JPH09135893A - Antibacterial material and antibacterial molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain a satisfactory antibacterial function for a long time even with a high concentration of germs by coating a medical plastic product with phenoxy resin which is obtained by substituting at least part of a hydroxyl group with a specified functional group. SOLUTION: At least a part of phenoxy resin is obtained through the reaction between bivalent phenol and epichlorohydrine is substituted with a functional group which is exhibited by a formula I (in the formula, A denotes a bonding group including ether group or ester group, and R denotes an alkylene group). In the functional group exhibited by the formula I, R preferably has a carbon number of 1 to 17 in view of the antibacterial function, and further, and in particular, has a carbon number of 1 to 11 since the antibacterial function is more preferable. Since the antibacterial functional group is fixed to the phenoxy resin through covalent bonding, it is safe for the human body, and sustains its effect for a long time. This antibacterial material can be suitable used for an arbitray molding, a medical equipment and the like which requires prevention of germ infection, by coating the outer surface of the same therewith.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial material that can be applied to a polymer substrate.

[0002]

2. Description of the Related Art In the medical field, a medical device made of a polymer material such as polyurethane is inserted into a patient's body.
Infection that occurs during detention is regarded as one of the complications. Conventionally, in order to prevent infectious diseases associated with the placement of medical devices, they are disinfected by immersing them in an aqueous solution containing an antibacterial agent or disinfectant such as chlorohexidine or povidone iodine immediately before use, or replaced during treatment. Frequent replacements are made for possible medical devices.
However, since the antibacterial agent / disinfectant disappears from the catheter surface with time, the effect of disinfection is not persistent, and it is clear that the effect gradually decreases when the medical device is used for a long period of time. Frequent replacement of medical equipment also places a heavy burden on healthcare professionals. Therefore, various antibacterial treatments have been applied to medical devices as one of means for further preventing infection. Typical examples thereof include a catheter whose surface is coated with a layer containing an antibacterial agent such as chlorohexidine and a metal such as silver / copper or a compound thereof. In these catheters, a system is employed in which a substance having an antibacterial action is gradually released in the body by a fixed amount at a time, and shows a better effect as compared with a case where the catheter is disinfected immediately before use.

[0003]

However, in a system in which an antibacterial substance is gradually released, it is unavoidable that the period of use is still limited and the efficacy gradually decreases. The pharmacokinetics of metals such as silver and its compounds after sustained release are unknown, and they may be harmful to the human body. In addition, if silver remains in the medical device waste after use, special treatment such as recovery is required at the time of disposal.

Therefore, a polymer having a quaternary ammonium group (Japanese Patent Publication No. 7-20846) has been developed as a polymer having antibacterial properties by itself, instead of the sustained release type.
These have a drawback that they are likely to adsorb proteins and acidic useful substances, and have a narrow antibacterial spectrum. In addition, an iodinated polystyrene fiber (Japanese Patent Publication No. 7-20845) was developed as an improved antibacterial spectrum. It has an excellent antibacterial spectrum, but since it is not a soluble polymer, it can be applied to various types of medical devices. There is a drawback that cannot be done.

In view of the problems of the prior art, the present inventors have formed a soluble and flexible film which can be applied to a medical device having a complicated shape, and have compatibility with various polymers. -An object of the present invention is to provide an antibacterial material having excellent adhesiveness and excellent antibacterial performance, and a molded article using the same.

[0006]

In order to achieve the above object, the present invention has the following constitution.

"At least a part of the hydroxyl groups is a functional group represented by the following general formula (wherein A represents a bonding group containing an ether group or an ester group, and R represents an alkylene group). An antibacterial material characterized by comprising a substituted phenoxy resin.

-A-R-I (1) "

[0009]

Next, the present invention will be described in more detail.

[0010] The phenoxy resin in the present invention, no substantial epoxide functionality obtained by reacting a dihydric phenol with epichlorohydrin general _{formula: [-D-O-CH 2} -CH (OH) -CH 2 -] _N (In the formula, D is a residue of a dihydric phenol, and n is 30 to
(An integer of 200) and is soluble in dimethylformamide or tetrahydrofuran by 5% or more. Here, as the dihydric phenol, 2,2-bis (4-hydroxyphenol) propane,
Bis (hydroxyphenyl) alkanes represented by bis (4-hydroxyphenylmethane), bis (4-)
Di (hydroxyphenyl) ethers represented by hydroxyphenyl) ether, di (hydroxyphenyl) represented by bis (4-hydroxyphenyl) sulfone
Sulfones and the like are included. Among them, a phenoxy resin using bisphenol A is industrially mass-produced, and thus has high versatility.

In the functional group represented by the formula (1) in the present invention, R is a methylene group, but preferably has 1 to 17 carbon atoms in view of antibacterial property, and further has 1 to 1 carbon atoms.
No. 1 has a particularly strong antibacterial property and is preferable. The bond between the phenoxy resin and the antibacterial functional group is formed by an ether bond or an ester bond. Specifically, for example, O-CO, OC
A linking group containing O-NH, O-CS-NH and the like is preferably used.

It is important that the antibacterial functional group of the formula (1) in the present invention is fixed to the phenoxy resin by a covalent bond. The content of the functional group is usually 0.1 mol per 1 mol of the repeating unit, but from the viewpoint of excellent antibacterial performance, it is particularly preferably 0.3 mol or more and 1.0 mol.

The method for producing the material having antibacterial properties according to the present invention is arbitrary, but will be described below with reference to examples.

A haloacyl group is introduced into a phenoxy resin which is a bisphenol A-epichlorohydrin polymer. Further, by reacting the haloacylated phenoxy resin with potassium iodide, the material having antibacterial properties of the present invention is produced. In addition, a method in which a haloalkylaminocarboxyl group is introduced into a phenoxy resin and the haloalkylaminocarboxylated phenoxy resin is subjected to a reaction treatment with potassium iodide can be used.

By applying the antibacterial material of the present invention to the surface, it can be suitably applied to any molded article required to prevent bacterial infection, such as medical equipment. In particular, a blood vessel catheter left in the body for a long period of time,
It can be suitably applied to drainage tubes, connectors, drainage bags, and the like. Compared with the material of the sustained release system, the antibacterial functional group is covalently immobilized on the phenoxy resin, so it is safe for the human body and the effect lasts. Further, as such molded products, polyurethane molded products, natural rubber, silicone resin molded products, polyvinyl chloride molded products and the like are preferably used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

[0017]

【Example】

Example 1 Commercially available phenoxy resin (manufactured by Union Carbide,
6.8 g of Phenoxy) is added to tetrahydrofuran (hereinafter referred to as T
Abbreviated as HF) After dissolving in 80 ml, chloroacetyl chloride
4.8 ml was added and reacted at room temperature for 15 hours. This solution was poured into methanol to precipitate a polymer, which was then washed with methanol and water and dried. Next, 9.32 g of this chloroacetylated phenoxy resin was added to dimethylformamide 180
After dissolving in ml, 120 ml of 26% potassium iodide (dimethylformamide solution) was added and reacted at 60 ° C for 2 hours. After pouring into water to precipitate the polymer, the polymer was washed with water and dried to obtain an antibacterial material having an iodine group. The amount of iodo group introduced was 0.7 mol per 1 mol of the repeating unit of the phenoxy resin.

Example 2 A 12.5 wt% THF solution of an antibacterial material was applied to the inner wall of a polystyrene petri dish and dried. Escherichia coli (MC1061 strain) after disinfecting the petri dish coated with the material with alcohol
Alternatively, physiological saline in which Staphylococcus aureus (FRI1169 strain) was suspended was added, and the viable cell count of the bacterial suspension was measured over time. As a control, a polystyrene petri dish not coated with the antibacterial material was also operated in the same manner. The results are shown in the table below.

[0019]

[Table 1] Example 3 The antibacterial material was applied to the tube by immersing the polyurethane tube in the axial direction of the 10 wt% THF solution of the antibacterial material shown in Example 1 and repeating the immersion and drying 7 times. The average thickness of the antibacterial material on the surface of the tube was 145 nm. After disinfecting the tube coated with the material with alcohol, E. coli (MC1061 strain) or Staphylococcus aureus (FRI116)
9 strains) were immersed in a physiological saline solution having a bacterial concentration of 10 ⁶ cells / ml and allowed to stand for 10 hours. After 10 hours, the number of bacteria attached to the tube was measured. As a control, the same operation was performed on a polyurethane tube to which the antibacterial material was not applied. As a result, in the case of Escherichia coli, the number of polyurethane tubes to which the antibacterial material was not applied was 1269 and that of the tube to which the antibacterial material was applied was 15. In the case of Staphylococcus aureus, use a tube not coated with the material.
There were 3312 and 0 in the tube coated with the material.

Example 4 20.0 g of a commercially available phenoxy resin similar to that used in Example 1 was dissolved in 140 ml of dimethylformamide, 13.0 ml of bromoundecanoyl chloride was added, and the mixture was reacted at 80 ° C. for 5 hours. After pouring the solution into methanol to precipitate the polymer,
It was washed with methanol and water and dried. Next, 3 g of this bromoundecanoylated phenoxy resin was dissolved in 72 ml of dimethylformamide, 50 ml of 24% potassium iodide (dimethylformamide solution) was added, and the mixture was reacted at 60 ° C. for 3 hours. After pouring into water to precipitate the polymer, the polymer was washed with water and dried to obtain an antibacterial material having an iodine group.

Example 5 A polyurethane tube was axially immersed in a 10 wt% THF solution of the antibacterial material shown in Example 4, and the immersion and drying were repeated 7 times to apply the antibacterial material to the tube. After disinfecting the tube coated with the material with alcohol, E. coli (MC1061 strain) or Staphylococcus aureus (FRI116)
9 strains) were immersed in a physiological saline solution having a bacterial concentration of 10 ⁶ cells / ml and allowed to stand for 24 hours. Twenty-four hours later, the number of bacteria adhered to the tube was measured. As a control, the same operation was performed on a polyurethane tube to which the antibacterial material was not applied. As a result, in the case of E. coli, the number of polyurethane tubes to which the antibacterial material was not applied was 1269 and that of the tube to which the antibacterial material was applied was 83. In the case of Staphylococcus aureus, it was 3312 in the tube not coated with the material and 0 in the tube coated with the material.

[0022]

INDUSTRIAL APPLICABILITY The antibacterial material of the present invention can be easily applied to plastic products, especially medical devices, etc., and exhibits a good antibacterial activity even at a high concentration of bacteria, and its effect lasts for a long time. An antibacterial functional group is covalently bonded to the product of the present invention,
Since the antibacterial functional group does not elute, the antibacterial performance continues for a long time and is harmless to the human body.

Claims (5)

[Claims] 1. A functional group in which at least a part of the hydroxyl groups is represented by the following general formula (wherein A represents a bonding group containing an ether group or an ester group, and R represents an alkylene group). An antibacterial material comprising a phenoxy resin substituted with. -A-R-I (1) 2. A bis (hydroxyphenyl) alkane,
The use of the antibacterial material according to claim 1, which is selected from di (hydroxyphenyl) ethers and di (hydroxyphenyl) sulfones. 3. An antibacterial molded article comprising a base material coated with the composition containing the antibacterial material according to claim 1 as a main component. 4. The antibacterial molded product according to claim 3, wherein the base material is selected from polyurethane molded products, natural rubber molded products, silicone resin molded products and polyvinyl chloride molded products. 5. The antibacterial molded article according to claim 3, wherein the base material is selected from a catheter, a tube, a connector, an access port, a drain bag and a blood circuit.