JPH1017663A - Antibacterial film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film having markedly improved antibacterial properties by mixing a phosphonium-substituted polymer with a hydrophilic substance. SOLUTION: This film contains a the polymer having phosphonium salt groups bonded to the main chain or the chains and a hydrophilic substance. it is desirable that polymer contains acid groups and phosphonium groups ironically bonded to the acid groups. It is desirable that the polymer is a copolyester mainly consisting of a dicarboxylic acid component and a glycol component and containing 1-50mol% phosphonium salt of a sulfoniated aromatic dicarboxylic acid, represented by the formula (wherein A is an aromatic group; X1 and X2 are each an esterifiable functional group; and R1 to R4 are each an alkyl, provided that at least one of them is a 10-20C alkyl), as a comonomer. It is desirable that the hydrophilic substance is a polyester containing 1-10mol% glycerol, polyglgcerol or the like as a comonomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial film and an antibacterial sheet comprising a polymer substance having a phosphonium base and a hydrophilic substance.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Nylon, polyethylene terephthalate and polyethylene naphthalate have excellent physical and chemical properties and are used for wallpaper, medical films, industrial films, agricultural films, packaging films, magnetic tape films and the like. Recently, antibacterial properties have been imparted to these films by a method such as filling or coating with an inorganic or organic antibacterial agent, and these films are appearing on the market as new antibacterial films.

At present, antibacterial agents mainly studied or used include natural products such as chitin and chitosan, inorganic products such as photooxidation catalyst titanium oxide particles, zinc oxide ultrafine particles, silver-containing zeolite, and organic ammonium salts. And synthetic products such as organic phosphonium salt compounds. Natural and inorganic antimicrobial agents are safe in terms of toxicity and have recently received attention, but are expensive. On the other hand, organic synthetic products generally have better antibacterial activity than natural products and inorganic products.However, surface treatment is mainly used to impart antibacterial properties to substrates such as films. And the like, which is easy to volatilize, desorb, and separate from the surface of the substrate, which is not preferable from the viewpoint of long-term stability of antibacterial properties and safety to the human body.

When an antibacterial agent is used for a film or the like,
It is preferable that the antibacterial agent does not dissolve in water or an organic solvent and is hardly released, detached, peeled, or dropped off from the film surface from the viewpoint of long-term stability of the antibacterial performance and safety to the human body. Under such circumstances, recently, an immobilized antibacterial agent has been disclosed in which an organic antibacterial agent is bonded to a polymer material serving as a raw material of a film or the like by ionic or covalent bonding. JP-A-54-
86584 discloses an antibacterial material mainly composed of a polymer substance containing an antibacterial agent component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid group. JP-A-61-245378
The publication describes a fiber made of a polyester copolymer containing an antibacterial agent component having a basic group such as an amidine group or a quaternary ammonium base. JP-A-57-20
Publications such as 4286, 63-60903, 62-114903, JP-A-1-93596 and JP-A-2-240090 disclose that, like various nitrogen-containing compounds, phosphonium salt compounds are organisms having a broad activity spectrum against bacteria. Known as biologically active chemicals.

[0005] There is disclosed an invention in which the above phosphonium salt is immobilized on a polymer substance to expand its use. JP-A-4-266912 discloses an antibacterial agent of a phosphonium salt-based vinyl polymer, and JP-A-4-814365 discloses an antibacterial agent of a vinylbenzylphosphonium salt-based vinyl polymer. Further, Japanese Patent Application Laid-Open No. Hei 5-3108
No. 20 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. In that example, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed.

Japanese Patent Application Laid-Open No. 6-41408 does not mention any antibacterial action, but it is useful for photographic supports, packaging, general industrial use, magnetic tapes, and the like, in which polyesters of phosphonium sulfonate and polyester are used. Modified polyesters and films comprising alkylene glycols are disclosed. The alkyl group bonded to the phosphonium salt described in the specification of the above patent is a type having a relatively short carbon number such as a butyl group, a phenyl group or a benzyl group, unlike the above-mentioned JP-A-5-310820. JP-A-4-266912, JP-A-4-814365, and JP-A-5-310820 were intensively studied, and a vinyl polymer containing a phosphonium base and a copolymerized polyester were synthesized according to the examples to form a film, a sheet, or the like. Was applied on other films and sheets to form a laminate, and its antibacterial properties were evaluated.
Antibacterial activity was insufficient. Furthermore, in order to improve the antibacterial property, a polyester in which at least 50 mol% of trinormal butyl dodecylphosphonium base was bonded was synthesized, and a film, a sheet, and the like were formed. Not only was the physical property significantly reduced, but also the antibacterial properties were insufficient.

[0007]

The object of the present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide a highly active antibacterial film, specifically, an antibacterial component in a polymer substance. An object of the present invention is to realize an improvement in antibacterial properties without unnecessarily increasing the amount of phosphonium base.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is achieved by an antibacterial film mainly composed of a hydrophilic substance and a polymer substance having a phosphonium base bonded to a main chain or a side chain. In a preferred embodiment, a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group, and in a further preferred embodiment, a dicarboxylic acid component and a glycol component are used as main components and represented by the following general formula: A copolymerized polyester obtained by copolymerizing a phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid having a content of 1 mol% or more and 50 mol% or less.

[0009]

Embedded image Wherein A is an aromatic group, X ₁ and X ₂ are ester-forming functional groups, R _1, R _2, R _{3 and} R ₄ are alkyl groups, at least one of which has 10 to 20 carbon atoms. Glycerin, polyglycerin, polyglycerin derivatives, polyalkylene glycols, polyalkylene glycol derivatives, alkali or ammonium salts of sulfoisophthalic acid, and polyesters obtained by copolymerizing 1 mol% or more and 10 mol% or less as hydrophilic substances. The object of the present invention is remarkably achieved by an antibacterial film containing at least one of the following.

[0010] The antibacterial film of the present invention is characterized in that the antibacterial activity is remarkably enhanced by adding a hydrophilic substance to a polymer substance containing a phosphonium base. Next, the present invention will be described in detail. A macromolecule is a substance in which a phosphonium base is bonded to the main chain or side chain.
Any polymer compound may be used. A typical example will be described below, but the present invention is not limited to this. One of the high-molecular substances is a phosphonium salt-based vinyl polymer represented by the following general formula.

Embedded image (R _1, R _{2 and} R ₃ are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxy group,
Or an alkyl group, an aryl group or an aralkyl group substituted with an alkoxy group, X- is an anion, and n is 2
Specific examples of the above R _1, R _{2, and} R ₃ include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, and aryl groups such as phenyl, tolyl, and xylyl. Substituted with an aralkyl group such as benzyl, phenyl and the like, a hydroxyl group, an alkoxy group and the like, and an alkyl group and an aryl group are particularly preferable. R _1,
R _{2 and} R ₃ may be the same group or different groups. X- is an anion, for example, a halogen ion such as fluorine, chlorine, bromine or iodine, a sulfate ion, a phosphate ion, a perchlorate ion and the like, and a halogen ion is preferable. n is not particularly limited, but is 2 to 500, preferably 1
0 to 300. Another example of the high molecular compound is a copolymerized polyester obtained by copolymerizing a phosphonium salt of a dicarboxylic acid component and a sulfonic acid group-containing aromatic dicarboxylic acid in an amount of 1 mol% or more and 50 mol% or less and a glycol component. The effect of adding the derivative is remarkable.

As the dicarboxylic acid component of the copolymerized polyester, aromatic dicarboxylic acid, alicyclic dicarboxylic acid,
Examples thereof include aliphatic dicarboxylic acids and heterocyclic dicarboxylic acids. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-dicarboxylic phenyl, and 4,4
-Dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane and derivatives thereof,
Alicyclic dicarboxylic acids include cyclohexane-1,4-dicarboxylic acid and derivatives thereof, and aliphatic dicarboxylic acids include adipic acid, sebacic acid, dodecanedioic acid, eicoic acid, dimer acid and derivatives thereof. Examples of the heterocyclic dicarboxylic acid include pyridine carboxylic acid and derivatives thereof. In addition to such a dicarboxylic acid component, it is also possible to include oxycarboxylic acids such as p-oxybenzoic acid and polyfunctional acids such as trimellitic acid, pyromellitic acid and derivatives thereof.

The glycol component includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexane Examples include dimethanol, an ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, it may contain a small amount of a compound containing an amide bond, urethane bond, ether bond, carbonate bond or the like.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid include tri-n-sulfoisophthalic acid.
Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate , Sulfoisophthalic acid tri-n-
Butyl dodecylphosphonium salt, tri-n-butyldecylphosphonium sulfoterephthalate, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, Tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n-butyldodecylphosphonium sulfoterephthalate, tri-n-butyldecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, 4-sulfonaphthalene-2,
7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt,
4-sulfonaphthalene-2,7-dicarboxylic acid tri-n
-Butyltetradecylphosphonium salt, tris-n-butyldodecylphosphonium salt of 4-sulfonaphthalene-2,7-dicarboxylic acid, etc., and tri-n-butylsulfoisophthalate from the viewpoint of antibacterial activity. Hexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, and tri-n-butyldodecylphosphonium sulfoisophthalate are particularly preferred.

The above phosphonium salts of aromatic dicarboxylic acids include aromatic dicarboxylic acids or their sodium, potassium, ammonium salts and the like, and tri-n-butylhexadecylphosphonium bromide and tri-n-butyltetradecylphosphonium. It is obtained by reacting a phosphonium salt such as bromide and tri-n-butyldodecylphosphonium bromide.

The reaction solvent is not particularly limited, but water is most preferred. For the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation, the copolymerized polyester has magnesium salts such as magnesium acetate and magnesium chloride, calcium salts such as calcium acetate and calcium chloride, and manganese salts such as manganese acetate manganese chloride and the like.
Salt, Zn salt such as zinc chloride, zinc acetate, etc., Co salt such as cobalt chloride, cobalt acetate etc. are each 300 p as a metal ion.
pm or less, phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester, phosphoric acid triethyl ester
, It is also possible to add 200 ppm or less. The total amount of the metal ions is 300 ppm, and the P amount is 200 ppm.
If it exceeds ppm, not only the coloring of the polymer becomes remarkable, but also the heat resistance and hydrolysis resistance of the polymer are remarkably reduced.

At this time, in terms of heat resistance, hydrolysis resistance, etc., the molar ratio of the total amount of P to the total amount of metal ions is 0.4 to 0.4.
It is preferably 1.0.

(Equation 1) When the molar atomic ratio is less than 0.4 or more than 1.0, coloring and generation of coarse particles of the film of the present invention become remarkable, which is not preferable. Although the molecular weight of the polymer substance is not particularly limited, when the polymer substance is a copolymerized polyester, the molecular weight is from 5,000 to 50,000, preferably 1,000.
It is 0 or more and 30000 or less, more preferably 15000 or more and 25,000. When the molecular weight is 5,000 or less, the mechanical strength of the antibacterial active layer of the present invention is insufficient, which is not preferable.

The method for producing the copolymerized polyester is not particularly limited, and a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed, a dimethyl ester of dicarboxylic acid and a glycol are used. A so-called transesterification method in which polycondensation is carried out after transesterification, and the like, may be mentioned, and any production method can be applied.

The timing of addition of the metal ions and phosphoric acid and derivatives thereof is not particularly limited. Generally, metal ions are added at the time of charging raw materials, that is, before transesterification or esterification, and phosphoric acid is added by polycondensation. It is preferably added before the reaction. The hydrophilic substance in the present invention is a substance that can be dissolved or dispersed in water, and has a hydroxyl group -OH,
A hydrophilic group such as an amino group —NH ₂ , a carboxyl group —COOH, a sulfo group —SO ₃ H or a derivative thereof, or an organic compound or a polymer compound containing two or more ether bonds in one molecule. Are polyalkylene glycols such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyethylene glycol (also known as polyethylene oxide), polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, glycerin, polyglycerin, etc., sulfoisophthalate A polyester obtained by copolymerizing an alkali salt or an ammonium salt of an acid in an amount of 1 mol% to 10 mol% is exemplified. In addition, the ends of these polyalkylene glycols and polyglycerin are alcohols, alkylphenols,
It may be blocked with a fatty acid or the like, for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide adduct, its fatty acid ester or aliphatic alcohol ether, polyglycerin fatty acid ester, polyglycerin fatty alcohol ether, polyglycerol Derivatives such as glyceryl glycidyl ether and its reaction product are exemplified. Among them, polyethylene glycol, polyglycerin and derivatives thereof are preferred in view of compatibility with polyester and high antibacterial property.

The molecular weight of the hydrophilic substance is not particularly limited, but is preferably 200 to 30,000, more preferably 1,000 to 25,000 in number average molecular weight.
The amount of the hydrophilic substance added is 0.1-2 with respect to the polymer substance.
0% by weight, preferably 0.5-10% by weight, more preferably 1-5% by weight. When the content is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and when it exceeds 20% by weight, the mechanical properties and heat resistance of the antibacterial active layer are undesirably reduced.

There is no particular limitation on the method of mixing the polymer substance and the hydrophilic substance, which are important in the expression of antibacterial properties, and any method may be used depending on the method of producing the polymer substance, its chemical properties and its physical properties. it can. For example, a method of heating and melting the two using an extruder or the like, a method of adding a hydrophilic substance into the reaction system during the reaction or after the reaction, during the production of the polymer substance, in the monomer before the polymerization reaction, Further, a method of mixing and dissolving or dispersing a polymer substance and hydrophilic substances in an appropriate solvent, for example, water, a mixed solvent of water / alcohol, an organic solvent such as acetone, methyl ethyl ketone, or the like, and then drying the solvent. There is.

In the above process, the hydrophilic substance may be present in the polymer substance in the form of a copolymer or in the form of a mixture, and there is no significant difference in the antibacterial effect between the two. The above-mentioned mixed system can be used alone to form a film. Further, a suitable thermoplastic resin, for example, a polyolefin such as polyethylene or polypropylene, a vinyl polymer such as polyvinyl chloride or polyvinylidene chloride, 6-nylon, , 6-nylon, 11-nylon, 12-nylon, etc., polyamides, aliphatic polyesters, aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polystyrene. It is possible. It is also possible to laminate the above mixture on at least one surface of a thermoplastic resin film of polyethylene, polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene or the like. The antibacterial film of the present invention had another organic antibacterial agent, or silver / zeolite particles, silver / zirconium phosphate particles, zinc oxide fine particles, and a photooxidation catalyst function for the purpose of further improving the antibacterial activity. It is also possible to add an inorganic antibacterial agent such as titanium oxide fine particles.

Further, the antibacterial film of the present invention has a slip property,
Calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), calcium fluoride (CaF ₃ ), for the purpose of improving physical properties such as abrasion resistance, blocking resistance, and concealing property.
₂ ), talc, kaolin, silicon oxide (SiO ₂ ), alumina (Al ₂ O ₃ ), titanium dioxide, zirconium oxide (ZrO ₂ ), iron oxide (Fe ₂ O ₃ ), alumina / silica composite oxide, etc. Inorganic particles; organic particles such as cross-linked polystyrene, cross-linked polymethacrylate, and cross-linked polyacrylate can also be added.

The above particles are described in more detail as follows. Calcium carbonate particles are classified into three crystal types, calcite classified into trigonal or hexagonal system, aragonite classified into orthorhombic system, and vaterite classified into hexagonal or pseudo hexagonal system, according to their crystal structures. However, any crystal form may be used, and the shape thereof may be arbitrarily selected, such as a sphere, a cube, a spindle, a column, a needle, a sphere, and an egg. The kaolin particles may be of any type, whether natural kaolin, synthetic kaolin, calcinable or unburned, and the shape thereof can be arbitrarily selected, such as plate, column, sphere, spindle, and egg. Examples of the alumina include crystalline alumina hydrates such as gibbsite, bayerite, nordstrandite, boehmite, diabore, and todite; amorphous alumina hydrates such as amorphous gel, boehmite gel, and bayerite gel; , Η, γ, χ,
Intermediate activated alumina such as κ, δ, and θ types or α-type alumina may be used.

The average particle size is not particularly limited, since it is necessary to change the average particle size according to the purpose. In general, the average primary particle size is preferably 0.01 μm or more and 5 μm or less. The following is preferred. 500 particles added
If it exceeds 00 ppm, coarse particles in the polymer substance become remarkable, coarse protrusions are conspicuous on the surface of the antibacterial film obtained therefrom, and the particles are liable to fall off, leading to deterioration of the film quality. The method of filling and mixing the fine particles into the antibacterial film is not particularly limited, and a method of adding the fine particles to the polymer substance (1) and adding the particles to the polymerization reaction system to complete the polymerization, and a method of melting the high molecular substance ( There is a method in which the particles are added and kneaded in 1), and both methods can be adopted. Usually, the former method is preferable from the viewpoint of dispersibility of the particles in the polymer substance (1). When the polymer (1) is a polyester, the particles are usually added to the reaction system as a slurry in addition to ethylene glycol.

The timing of the addition depends on the type of fine particles used, the particle size, the chloride ion concentration, the slurry concentration, the temperature of the slurry, etc., but is usually preferably before the start of the polyester polymerization reaction or at the oligomer formation stage. When the slurry is added to the reaction system, it is preferable to heat the slurry to the boiling point of ethylene glycol from the viewpoint of improving the dispersibility of the particles. When adding fine particles to the antibacterial film,
The thermoplastic resin to which fine particles have been added in advance can be mixed with the polymer substance (1). The method for producing the antibacterial film of the present invention is not particularly limited. The polymer substance (1), the hydrophilic substance, and if necessary, other thermoplastic resins and the above-mentioned various additives are mixed at a predetermined ratio. A method of extruding in a single layer, a method of extruding a melt containing a polymer substance and a hydrophilic substance and other molten resin bodies into multiple layers,
A method of laminating a melt containing a polymer substance (1) and a hydrophilic substance on a film or sheet, dispersing or dissolving the polymer substance (1) and a hydrophilic substance in an appropriate solvent, and extruding the liquid. And a method of forming a film or sheet by scattering the solvent, or a method of laminating a dispersion or solution thereof on an appropriate film or sheet by a coating method or the like. The antibacterial film of the present invention may be any of an unstretched film, a uniaxially oriented film, and a biaxially oriented film, and the thickness of the film is not particularly limited. The antibacterial film of the present invention is, for example, a film for wallpaper, a film for food packaging, a label, a base film for magnetic tape, a semiconductor,
It is suitable for packaging films of electronic materials and the like, magnetic cards, sheets of OHP and the like.

(Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Hereinafter, methods for measuring the physical properties of the antibacterial films obtained in Examples and Comparative Examples will be described. Antibacterial test 0.1 ml of a bacterial solution (concentration: 107 cells / ml) of S. aureus (Staphylococcus aureus) diluted with 1/50 broth was dropped on a 5 cm * 6 cm film which had been sterilized with high pressure steam in advance. Then, a Saran wrap film sterilized by high pressure steam was brought into close contact with the film. The test piece was transferred to a sterile petri dish and cultured at 37 degrees for 24 hours. Then, the bacteria on the film were washed with 10 ml of SCDLP medium, diluted 10-fold, and spread on an ordinary agar plate. After 24 hours, the number of bacteria was counted.

Example 1 9 moles of dimethyl terephthalate, 1 mole of tri-n-butylhexadecylphosphonium salt of dimethyl 5-sulfoisophthalate, 22 moles of ethylene glycol, based on theoretical amount of copolymerized polyester Zinc acetate as zinc (Zn)
0 ppm was added, and the transesterification reaction was performed while methanol generated by elevating the temperature from 140 ° C. to 220 ° C. was distilled out of the system. After completion of the transesterification reaction, 250 ppm of antimony oxide as antimony (Sb) and 80 ppm of trimethyl phosphate as P were added at 250 ° C. based on the theoretical amount of the copolymerized polyester, and the mixture was stirred for 15 minutes. 2000 ppm of spherical silica was added. A polycondensation reaction was performed at 260 ° C. under vacuum for 30 minutes to obtain a copolymerized polyester resin having an intrinsic viscosity η = 0.55.
3 parts by weight of polyethylene glycol having a molecular weight of 10,000 (Nacalai Co., Ltd.) was mixed with 97 parts by weight of the polymer,
This was melt-extruded at 250 degrees using a twin-screw extruder, and cooled with a cooling roll at 30 ° C to a thickness of about 180 µm.
Was obtained. 80 ° C.
Stretched 3.5 times in a longitudinal direction between a pair of rolls heated at different peripheral speeds, then stretched 3.5 times in a transverse direction at 120 ° C. by a tenter, and heat-fixed at 190 to 200 ° C. A biaxially stretched copolyester film having a thickness of 14.5 μm was obtained. Table 1 shows the evaluation results of the antibacterial properties of the obtained films.

(Examples 2 to 5) An antibacterial film was obtained in the same manner as in Example 1 except that the kind and amount of polyethylene glycol in Example 1 were changed as shown in Table 1. Antimicrobial evaluation was performed. Table 1 shows the obtained results.

(Comparative Example 1) A stretched film was prepared and the antibacterial property was evaluated in the same manner as in Example 1 except that polyethylene glycol was not added, and the results were summarized in Table 1.

(Example 6) In the synthesis of the copolymerized polyester in Example 1, a polymerization reaction was carried out using terephthalic acid alone as an acid component to obtain polyethylene terephthalate (PET). 50 parts by weight of the copolyester, 47 parts by weight of PET and an average molecular weight of 100 in Example 1.
Preparation of antibacterial film and evaluation of antibacterial properties were performed in the same manner as in Example 1 using 3 parts by weight of polyethylene glycol of Example No. 00, and the results in Table 1 were obtained.

Comparative Example 2 An antibacterial film was produced and evaluated in the same manner as in Example 6 except that polyethylene glycol was not added. Table 1 summarizes the results.

(Examples 7 to 11) Instead of polyethylene glycol in Example 1, three types of polyglycerin, polyglycerin # 310, and polyglycerin # 5 shown in Table 1 were used.
An antibacterial film was obtained in the same manner as in Example 1 except that polyglycerin # 750 (Sakamoto Yakuhin Kogyo Co., Ltd.) was used, and the antibacterial property was evaluated in the same manner as in Example 1. Table 2 shows the obtained results.

[0033]

Since the antibacterial film of the present invention has remarkably excellent antibacterial properties, it is suitable as a general packaging film, a magnetic tape, an industrial film for packaging electronic parts, etc., and an interior film such as wallpaper for wallpaper.

[0034]

[Table 1]

[0035]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiro Seko 2-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Co., Ltd. Research Institute (72) Inventor Masakazu Tanaka 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (4)

[Claims] 1. An antibacterial film containing a hydrophilic substance and a polymer substance having a phosphonium base bonded to a main chain or a side chain. 2. The antibacterial film according to claim 1, wherein the polymer substance contains an acidic group and a phosphonium base ionically bonded to the acidic group. 3. A high molecular substance comprising a dicarboxylic acid component and a glycol component as main components, and a phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid represented by the following general formula:
3. The antibacterial film according to claim 1, which is a copolymerized polyester copolymerized in an amount of l% to 50 mol%. Embedded image In the formula, A is an aromatic group, X ₁ and X ₂ are ester-forming functional groups,
R _2, R _2, R _{3 and} R ₄ are alkyl groups, at least one of which is an alkyl group having 10 to 20 carbon atoms. 4. A polyester wherein the hydrophilic substance is copolymerized with glycerin, polyglycerin, polyglycerin derivative, polyalkylene glycol, polyalkylene glycol derivative, alkali salt or ammonium salt of sulfoisophthalic acid in an amount of 1 mol% to 10 mol%. 4. The antibacterial film according to claim 1, wherein the film comprises one kind.