JPH09194629A - Antibacterial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial compsn. which has a good antibacterial activity, can maintain the activity for a long period of time, and has a high safety and excellent mechanical properties by incorporating a particular phosphonium salt compd. into a synthetic polymer. SOLUTION: This compsn. comprises a synthetic polymer and a phosphonium salt compd. incorporated in a free form into the synthetic polymer. The phosphonium salt compd. has a structure represented by the formula (wherein R1 and R2 represent each a 3-18C alkyl and R3 to R6 represent each a 1-18C alkyl, a 7-20C aralkyl with at least one of R3 to R6 representing a 6C or higher alkyl. The amt. of the phosphonium salt compd. added to the synthetic polymer is generally 0.05 to 25 pts.wt. based on 100 pts.wt. base polymer. The addition of a plasticizer to the synthetic polymer is pref. because, by virtue of a synergistic effect, a satisfactory effect can be attained by the addition of a small amt. of an antibacterial agent. Polyvinyl chloride and polyvinylidene chloride are most pref. as the synthetic polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial composition, and by using a phosphonium salt compound in a synthetic polymer, it is possible to impart a durable antibacterial property to a synthetic polymer.
It is given together with plasticity. INDUSTRIAL APPLICABILITY The antibacterial composition of the present invention can be widely used in the fields of health, hygiene and medical care such as food packaging films, various antibacterial goods, various therapeutic catheters and prevention of nosocomial infections. Is.

[0002]

2. Description of the Related Art Conventionally, various types of antibacterial agents have been used in many fields for the purpose of preventing bacterial infection and putrefaction and protecting them from harmful microorganisms. In this case, the ideal requirements for the antibacterial agent are: Broad antibacterial spectrum 2. High sterilization rate and long-term durability 3. 3. No inhibition of antibacterial activity by organic compounds 4. High chemical stability 5. 5. Low toxicity and low irritation to animal cells Easy to use 7. Colorless and odorless 8. Although it is important to have low price, it is the current situation that an antibacterial agent that can satisfy all of these has not yet been developed.

Of these required characteristics, there are often problems with durability. This is because the monomer-type antibacterial agent is generally highly soluble in water or an organic solvent and is eluted during use to deactivate its antibacterial property. Therefore, recent attempts to improve antibacterial agents have been widely attempted to immobilize the antibacterial agent on the main chain or side chain of the polymer. As the immobilized antibacterial agent, it has been reported that an antibacterial component is pendantly immobilized on a polymer chain such as polyester or polyvinyl. For example, an alkylpyridinium salt or an alkyldimethylbenzylammonium salt fixed to a polyvinyl chain, a polyacrylate or polymethacrylate in which a piguanite is fixed to a side chain, and a quaternary ammonium salt is incorporated into the main chain. Reported polyamides and the like. However, these attempts also have problems in terms of antibacterial effect, durability, toxicity and the like.

On the other hand, phosphonium salt compounds, like various nitrogen-containing compounds, are often used as compounds having a broad antibacterial spectrum against bacteria, fungi and algae. For example, JP-A-57-204286 discloses control of algae reproduction by adding a quaternary phosphonium chloride to water.
Describes an antibacterial agent mixture relating to the combined use of a quaternary ammonium compound and a quaternary phosphonium salt.
3596 describes that certain novel thiazol-4-ylphosphonium salts have bactericidal activity. Further, JP-A-2-24090 discloses that a water-soluble trihydroxymethylphosphonium salt is used as a biocide. There is a description of the composition. However, the usage of these phosphonium salts is only dissolved in water and other solvents to be used in the fields of water treatment, agricultural applications, etc., and there is no way to make the polymer material itself antibacterial. Not listed. Japanese Patent Laid-Open No. 5-310820 discloses an ion of a sulfonic acid having an unsaturated bond and a phosphonium salt as an antibacterial material mainly composed of a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group. A method for obtaining antibacterial properties by copolymerizing a bound complex with a vinyl compound, a method for copolymerizing a complex of sulfoisophthalic acid and phosphonium base in polyester to obtain antibacterial properties, and the like are disclosed. However, when copolymerized in polyester,
The antibacterial effect is greatly reduced, probably because the desorption rate of phosphonium ions is very slow. That is, regarding the addition of the antibacterial agent to the synthetic polymer, when the antibacterial agent monomer as conventionally known is simply added by kneading or the like, the antibacterial agent is easily eluted and the antibacterial effect is obtained in a short period of time. At the same time as it disappears, toxicity due to elution of the antibacterial agent becomes a problem. On the other hand, when the antibacterial agent is immobilized on the synthetic polymer, elution of the antibacterial agent can be surely prevented, but there are many drawbacks such that the antibacterial effect is remarkably reduced. The current situation is that it has not yet arrived.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its purpose is not only to have good antibacterial properties, but also to maintain its effects for a long time and also to ensure safety. It is an object of the present invention to provide a synthetic polymer composition having high antibacterial properties, which has high mechanical properties.

[0006]

Means for Solving the Problems As a means for solving the above problems, an antibacterial composition is characterized in that a synthetic polymer contains a phosphonium salt compound in a free state. The above phosphonium salt compound is
And the synthetic polymer is polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyester or polyamide. Furthermore, a plasticizer is added to the above synthetic polymer, in particular, the synthetic polymer is polyvinyl chloride or polyvinylidene chloride, and the plasticizer is a phthalate ester plasticizer or an aliphatic polyester plasticizer. It is characterized by being an agent.

The antibacterial composition of the present invention is obtained by incorporating a phosphonium salt compound into a synthetic polymer in a free state. In the present invention, inclusion in the free state does not mean that the phosphonium salt compound is immobilized on the synthetic polymer by a chemical reaction, bonding, copolymerization or the like, and the phosphonium salt compound is in a free state. In the state of coexistence. Specific examples of the phosphonium salt compound represented by Chemical Formula 1 in the synthetic polymer include linear or branched C 3-18 alkyl groups for R ₁ and R ₂ on the sulfonic acid ester side, and are preferable. Is 4 to 15, more preferably 5 to 1
2. Alkyl group forming an ester (R ₁ , R
_{If 2} ) deviates above or below this chain length, the plasticizing effect of the antibacterial agent on the synthetic polymer will decrease, and as a result, it will be more likely to elute under water washing or other conditions, and the antibacterial effect will be maintained for a long time. At the same time, it becomes difficult, and the point of toxicity due to elution becomes a problem. On the other hand, regarding R ₃ , R ₄ , R ₅ and R ₆ which are alkyl groups on the phosphonium salt side, a linear or branched alkyl group having 1 to 20 carbon atoms or 7 carbon atoms
To 20 aralkyl groups, at least one of which has 6 or more carbon atoms, preferably 10 or more carbon atoms, and more preferably 12 or more carbon atoms. It may also be an aralkyl group such as a benzyl group. R ₃ , R ₄ , R
₅ and R ₆ may be the same or different.

The addition amount of the phosphonium salt of the above chemical formula 1 to the synthetic polymer is 20 to 7000 ppm in terms of P (phosphorus atom) content, and the addition amount in the weight ratio of the whole compound is Generally, the amount is 0.05 to 25 parts by weight with respect to 100 parts by weight of the base polymer (hereinafter, the number of added parts by weight per 100 parts by weight of the base polymer is abbreviated as phr). Yes, preferably 0.2-2
0 phr, more preferably 0.5 to 15 phr.
If the addition amount of the antibacterial agent of the above chemical formula 1 is less than the preferable range, sufficient antibacterial property cannot be exhibited, and conversely, if it exceeds the preferable range, the antibacterial agent is easily bled out on the surface, and in terms of safety. The problem arises.

Examples of synthetic polymers to which the antibacterial agent of Chemical Formula 1 (hereinafter abbreviated as antibacterial agent) is added include polyvinyl chloride (hereinafter abbreviated as PVC), polyvinylidene chloride,
Polyurethane, polyester, polyamide, polyethylene, polypropylene, polystyrene and polystyrene-
Examples thereof include a butadiene copolymer and the like, but the invention is not particularly limited to these and can be applied to synthetic polymers that will be developed in the future. Among the above synthetic polymers, PVC
And a composition in which a necessary amount of an antibacterial agent is added to polyvinylidene chloride is most preferable. The antibacterial properties of a composition obtained by adding an antibacterial agent to a synthetic polymer (hereinafter abbreviated as composition) have little effect when an antibacterial agent is added alone, and an appropriate plasticizer that reduces the crystallinity of the synthetic polymer is added at the same time. By doing so, a synergistic effect is exerted, and it becomes possible to exert a sufficient antibacterial effect by adding a small amount of the antibacterial agent.

As the plasticizer exhibiting a synergistic effect with the above-mentioned antibacterial agent, a polymer having a high compatibility with each synthetic polymer and an effect of lowering the crystallinity of the polymer can be used. Examples of the plasticizer used in the case of PVC and vinylidene chloride, which are the most preferable compositions, are effective regardless of, for example, di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) and Examples thereof include phthalic acid ester type compounds such as di-n-octyl phthalate, and aliphatic polyesters obtained from adipic acid and a diol having 2 to 8 carbon atoms, such as di-2-ethylhexyl phthalate and diester. It is particularly preferable to use -n-octyl phthalate. The amount of these plasticizers used is 1 to 120 phr, preferably 5 to 110 phr, more preferably 10
~ 100 phr.

The mixing of these plasticizer and antibacterial agent with the synthetic polymer is carried out by dissolving a solution of the synthetic polymer, the antibacterial agent and the plasticizer in an appropriate amount in a solvent that dissolves each of them. , Pillars, tiles, etc.) and tools (urinary tract catheters, aseptic boots, films, etc.) to expose the solvent to prevent sterilization on the surface of tools and surfaces And a synthetic polymer, an antibacterial agent and a plasticizer are added to the mixture, and the mixture is stirred at a constant temperature for a constant time. (For example, in the case of PVC, a ribbon blender is used although the conditions vary greatly depending on the kneading device. In the case of 70-100 ° C
The mixture is mixed and stirred for 10 to 120 minutes) to absorb the antibacterial agent, plasticizer and various stabilizers into PVC, and then pelletized using a granulator, and the pellets are melted to give a desired form. (Film, tube, catheter, etc.), but any of these methods may be used.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial composition of the present invention is thus obtained. Although the detailed mechanism is not clear, it has excellent compatibility with synthetic polymers, especially PVC and polyvinylidene chloride, and when used in combination with a phthalate ester type plasticizer, a small amount of addition shows sufficient antibacterial properties. At the same time, P
Since the compatibility of the antibacterial agent with VC is excellent, elution is suppressed, and an antibacterial composition excellent in safety can be obtained.

By taking advantage of the characteristics of the composition having excellent antibacterial properties, low elution properties and good mechanical properties, the composition itself is molded and processed as described above to form films, tubes and various medical products. It can be used in the field where antibacterial properties are required, such as a catheter. It is also possible to impart antibacterial properties by dissolving this composition in a suitable solvent or coating solution and applying it on the surface or place where antibacterial properties are required. Specific uses of these compositions include wallpaper and flooring materials for kitchens, bathrooms, toilets, food factories and hospitals, food packaging films, and the like.
Cleaner hood, antibacterial paint, sanitary products such as diapers, masks, gazes and sanitary products by surface treatment of fibers, urinary catheters, various categories such as high calorie infusion tube -Ters, but not limited thereto.

[0014]

The present invention will be described below with reference to examples. In the examples, all parts are parts by weight. <Example 1> 5.0 parts of di-n-octyl sodium 5-sulfoisophthalate was dissolved in 200 parts of water to prepare tri-n-
A solution prepared by dissolving 4.4 parts of butyl tetradecylphosphonium chloride in 200 parts of water was added dropwise at room temperature and reacted for 1 hour. After completion of the reaction, the product was extracted with 200 ml of diethyl ether. The solvent was distilled off with an evaporator and the residue was dried to obtain 7.7 parts of a complex of phosphonium salt and di-n-octyl isophthalate (this compound is referred to as complex A).

Next, to 100 parts of PVC having a polymerization degree of 1000, 60 parts of DOP, 5 parts of epoxidized soybean oil, and complex A
2 parts and 1 part of zinc stearate and 0.5 part of calcium stearate are mixed in a ratio of 8 parts, and this mixture is steam-heated 8 inch mixin roll (roll temperature 150 to 160).
(° C) for 10 minutes to make a polyvinyl chloride composition. At this time, the polyvinyl chloride composition was drawn out from the mixin roll into a sheet shape to prepare a sheet having a thickness of 0.5 mm. The pressing conditions are a pressing temperature of 160 to 170 ° C., a pressing time of 3 minutes, and a pressure of 100 to 150 kg / cm.
² , cooling time 5 minutes and pressure 130-150 kg / cm
Done in ² . The film thus obtained is referred to as film A. Table 1 below shows the results of evaluation of the antibacterial performance and the eluate test of the film A and the film a (comparative example) obtained from the composition having the above-mentioned composition and not adding the complex A by the methods described below.

<Antibacterial test> Staphylococcus aureus solution prepared by broth solution (diluted 50 times with sterilized physiological saline solution) to about 1 × 10 ⁷ cells / ml (hereinafter, this bacterial solution is referred to as a stock solution). Call)
Was prepared. The concentration of this stock solution was measured as follows. After diluting the stock solution 10 ⁴ times, 100 μl was wound on an ordinary agar plate, and the number of colonies formed after 24 hours was counted. Assuming that the number of colonies is N, the concentration C of the stock solution is C
Is shown as C = 10 ⁴ × N / 0.1 = 10 ⁵ × N [pieces / ml]. 10 μl of this bacterial stock solution was previously added to 5 cm
Cut into 5 cm pieces, sterilized with ethylene oxide gas, dropped onto film A placed on a sterile dish, covered with a sterilized commercial food packaging wrap of the same size, covered, and incubated at 37 ° C for 24 hours. did. After culturing, the coated wrap was peeled off, and the SCDLP medium 10
The bacteria were washed out with ml, diluted 10-fold, and spread on ordinary agar medium. After 24 hours, the number of colonies of Staphylococcus aureus formed on the ordinary agar medium was counted. This colony
When the number is N ′, the number of bacteria N _a after contact with the 25 cm ² film A is given by the following equation. The concentration of the bacterium stock solution before contacting with N _a = 10 ² × N ′ film A is as described in C above, and the stock solution used was 10 μl. Therefore, the number of bacteria N _b before contacting with film A was N _b = 10. ³ × N. N _b → N on a film with a size of 25 cm ²
The change in the number of _a 's is shown in Table 1 below. The decrease in the number of bacteria by contact indicates that the antibacterial property of the film is exhibited.

<Safety test> 1.5 g of dried broth (manufactured by Nissui Pharmaceutical Co., Ltd.) was dissolved in 50 ml of distilled water with heating to 121 ° C.
Staphylococcus aureus was cultivated in a liquid medium prepared by high-pressure steam sterilization for 20 minutes, and 100 μl of a bacterial solution adjusted to have a bacterial count of 7.5 × 10 ⁸ cells / ml was used as a normal agar medium in a petri dish of 9 cm in diameter. It was sprinkled on top and applied uniformly using a Conrad stick. A circular test film with a diameter of 5 cm that had been sterilized with ethylene oxide gas in advance was affixed to the center of this agar medium, and after incubation at 37 ° C for 24 hours, the growth of the bacteria caused by the eluted antibacterial agent at the edges of the film was inhibited. The distance of the strip from the film edge was measured. The absence or very small growth inhibition zone indicates that the elution is small, the antibacterial action is specifically exerted only on the part in contact with the film, and the safety is high.

<Eluted substance test> The test film has a surface area of 1
It was shredded to be 00 cm ² and put in a 200 ml Erlenmeyer flask, 100 ml of PBS (−) was added, and the mixture was extracted at 37 ° C. for 24 hours. Using this extract, 0.01N of a blank test conducted without using a film, in accordance with the potassium permanganate reducing substance in the eluate test of the dialysis type artificial kidney device approval standard (Yakuhin 494). The difference from the consumption of the potassium permanganate solution was measured. The small difference in the amount of consumption means that the substance eluted in PBS (-) is small and the safety is high. Note that the standard value set for the potassium permanganate reducing substance, which is the approval standard for dialysis type artificial kidney device, is 1 ml or less. The PBS (−) was replaced every day, and the antibacterial properties after extraction at 37 ° C. for 14 days were also measured using the above antibacterial property test, and the durability of the antibacterial agent by elution was also tested. The test results are summarized in Table 1.

[0019]

[Table 1] N. in the table. D. Means less than 100/25 cm ² . As is clear from the results in Table 1, the examples of the present invention have excellent antibacterial properties and durability due to elution. The amount of elution is very small, indicating that it is also excellent in safety.

Example 2 Various dialkyl sodium 5-sulfoisophthalates and tributylhexadecylphosphonium chloride were reacted in the same manner as in Example 1 to give various complexes of phosphonium salts and dialkyl 5-sulfoisophthalates, that is, , The alkyl group of 5-alkyl disulfoisophthalate is a methyl group (complex B), an ethyl group (complex C) (the above comparative examples), a butyl group (complex D), a hexyl group (complex E), and a 2-ethylhexyl group ( Complex F)
(The above is the example). Films BF were obtained in the same manner as in Example 1 using the complexes BF. Table 2 shows the results of the same tests as in Example 1 using these films.

[0021]

[Table 2] N. in the table. D. Means less than 100/25 cm ² . As is clear from the results of Table 2, the examples have excellent antibacterial properties and durability, and the consumption amount of potassium permanganate is within the standard, whereas the comparative examples show a marked decrease in antibacterial properties after elution. At the same time, the consumption amount of potassium permanganate also exceeded the standard value, indicating that the antibacterial agent is more likely to be eluted than in the examples.

Example 3 0.5 part, 1.0 part, 5 parts and 10 parts of the complex A were added to 100 parts of PVC, and DOP was mixed with 30 parts of each, and the mixture was mixed with tetrahydrofuran (hereinafter THF). Abbreviated as 10% TH)
A solution F was prepared, and the solution was spread on a glass plate kept horizontally, and 10 parts of test films G to J and a complex A having a thickness of 0.5 mm were added (DOP-free) THF.
The results of the antibacterial test and the eluate test of the film K prepared from the solution are shown in Table 3.

[0023]

[Table 3] N. in the table. D. Means less than 100/25 cm ² . As is clear from the results in Table 3, Complex A
The system to which DOP and DOP were added exhibited excellent antibacterial properties and low elution properties by adding a small amount of antibacterial agent. On the other hand, the system to which DOP was not added had an antibacterial property, but its effect was significantly reduced as compared with the system containing DOP. As described above, the antibacterial agent of the present invention and DOP have a synergistic effect.
It is clear that the presence of P significantly enhances the antibacterial property.

[0024]

The antibacterial composition of the present invention comprises a base polymer.
By adding the antibacterial agent represented by Chemical Formula 1 above, the antibacterial property can be easily imparted, and its performance is maintained even after a long-term elution operation, and it is excellent in durability and at the same time safe because of its low elution property. The point of sex is also very excellent. As the base polymer in the antibacterial composition of the present invention, excellent antibacterial properties are exhibited particularly when polyvinyl chloride and polyvinylidene chloride are used. Further, when polyvinyl chloride and polyvinylidene chloride are used, co-existence of a plasticizer such as DOP can also exert an additive effect of further enhancing its antibacterial property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 75/04 NGD C08L 75/04 NGD 77/00 KLB 77/00 KLB 101/00 101/00 ( 72) Inventor Shigetsuji Ogaya Inside 1-1, Toyobo Co., Ltd. 1-1-1, Katata, Otsu City, Shiga Prefecture

Claims (5)

[Claims] 1. A synthetic polymer containing a phosphonium salt compound,
An antibacterial composition characterized by being contained in a free state. 2. The antibacterial composition according to claim 1, wherein the phosphonium salt compound is represented by the following chemical formula 1. Embedded image In the formula, R ₁ and R ₂ represent a linear or branched alkyl group having 3 to 18 carbon atoms, which is the same or different. R ₃ ,
R ₄ , R ₅ and R ₆ represent a linear or branched alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, at least one of which is an alkyl group having 6 or more carbon atoms. is there. R ₃ , R ₄ , R ₅ and R ₆ may be the same or different. 3. The antibacterial composition according to claim 1 or 2, wherein the synthetic polymer is polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyester or polyamide. 4. The antibacterial composition according to claim 1, 2 or 3, wherein a plasticizer is added to the synthetic polymer. 5. The antibacterial agent according to claim 1, 2, 3 or 4, wherein the synthetic polymer is polyvinyl chloride or polyvinylidene chloride, and the plasticizer is a phthalate ester plasticizer or an aliphatic polyester plasticizer. Sex composition.