it became, and then added to 12 times the amount of water to prepare a milk-colored suspension liquid having a copolymer concentration of 2% by weight.

Hydrochloric acid / copolymer =
5-12% hydrochloric acid aqueous solution was added at a ratio of 0.78 g / g,
The copolymer was floated. The lower layer light yellow transparent liquid was removed, and the light yellow copolymer was washed with water for 5 minutes to obtain a white solid. This was vacuum dried at 80 ° C. to obtain an ultrathin yellow solid vinyl copolymer with a yield of 41%.

Comparative Example A brown upper layer obtained by adding an equal amount of 5% sodium hydroxide aqueous solution to a mixed solution of styrene and 4-vinylpyridine monomer and separating the mixture was further added with an equal amount of water to obtain a brown upper layer. Using liquid 4-vinylpyridine / styrene monomer,
Vinyl pyridine and styrene are added to 4-vinyl pyridine /
Styrene = 1 / 2.75 mol was mixed and AIBN / (4-vinylpyridine + styrene) = 0.2 mol% was added as a radical polymerization initiator to this, and alcohol was further added to 4-vinylpyridine. + Styrene = 54
As a weight% alcohol solution, under a nitrogen atmosphere, 80
After copolymerization at 6 ° C. for 6 hours, a polymerization inhibitor was added by adding a hydroquinone polymerization inhibitor in an equimolar amount to AIBN.

Then, benzyl chloride was added to this copolymer solution at a ratio of 4-vinylpyridine / benzylic acid chloride = 1 / 1.2 mol and subjected to a quaternization treatment at 80 ° C. for 6 hours. The obtained vinyl-based copolymer was diluted with alcohol until its concentration became 20% by weight, and the diluted vinyl-copolymer was added to 7 times the amount of water to prepare a suspension liquid.

Hydrochloric acid / copolymer =
5-12% hydrochloric acid aqueous solution was added at a ratio of 0.56 g / g,
The copolymer was allowed to settle. The supernatant was removed, the copolymer was washed with water, and vacuum dried at 80 ° C. to obtain a light yellow solid copolymer with a yield of 57%.

Regarding the vinyl-based copolymer (1) of the example and the copolymer (2) of the comparative example, alcohol solubility, DM
F solubility, water solubility, decomposition temperature, and sterilization rate were measured. The results are shown in Table 1. The decomposition temperature in Table 1 is TG-DT.
It was determined by A measurement. Similarly, the sterilization rate A (%) in Table 1 is
This is a value obtained by a viable cell count method using rayon nonwoven fabric (WE, RX-9450) impregnated with an alcohol solution having a copolymer concentration of 1% by weight, which was contacted with an Escherichia coli solution for 2 hours. Similarly, the sterilization rate B (%) in Table 1 is a numerical value determined by the viable cell count method when the contact time is 4 hours. Further, the water solubility of Comparative Examples in Table 1 is 100 g in water (room temperature, 27 days) = 0.031 g, and the water solubility of Examples is 100 g in water (room temperature, 27 days) =
It was 1.048 g. (Below margin)

[0033]

[Table 1]

Antibacterial Property Test 1 Next, an antibacterial property test was conducted on the copolymers of the above Examples and Comparative Examples and the nonwoven fabrics to which these copolymers were attached. About 7 × 10 ⁸ cells / mole of Escherichia coli was transferred to 0.2 ml of a 3.85 wt% SCD agar plate medium,
The cells were cultured at 30 ° C for 1 day. Also, 1% by weight or 15% by weight of the copolymer of Example was added to 0.85% by weight of physiological saline, and 1% by weight or 15% by weight of the copolymer of Comparative Example was also added. After being placed and stirred for 1 day, the swollen copolymer was transferred onto the agar medium and cultured at 30 ° C. The presence or absence of antibacterial properties was examined by visually observing changes in the samples after 1 day and 13 days. The results are shown in Table 2.

Similarly, using the copolymers of the above-mentioned Examples and Comparative Examples, alcohol was added to them to prepare an alcohol solution having a copolymer concentration of 1% by weight or 15% by weight, which was then made into a rayon nonwoven fabric (RX-9450, WE). ) And dried, the white non-woven fabric was placed on the agar medium and examined for antibacterial properties. The results are shown in Table 2. (Below margin)

[0036]

[Table 2]

From Table 2, the contact surface of the copolymer or the non-woven fabric of the comparative example was discolored, but it was not possible to determine whether this phenomenon was due to the growth of bacteria or the lysis phenomenon. On the other hand, since the contact surface of the copolymer or the nonwoven fabric of the Example after 1 day and the nonwoven fabric after 13 days were not discolored, it is considered that there was no growth of bacteria, and the copolymer of the Example had antibacterial properties. it seems to do. In addition, discoloration occurred in the copolymer of the Example after 13 days. This is because although the amount of the copolymer eluted was extremely small, the number of bacteria was too large and the limit of antibacterial performance was exceeded. It was unclear whether it was because of this, or whether the lytic phenomenon occurred.

Antibacterial property test 2 Using the sample used in the above antibacterial property test, lightly wipe the surface of the copolymer or nonwoven fabric of each of the examples and comparative examples and the agar in contact with them with a sterilized platinum loop, and SCD After transplanting to an agar medium and culturing at 30 ° C. for 1 day or 3 days, the presence or absence of propagation of Escherichia coli was observed, and the presence or absence of antibacterial property was examined. The results are shown in Table 3.

[0039]

[Table 3] The presence or absence of antibacterial properties is determined by the presence or absence of Escherichia coli growth visually. No growth:-, Growth: + (the number of colonies is tens)

From Table 3, it is suggested that the copolymers of Comparative Examples have no antibacterial properties, whereas the copolymers of Examples have antibacterial properties.

[0041]

According to the present invention, the above-mentioned structure is provided.
Since the above-mentioned antibacterial polymer has excellent microbial adsorption performance and antibacterial performance, it is not necessary to use a bactericide in combination, and microorganisms can be adsorbed and sterilized efficiently.

Further, since this antibacterial polymer is insoluble or sparingly soluble in water, it does not elute in the liquid to be treated even when used in an aqueous system, and it does not adversely affect humans or the environment and is safe. Is. In addition, since this antibacterial polymer is soluble in a solvent, it can be applied to a substrate in the form of a solvent solution or dispersion, and an antibacterial having a high microbial adsorption performance and antibacterial performance. The material can be obtained.

The antibacterial polymer according to claim 2 has a ratio of vinylpyridine monomer to monovinyl monomer in the molecule of 10:90 to 90:10. Antibacterial performance can be secured.

In the method for producing an antibacterial polymer according to claim 3, the pyridine group of the copolymer is quaternized with hydrohalic acid to obtain excellent antibacterial properties and excellent antibacterial properties. The molecule can be obtained, and it is not necessary to provide a special process for imparting antibacterial properties to the polymer production process.

In the antibacterial material according to claim 4, since the antibacterial polymer is adhered to the substrate, the antibacterial polymer is molded into a bead shape, a block shape or a plate shape, and the polymer itself is formed. Compared with the use as an antibacterial material, the polymer has a large active area and has high microbial adsorption performance and high antibacterial performance.

In the antibacterial material according to claim 5, since the antibacterial polymer adheres to the porous base material having a large surface area, the active area of the antibacterial polymer adhering to the base material also increases, It has higher microbial adsorption performance and antibacterial performance.

In the antibacterial material according to claim 6, since a nonwoven fabric having a three-dimensional structure, a large surface area and a low pressure loss is used as the base material, the active area per unit weight of the antibacterial polymer is Will be significantly larger and will have higher microbial adsorption and antibacterial properties.

In the method for producing an antibacterial material according to claim 7, since the antibacterial polymer is applied to the substrate in the form of a solvent solution and dried, the antibacterial polymer is applied thinly and uniformly to the substrate. As a result, an antibacterial material having higher microbial adsorption performance and antibacterial performance can be obtained.

In the method for producing an antibacterial material according to claim 8, since the antibacterial polymer is applied to the substrate in the form of a dispersion and dried, the antibacterial polymer is applied thinly and uniformly to the substrate. As a result, an antibacterial material having higher microbial adsorption performance and antibacterial performance can be obtained.

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Claims (8)

[Claims] 1. A general formula: (Wherein R is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic ester Group or aryl group), which is an antibacterial polymer composed of a vinyl-based copolymer. 2. The ratio of n: m in the general formula is from 10:90.
The antibacterial polymer according to claim 1, which is 90:10. 3. A method for producing an antibacterial polymer, which comprises copolymerizing a vinylpyridine monomer and a monovinyl monomer and then quaternizing the pyridine group with hydrohalic acid. 4. A general formula: (Wherein R is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic ester An antibacterial polymer having an antibacterial polymer composed of a vinyl-based copolymer represented by a group or an aryl group) attached to a substrate. 5. The antibacterial material according to claim 4, wherein the antibacterial polymer is attached to a porous substrate. 6. The antibacterial material according to claim 4, wherein the antibacterial polymer is attached to a nonwoven fabric. 7. A chemical formula: (Wherein R is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic ester Group or an aryl group), and a method for producing an antibacterial material, which comprises applying an antibacterial polymer composed of a vinyl-based copolymer represented by a group or an aryl group) to a base material in the form of a solvent solution and drying. 8. embedded image (Wherein R is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, a C _{1 to} C ₃ alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic ester Group or aryl group), and a method for producing an antibacterial material, which comprises applying an antibacterial polymer composed of a vinyl-based copolymer represented by the formula (1) or an aryl group) to a substrate in the form of a dispersion and then drying.