JPH10245305A - Antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for producing an antimicrobial fiber and an antimicrobial molding product, by including an inorganic and/or an organic antimicrobial agent and a hydrophilic substance. SOLUTION: This composition comprises an inorganic antimicrobial agent (metal fine particles of at least one of silver, zinc and copper and/or an inorganic compound supporting the metal ion and/or an organic compound bonded to the metal ion) and/or an organic antimicrobial agent (a polymer containing at least one of an ammonium base, a phosphonium based and a sulfonium base in a main chain and/or a side chain) and a hydrophilic substance (a polymer containing at least one of hydroxyl group, amino group, amide group, etc.) or a polymer obtained by copolymerizing an organic antimicrobial agent with a hydrophilic substance component. The amount of the inorganic and/or the organic antimicrobial agent in the molding product or on the surface of the molding product is scarcely increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial composition comprising an inorganic and / or organic antibacterial agent and a hydrophilic substance, and particularly to an antibacterial fiber, an antibacterial fabric, an antibacterial sheet, an antibacterial film, and an antibacterial agent. The present invention relates to an antibacterial composition suitable for producing a molded article, an antibacterial binder and the like.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins, especially polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, nylon, polyethylene terephthalate and polyethylene naphthalate have excellent physical and chemical properties, Widely used for films, sheets, molded products, adhesives, etc. Recently, various antibacterial products in which an inorganic or organic antibacterial agent is filled or coated with these are appearing on the market.

At present, antibacterial agents mainly studied or used include natural products such as chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract, etc., photooxidation catalyst titanium oxide particles, and zinc oxide superoxide. Examples include inorganic compound products such as fine particles, silver-containing zeolite and silver-containing zirconium phosphate, and organic compound products such as organic ammonium salt-based and organic phosphonium salt-based compounds. Antibacterial agents composed of natural products and inorganic compounds represented by silver are safe in terms of toxicity and have recently received attention, and the following inventions have already been disclosed.

JP-A-3-83905 discloses a phosphate-based antibacterial agent containing silver ions, and JP-A-3-161409 discloses a method in which a fixed volume of zeolite having a specific ion exchange capacity is replaced with silver ions. An antimicrobial agent is disclosed.

[0005] According to the contents disclosed therein, a film,
Sheets, fibers, plastic molded products such as molded products were prepared and their antibacterial properties against Staphylococcus aureus, Escherichia coli, etc. were evaluated, but antibacterial activity was insufficient if the amount added was relatively modest in order to maintain transparency. In order to improve the antibacterial activity, transparency has to be sacrificed, and there is room for practical improvement.

On the other hand, antibacterial agents of organic compounds are generally superior in antibacterial activity to fungi and the like to natural products and inorganic compounds, but these antibacterial agents are applied to the surface of molded products such as films. When applied or filled into a molded product, the antibacterial agent has a low molecular weight, so it is easy to volatilize, desorb, and separate from the surface of a molded product such as a film. It is not preferable from the viewpoint of safety. When an antibacterial agent is used in films, etc., the antibacterial agent does not dissolve in water or organic solvents, and is unlikely to be released, detached, peeled off, or dropped off from the film surface. It is preferable from the viewpoint of safety.

Under such circumstances, recently, an immobilized antibacterial agent in which an organic antibacterial agent is bonded to a polymer serving as a raw material of a molded product such as a film or a fiber by an ionic bond or a covalent bond has been disclosed. .

Japanese Patent Application Laid-Open No. 54-86584 discloses an antibacterial agent mainly composed of a polymer 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. Materials are described.

Japanese Patent Application Laid-Open No. 61-245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a basic group such as an amidine group or a quaternary ammonium base.

JP-A-57-204286, JP-A-63-60903, JP-A-62-114903, JP-A-1-93596, JP-A-2-240
The publication No. 090 describes that, like various nitrogen-containing compounds, phosphonium salt compounds are biologically active chemicals having a broad activity spectrum against Tsumugi fungi,
The phosphonium salt is immobilized in a polymer to expand its use.

JP-A-4-266912 describes an antibacterial agent comprising a phosphonium salt-based vinyl polymer, and JP-A-4-814365 describes an antibacterial agent comprising a vinylbenzylphosphonium-based vinyl polymer. .

Further, JP-A-5-310820 discloses an antibacterial agent mainly composed of a polymer 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.

The present inventors have disclosed Japanese Patent Application Laid-Open No. Hei 4-26691.
No. 2, JP-A-4-814365, JP-A-5-514
Examining Japanese Patent No. 382020, synthesizing a phosphonium base-containing vinyl polymer and a copolymerized polyester in accordance with those examples to form fibers, films, sheets, and the like,
A laminate was formed by applying the copolymerized polyester onto a fiber, film, or sheet surface, and its antibacterial activity was evaluated. However, the antibacterial activity was insufficient. Furthermore, in order to improve the antibacterial properties, a copolymerized polyester in which trinormal butyldodecylphosphonium base was bonded at 50 mol% or more was synthesized, and films and sheets were formed therefrom. The antibacterial properties as well as the decrease in mechanical properties were insufficient.

Further, the above-mentioned inorganic antibacterial agent and organic antibacterial agent are used alone or in combination to form fibers, fabrics, films, sheets, molded products and the like, and their antibacterial properties against Staphylococcus aureus, Escherichia coli and the like are evaluated. However, the antibacterial activity is insufficient,
It was insufficient for practicality.

[0015]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems, and provides a highly active antibacterial composition, more specifically, an inorganic and / or organic antibacterial agent in or on a molded article. An object of the present invention is to provide an antibacterial composition that improves antibacterial activity without increasing the amount as much as possible.

[0016]

In order to achieve the above-mentioned object, the antibacterial composition of the present invention is characterized by containing an inorganic and / or organic antibacterial agent and a hydrophilic substance.

The antibacterial composition of the present invention having the above-mentioned constitution can significantly improve the original antibacterial activity of an inorganic and / or organic antibacterial agent, and can obtain a sufficient antibacterial activity with a low concentration of an antibacterial agent. .

In a preferred embodiment of the present invention, the inorganic antibacterial agent is at least one metal fine particle of silver, zinc or copper and / or an inorganic compound carrying a metal ion and / or an organic compound having the metal ion bonded thereto. This is achieved by including a compound or titanium oxide or zinc oxide.

A further preferred embodiment is achieved by an antibacterial composition in which the organic antibacterial agent is a polymer having at least one of an ammonium base, a phosphonium base and / or a sulfonium base in a main chain and / or a side chain. You.

In a more preferred embodiment, the hydrophilic substance is a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, an amine base,
This is achieved by an antimicrobial composition that is a polymer having at least one of a polyester chain or a polyamine chain.

In another preferred embodiment, this is achieved by an antibacterial composition which is a polymer obtained by copolymerizing an organic antibacterial agent component and a hydrophilic substance component.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the antibacterial composition of the present invention will be described in detail.

The inorganic antibacterial agent used in the present invention is a general term for inorganic compounds containing metals or metal ions, which exhibit antibacterial activity against Staphylococcus aureus and Escherichia coli, and may be in any form of gas, liquid and solid. Examples thereof include silver, zinc, and copper fine particles having antibacterial activity, metal oxides such as silica, metal oxides such as silica, zeolite, and synthetic zeolites.
Zirconium phosphate, calcium phosphate, zinc calcium phosphate, ceramics, soluble glass powder, fine particles supported on inorganic compounds such as alumina silicon, titanium zeolite, apatite, calcium carbonate, etc., and organic compounds combined with metal ions such as amino acid metals Sol-gel thin films of metal oxides having photo-oxidation catalytic activity such as soap, zinc oxide, titanium oxide and molybdenum oxide or their fine particles, sol-gel thin films and fine particles are subjected to surface treatment with inorganic or organic compound reagents, sol-gel method, etc. And composite particles and the like whose surface is laminated, covered, or included / embedded with another inorganic oxide, composite oxide, or the like. In addition, it is also possible to add the above-mentioned inorganic antibacterial agent to a metal alcoholate as a raw material when forming a metal sol-gel and use it as a composite system.

As specific examples of such an inorganic antibacterial agent,
Novalon (manufactured by Toagosei Co., Ltd.), Bactekiller (manufactured by Kanebo Kasei Co., Ltd.), antibacterial spherical ceramic fine particles S
1, S2 and S5 (all manufactured by Admatechs Co., Ltd.), Holon Killer (manufactured by Nikko Corporation), Zeomic (manufactured by Shinagawa Fuel Co., Ltd.), Amenitop (Matsushita Electric Industrial Co., Ltd.)
Silver-based antibacterial agents such as IONPURE (manufactured by Ishizuka Glass Co., Ltd.), zinc-based antibacterial agents such as Z-Nove (manufactured by Mitsui Kinzoku Mining Co., Ltd.), P-25 (manufactured by Nippon Aerosil Co., Ltd.) , ST
Titanium dioxide fine particles such as -135 (manufactured by Ishihara Sangyo Co., Ltd.) and sol-gel bodies, but are not limited thereto. As examples of the composite particles, fine particles obtained by coating titanium dioxide with silica, GYT (Goyo Paper Industries Co., Ltd.)
), But is not limited thereto.

The organic antibacterial agent used in the present invention is a general term for natural extracts, low molecular weight organic compounds and polymers having antibacterial properties, and generally contains elements such as nitrogen, sulfur and phosphorus. For example, natural extracts include chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract, etc., and low-molecular-weight organic compounds such as allyl isothiocyanate, polyoxyalkylene trialkyl ammonium, and benzalkonium chloride. , Quaternary ammonium salts such as hexamethylene biguanide hydrochloride, organic silicon quaternary ammonium salts, tri-n-butyldodecylphosphonium chloride, tri-n-butyltetradecylphosphonium chloride, tri-n-butylhexadecyl Examples include, but are not limited to, quaternary ammonium salts such as phosphonium chloride, phenylamides, diguanides, tetraalkylphosphonium sulfoisophthalates or diesters thereof. As the polymer, an ammonium base, a phosphonium base, an onium salt such as a sulfonium base, a polymer in which an antibacterial active group such as a phenylamide group or a digamide group is bonded to a main chain or a side chain,
An antibacterial agent comprising a polymer having a phosphonium base is most preferred from the viewpoint of improving the antibacterial properties of the hydrophilic substance. An example is shown below, but the present invention is not limited to this.

One of the organic antibacterial agents comprising a polymer is a phosphonium salt vinyl polymer represented by the following general formula.

[0027]

Embedded image

(R ₁ , R ₂ and R _{3 each} represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, an alkyl group substituted with a hydroxyl group or an alkoxy group, an aryl group Or an aralkyl group;
^- represents an anion. n is an integer of 2 or more. )

Examples of the above R ₁ , R ₂ and R ₃ include methyl,
Alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, phenyl,
Preferred are aryl groups such as tolyl and xylyl, aralkyl groups such as benzyl and phenyl, alkyl groups and aryl groups substituted with hydroxyl groups, alkoxyl groups and the like. 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, with a halogen ion being preferred. n is not particularly limited, but 2 to 500, preferably
10 to 300.

Preferred examples of other phosphonium group-containing polymers include copolymerized polyesters comprising a dicarboxylic acid component containing 1 to 50 mol% of a phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid and a glycol component.

Specific examples of the dicarboxylic acid component constituting the copolymerized polyester include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and heterocyclic dicarboxylic acids. As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, phthalic acid, 2,6-
There are naphthalenedicarboxylic acid, 4,4-dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane and derivatives thereof, and the alicyclic dicarboxylic acid includes cyclohexane-1,4-dicarboxylic acid and derivatives thereof. Aliphatic dicarboxylic acids include adipic acid, sebacic acid, dodecanedioic acid, eicosandioic acid, dimer acid and derivatives thereof, and heterocyclic dicarboxylic acids include pyridine carboxylic acid and derivatives thereof. In addition to such a dicarboxylic acid component, p
It is also possible to include polyfunctional groups such as oxycarboxylic acids such as oxybenzoic acid, trimellitic acid, pyromellitic acid and derivatives thereof.

The glycol component constituting the copolymerized polyester includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4
-Butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, an ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. In addition, a compound containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be contained.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid constituting the copolymerized polyester include:
Tri-n-butyldecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium salt sulfoisophthalate, Tri-n-butyldodecylphosphonium salt of sulfoisophthalic acid,
Tri-n-butyldecylphosphonium sulfoterephthalate, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, Tri-n-butyldodecylphosphonium sulfoterephthalate,
4-sulfonaphthalene-2,7-dicarboxylic acid tri-n
-Butyldecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-sulfophthalic acid Naphthalene-2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt and the like, and sulfoisophthalic acid in terms of antibacterial activity Tri-n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n sulfoisophthalate
-Butyldodecylphosphonium salt is particularly preferred.

The aromatic phosphonic acid salt of a dicarboxylic acid forming the copolymerized polyester may be an aromatic dicarboxylic acid or its sodium, potassium, ammonium salt or the like, tri-n-butylhexadecylphosphonium bromide,
It is obtained by reacting a phosphonium salt such as tri-n-butyltetradecylphosphonium bromide and tri-n-butyldodecylphosphonium bromide.
The reaction solvent is not particularly limited, but water is most preferable.

For the purpose of improving the heat resistance so that the copolymerized polyester is free from coloring, gelation and the like, in addition to a polymerization catalyst such as antimony oxide, germanium oxide and titanium compound, magnesium salts such as magnesium acetate and magnesium chloride; Calcium salts such as calcium acetate and calcium chloride, manganese salts such as manganese acetate and manganese chloride are each 300 ppm or less as metal ions, and phosphoric acid or phosphate derivatives such as trimethyl phosphate and triethyl phosphate are 200 ppm as phosphorus atoms.
It is also possible to add the following.

The total amount of metal ions other than the polymerization catalyst is 3
If the amount exceeds 00 ppm or the amount of phosphorus atoms exceeds 200 ppm, not only the coloring of the polymer becomes remarkable, but also the heat resistance and hydrolysis resistance of the polymer are significantly reduced.

In terms of heat resistance, hydrolysis resistance and the like of the antibacterial material, the molar ratio of the total amount of phosphorus to the total amount of metal ions (formula 1 below) is preferably 0.4 to 1.0. preferable.

The molar ratio of the additive = (total number of moles of phosphorus in phosphoric acid, alkyl phosphate or its derivative) / (total number of moles of Mg ion, Ca ion, Mn ion, Zn ion, Co ion) --- (Equation 1)

When the molar ratio of the above formula is less than 0.4 or more than 1.0, coloring of the polymer and generation of coarse particles become remarkable, and it is difficult to apply the polymer to molded articles such as fibers, films and molded articles. Becomes

When the organic antibacterial agent is a polymer, its molecular weight is not particularly limited. In the case of a copolymerized polyester, the molecular weight is 5,000 to 50,000, preferably 10,000.
~ 30000, more preferably 15000 to 2500
0. If the molecular weight is less than 5,000, the antibacterial composition of the present invention has insufficient mechanical strength, which is not practically preferable.

The production method of the above-mentioned copolymerized polyester is not particularly limited, but 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 a dicarboxylic acid and a glycol are used. A so-called transesterification method in which a transesterification reaction is performed followed by polycondensation, and the like, can be used, and any production method can be applied.

The timing of adding the metal ions and phosphoric acid and derivatives thereof is not particularly limited, but generally, the addition of phosphoric acids is heavy at the time of charging raw materials, that is, before transesterification or esterification. It is preferably added before the condensation reaction.

The synthesis of the phosphonium base-containing polymer is not limited to the above-mentioned method. Other synthesis methods include a sulfonic acid group (or its alkali metal base) or a carboxylic acid group (or its alkali metal base). The reaction of the polymer with a phosphonium salt such as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, and tri-n-butyldodecylphosphonium bromide can be mentioned.

The hydrophilic substance in the present invention is a substance having an excellent affinity for water, and is a substance which can be dissolved, dispersed or water-retaining, moisturizing and swellable in water, and is generally a hydroxyl group, an amino group, an amide group. An organic compound or polymer having a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base or an amine base, or an organic compound having at least one of a polyether chain or a polyamine chain, or It is a polymer.
Polyether is a polymer containing two or more ether bonds in one molecule, and typically includes a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain. Polyamine is a polymer containing a basic nitrogen atom in the main chain, and typical examples include polyethyleneimine and polyalkylenepolyamine (for example, polyethylenepolyamine).

Specific examples of the hydrophilic substance include polyvinyl alcohol, polyacrylamide, poly (N, N-dimethylaminomethylacrylamide), poly (N, N-dimethylaminoethyl acrylate), and poly (N, N-dimethylamino). Ethyl methacrylate), polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, polyvinylimidazole, homopolymer or copolymer of polyacrylic acid, homopolymer or copolymer of polymethacrylic acid, homopolymer or copolymer of maleic anhydride (for example, , Maleic anhydride / styrene copolymer), polyvinyl sulfonic acid or copolymer thereof or an alkali metal salt thereof, polystyrene sulfonic acid or copolymer thereof or an alkali metal salt thereof, or a quaternary ammonium salt of polystyrene. Body, polyvinyl imidazoline salt, polyallylamine salt, polyethylene glycol (also known as polyethylene oxide), polypropylene glycol Ichiru,
Polyethylene glycol such as propylene glycol, polytetramethylene glycol, polyols such as glycerin and polyglycerin or polymers thereof,
A polyester obtained by copolymerizing an alkali salt or an ammonium salt of sulfoisophthalic acid in an amount of 1 to 10 mol% can be used. Further, these polyalkylene glycols and polyglycerols may be polyether derivatives whose terminals are blocked with alcohols, alkylphenols, fatty acids, amines, etc., for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide addition. And derivatives thereof such as fatty acid esters or fatty alcohol ethers thereof, polyglycerin fatty acid esters, polyglycerin fatty alcohol ethers, polyglycerin glycidyl ethers, and reaction products thereof. Among them, polyethylene glycol, polyglycerin and derivatives thereof are preferred in terms of improving compatibility with polyester and antibacterial properties.

The molecular weight of the above-mentioned hydrophilic substance is not particularly limited. In the case of polyethylene glycol, the number average molecular weight is preferably about 200 to 30,000, more preferably 1,000 to 30,000.
25000 is preferred. The amount of the hydrophilic substance (in the case of being a copolymer, the hydrophilic substance occupying in the copolymer) is not particularly limited. However, when polyethylene glycol is added as the hydrophilic substance, The amount is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount of the inorganic and organic antibacterial agents. If it is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and if it exceeds 20% by weight, the mechanical properties and the heat resistance and weather resistance of the antibacterial composition decrease, and both are not preferred.

The method for incorporating the hydrophilic substance into the inorganic and / or organic antibacterial agent is not particularly limited.
Any method such as mixing, melt-kneading, ionic bonding, covalent bonding, and copolymerization can be adopted depending on the production method, chemical properties, and physical properties of the organic antibacterial agent. In particular, the addition of the hydrophilic substance to the organic polymer-based antibacterial agent can take any form of mixing or copolymerization.

For example, a polyester having the above-mentioned antibacterial component is obtained by adding a copolymerizable hydrophilic substance (monomer) such as the above-mentioned glycol, polyol, alkali or ammonium salt of sulfoisophthalic acid, vinylpyrrolidone, acrylic acid, styrenesulfonic acid and the like. Bonding to the main chain or side chain of a polymer such as polyamide or polyolefin prevents bleeding out of the hydrophilic substance out of the system, that is, from the viewpoint of maintaining the high antibacterial activity of the antibacterial composition of the present invention for a long period of time. preferable. Furthermore, a method of heating and melting and mixing an inorganic and / or organic antibacterial agent and a hydrophilic substance using an extruder or the like, during the production of an organic polymer antibacterial agent, in a monomer before the polymerization reaction, or during the polymerization reaction. Alternatively, a method in which a hydrophilic substance or a monomer is added to the reaction system after the reaction is completed, or an inorganic or organic antibacterial agent and a hydrophilic substance are mixed in a suitable solvent, for example, water, a mixed solvent of water / alcohol, acetone, methyl ethyl ketone. After mixed dissolution or dispersion in organic solvents such as,
There is a method such as drying the solvent.

The hydrophilic substance in the antibacterial composition obtained by the above-mentioned process exists in any form such as covalent bond, ionic bond, copolymerization or mixture with the inorganic antibacterial agent and / or the organic antibacterial agent. However, in the case of an organic antibacterial agent, it is preferable that the hydrophilic substance is present in a copolymerized form from the viewpoint of the life of the antibacterial activity.

For the purpose of improving physical properties such as slipperiness, abrasion resistance, blocking resistance, concealing property and the like, calcium carbonate, calcium phosphate,
Inorganic fine particles such as apatite, barium sulfate, calcium fluoride, talc, kaolin, silicon oxide, alumina, titanium dioxide, zirconium oxide, iron oxide, alumina / silica composite oxide; polystyrene, polymethacrylate, polyacrylate, It is also possible to add organic fine particles such as a copolymer thereof or a crosslinked product thereof.

The details of the fine particles are as follows. Calcium carbonate fine particles are classified into three crystal types, calcite classified into trigonal or hexagonal system, aragonite classified into orthorhombic system, and paterite 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 above-mentioned kaolin fine particles may be of any type, whether natural kaolin, synthetic kaolin, calcined or unfired, and the shape thereof can be arbitrarily selected, such as plate-like, column-like, spherical, spindle-like, and egg-like. Examples of the alumina include crystalline alumina hydrates such as gypsite, paierite, nortostrandite, boehmite, diabore, and todite; and amorphous alumina hydrates such as amorphous gel, boehmite gel, and bayerite gel. And intermediate activated alumina such as ρ, η, γ, χ, κ, δ, and θ or α-type alumina.

The average particle size of these fine particles is not particularly limited since it is set according to the purpose of use, but generally, the average primary particle size is preferably 0.01 to 5 μm, and the amount of addition is preferably 5% by weight or less. preferable. 5000 particles added
When it exceeds 0 ppm, the expression of coarse particles in the inorganic or organic antibacterial agent becomes remarkable, coarse protrusions are conspicuous on the surface of the antibacterial film obtained from the antibacterial agent, the fine particles easily drop off, and the quality of the film deteriorates. Invite.

The method of filling and mixing the above-mentioned fine particles into the antibacterial composition is not particularly limited, but a method of dispersing or dissolving an organic antibacterial agent in a predetermined solvent and dispersing the above fine particles in the system, And a method of adding and dispersing the fine particles in the synthetic polymerization reaction system of the above, and, particularly, when the organic antibacterial agent is a thermoplastic polymer, adding the fine particles to the polymer and melt-kneading the polymer. When the organic antibacterial agent is a polyester, the fine particles are usually added as a slurry to the polyester polymerization reaction system in addition to ethylene glycol. The timing of the addition depends on the type of fine particles to be used, the particle size, the chloride ion concentration, the slurry concentration, the slurry temperature, and the like, 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 fine particles are added to the antibacterial composition, a predetermined thermoplastic resin to which fine particles have been added in advance can be mixed with an inorganic or organic antibacterial agent.

The antimicrobial composition of the present invention can be used alone to obtain a molded article, and furthermore, a suitable thermoplastic or thermosetting polymer such as polyolefin such as polyethylene and polypropylene, polyvinyl chloride, and polyvinyl chloride. Vinyl polymers such as vinylidene, polyamides such as 6-nylon, 6,6-nylon, 11-nylon, 12-nylon,
To obtain a molded product of the aromatic polyester, polyethylene terephthalate, aromatic polyester such as polyethylene naphthalate, polycarbonate, polystyrene, acrylic resin, polyurethane resin, amino alkyd resin, acrylic silicone resin, melamine resin, etc. Is also possible.

In addition, inorganic compounds such as water-insoluble alkali silicates, organoalkoxysilanes and tetrasilane zirconium alkoxides, and hybrid resins such as alkali silicate alkali emulsions, organoalkoxysilane melamine resins and tetrasilane zirconium alkoxide polyurethane resins are also used in the present invention. It is also possible to mix and use antimicrobial compositions.

The above mixture is melt-extruded or coated by a fiber, a woven fabric, a non-woven fabric made of polyethylene, polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene, polyurethane, polyamide, polyimide, polyamideimide or the like. Fabric, film, sheet, synthetic paper, filter,
Laminated on at least one surface of an organic substrate such as plastic, paper, wood, etc., or an inorganic substrate such as a glass plate, a stainless plate, a steel plate, an aluminum plate, an aluminum foil, a metal thin film, a metal oxide thin film, and ceramics. Is also possible. At this time, by mixing and adding a crosslinkable substance to the antibacterial composition layer, it is possible to provide a three-dimensional crosslinked structure on the laminated surface of the antibacterial composition and improve the surface strength. It is also possible to provide a thin layer of a natural polymer such as gelatin or a linear or crosslinked synthetic polymer such as polyester or polyamide on the surface of the antimicrobial composition layer.

The antibacterial fiber, antibacterial film, antibacterial sheet, antibacterial sheet, laminated metal plate and the like obtained by using the antibacterial composition of the present invention can be used even if the fiber, film or sheet is not stretched. The film may be stretched, and examples of the stretched film may be either a uniaxially oriented film or a biaxially oriented film, and the thickness of the film is not particularly limited. Antibacterial films and sheets obtained using the antibacterial composition of the present invention include, for example, films and sheets for wallpaper, films and sheets for food packaging, shrink films, shrink labels, base films for magnetic tape, semiconductors, electronic materials, and the like. Packaging film, magnetic card, OH
P, photographic support, thermal paper, etc.

[0058]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to the following Examples. Next, methods for measuring the properties of the antibacterial compositions obtained in the examples and comparative examples will be described.

[0059] (Antimicrobial test) 1/50 5 cm × a previously autoclaved to 0.1cc of S.aureus diluted in broth bacterial suspension of (Staphylococcus aureus) (concentration 10 ⁷ / cc)
The film was dropped onto a film having a size of 6 cm, and a Saran wrap film sterilized by high-pressure steam was adhered to the film.
The test piece was transferred to a sterile petri dish and cultured at 37 ° C. for 24 hours. The bacteria on the film were then transferred to SCDLP medium 10
After washing with cc, the mixture was diluted 10-fold, seeded on a normal agar plate, and the number of bacteria was counted initially and 24 hours later.

Example 1 9 mol of dimethyl terephthalate, 1 mol of tri-n-butylhexadecylphosphonium salt of dimethyl 5-sulfoisophthalate,
A transesterification reaction was carried out while adding 22 ppm of ethylene glycol and 200 ppm of zinc acetate as a zinc amount based on the theoretical amount of the copolymerized polyester, and raising the temperature to 140 to 220 ° C. while distilling off the generated methanol out of the system. After the transesterification, the molecular weight is 10,000 at 250 ° C.
0.12 mol of polyethylene glycol (PEG10000) (manufactured by Nacalai Co., Ltd.), 250 ppm of antimony oxide as antimony oxide and 80 ppm of trimethyl phosphate as phosphorus based on the theoretical amount of the formed copolymerized polyester, and stirred for 15 minutes. Subsequently, 2000 ppm of spherical silica having an average particle size of 0.9 μm was added. 26
A polycondensation reaction was performed at 0 ° C. under vacuum for 60 minutes to obtain a copolymerized polyester having an intrinsic viscosity (η) = 0.50.

The above polymer was converted to 25 using a twin screw extruder.
It was melt-extruded at 0 ° C. and cooled with a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of about 180 μm. This unstretched film is stretched 3.5 times in a longitudinal direction between a pair of rolls heated to 80 ° C. and having different peripheral speeds, and then stretched 3.5 times in a transverse direction at 120 ° C. by a tenter.
It was heat-set at 0 to 200 ° C. to obtain a biaxially stretched copolymerized polyester film having a thickness of 14.5 μm. Table 1 shows the evaluation results of the antibacterial properties of the obtained films.

(Examples 2 to 8) 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. An antibacterial evaluation was performed. Table 1 shows the obtained results.

(Examples 9 to 10) An antibacterial film was obtained in the same manner as in Example 1 except that the kind and amount of the phosphonium salt in Example 1 were changed as shown in Table 1. An antibacterial evaluation was performed. Table 1 shows the obtained results.

(Comparative Examples 1 to 3) Preparation of a stretched film was performed in exactly the same manner as in Examples 1, 9 and 10 except that polyethylene glycol was not used.
The antibacterial properties were evaluated and the results are summarized in Table 1.

[0065]

[Table 1]

T: terephthalic acid C16: tri-n-butylhexadecylphosphonium salt of 5-sulfoisophthalic acid C14: tri-n-butyltetradecylphosphonium salt of 5-sulfoisophthalic acid C12: tris of 5-sulfoisophthalic acid -N-butyldodecylphosphonium salt EG: ethylene glycol PEG: polyethylene glycol, and the numbers after indicate the molecular weight.

(Example 11) (A) Preparation of base film Calcium carbonate fine particles having an average particle size of 0.5 μm
The polyethylene terephthalate dispersed at a concentration of ppm was melt-extruded at 290 ° C. and cooled with a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of about 180 μm. The unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated to 85 ° C. and having different peripheral speeds to obtain a base film.

(B) Preparation of coating solution for antibacterial composition Example 1 was repeated except that a mixture of 5 mol of dimethyl terephthalate and 4 mol of dimethyl isophthalate was used in place of 9 mol of dimethyl terephthalate. In the same manner as in the above, an antibacterial composition was obtained. Dissolve the antimicrobial composition in a commercial grade reagent methyl ethyl ketone
% Solution.

(C) Preparation of Laminated Polyester Film The antimicrobial composition coating solution obtained in (B) was passed through a filter having a pore size of 0.1 μm, and then a bar coater was applied to the surface of the base film obtained in (A). It was applied by a method and dried with hot air at 70 ° C. Next, the film was stretched 3.5 times in the longitudinal direction at 130 ° C. with a tenter, and then heat-set at 200 to 210 ° C. to obtain a biaxially stretched laminated polyester film having a thickness of 14.5 μm. The final coating amount of the coating agent (antimicrobial composition) on the film was about 0.2 g / m ² . Table 2 shows the results of the antibacterial evaluation of the obtained coated film.

(Example 12) The coating solution of the antibacterial composition obtained in Example 11 was applied to a 75 µm thick biaxially stretched transparent PET film (manufactured by Toyobo Co., Ltd.) so as to have a solid content of 0.3 µm. . The antibacterial property of this coated film was evaluated in the same manner as in Example 11, and the results shown in Table 2 were obtained.

(Example 13) The coating solution of the antibacterial composition obtained in Example 11 was applied on a 75 μ thick white PET synthetic paper Crisper (manufactured by Toyobo Co., Ltd.) to a solid content of 0.3 μ. did. The antibacterial property of this coated film was evaluated in the same manner as in Example 11, and the results shown in Table 2 were obtained.

(Examples 14 to 16) Coated films were obtained in the same manner as in Example 11 except that the kind and amount of the phosphonium salt were changed as shown in Table 2, and the antibacterial properties were evaluated. Table 2 shows the obtained results.

Comparative Examples 4 to 6 Copolymers were synthesized in exactly the same manner as in Example 1 except that polyethylene glycol was not added.
In the same manner as in Examples 2 and 13, the base film was coated, a coated film was prepared, and the antibacterial property was evaluated.
Table 2 shows the obtained results.

[0074]

[Table 2]

T: terephthalic acid I: isophthalic acid C16: tri-n-butylhexadecylphosphonium salt of 5-sulfoisophthalic acid C14: tri-n-butyltetradecylphosphonium salt of 5-sulfoisophthalic acid C12: 5-sulfo Tri-n-butyldodecylphosphonium salt of isophthalic acid EG: ethylene glycol PEG: polyethylene glycol, and the numbers after indicate the molecular weight.

Example 17 A mixture of terephthalic acid // ethylene glycol / polyethylene glycol (molecular weight: 1000) (100 // 95/5 molar ratio) in which calcium carbonate fine particles having an average particle size of 0.5 μm were dispersed at a concentration of 4000 ppm. 1 part by weight of silver / zirconium phosphate antibacterial filler per 100 parts by weight of polymer, Novalon (Toa Gosei Co., Ltd.)
Was mixed and extruded at 280 ° C.
It was cooled by a cooling roll at 0 ° C. to obtain an unstretched film having a thickness of about 180 μm. The unstretched film is vertically stretched between a pair of rolls heated to 85 ° C. and having different peripheral speeds.
The film was stretched 3.5 times in a transverse direction at 130 ° C. with a tenter, and then heat-set at 200 to 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 14.5 μm. Table 3 shows the results of evaluating the antibacterial properties of the obtained films.

(Examples 18 to 19) The same procedures as in Example 17 were carried out except that the inorganic antibacterial agents shown in Table 3 were used instead of the silver / zirconium phosphate antibacterial filler (manufactured by Toagosei Co., Ltd.). An antibacterial film was obtained in the same manner, and the antibacterial property was evaluated in the same manner as in Example 17. Table 3 shows the obtained results. The antibacterial property of the P-25-containing system was evaluated while illuminating a black light at a distance of 40 cm.

(Comparative Examples 7 to 9) Preparation of antibacterial films and evaluation of antibacterial properties were performed in exactly the same manner as in Examples 17, 18 and 19 except that polyethylene terephthalate PET was used instead of the copolymer in Example 17. The results in Table 3 were obtained.

[0079]

[Table 3]

Novalon: silver-based antibacterial agent manufactured by Toagosei Co., Ltd. Z-Nove: zinc-based antibacterial agent of Mitsui Kinzoku Mining Co., Ltd. P-25: titanium dioxide of Nippon Aerosil Co., Ltd. EG: ethylene glycol PEG: polyethylene glycol, later Indicates the molecular weight. ND: not detected

(Example 20) (A) Preparation of sulfonic acid group-containing polyester and aqueous dispersion First, a sulfonic acid group-containing polyester was prepared by the following method. A transesterification reaction and a polycondensation reaction were carried out by a conventional method using 95 mol% of dimethyl isophthalate and 5 mol% of sodium 5-sulfoisophthalate as a dicarboxylic acid component and 100 mol% of diethylene glycol as a glycol component. The glass transition point of the obtained sulfonic acid group-containing polyester (PES-SO ₃ Na) was 69 ° C. 300 parts of this sulfonic acid group-containing polyester and 150 parts of n-butyl cellosolve are heated and stirred to form a viscous solution, and 550 parts of water are gradually added with further stirring to obtain uniform pale white water having a solid content of 30%. A dispersion was obtained. This dispersion was further added to a mixture of equal amounts of water and isopropanol to prepare an aqueous dispersion of a sulfonic acid group-containing polyester having a solid content of 5%.

(B) Preparation of mixed coating solution 0.1 part by weight of silver / zirconium phosphate antibacterial filler, Novalon (manufactured by Toagosei Co., Ltd.) was added to 100 parts by weight of the above (A) aqueous dispersion of sulfonic acid group-containing polyester. Add to the mixture,
Finely dispersed to obtain a coating solution.

(C) Preparation of Film A base film was prepared in the same manner as in Example 11 except that the coating solution was changed, and then a laminated film was prepared. The final coating coverage of the film was about 0.5 g / m ² . Table 4 shows the evaluation results of the antibacterial properties of the obtained films.

(Examples 21 to 22) The same procedures as in Example 20 were carried out except that the inorganic antibacterial agents shown in Table 4 were used instead of the silver / zirconium phosphate antibacterial filler (manufactured by Toagosei Co., Ltd.). An antibacterial film was obtained in the same manner, and the antibacterial property was evaluated in the same manner as in Example 17. Table 4 shows the obtained results. The antibacterial property of the P-25-containing system was evaluated while illuminating a black light at a distance of 40 cm.

[0085]

[Table 4]

Novalon: a silver-based antibacterial agent manufactured by Toagosei Co., Ltd. Z-Nove: a zinc-based antibacterial agent manufactured by Mitsui Kinzoku Mining Co., Ltd. P-25: Nippon Aerosil Co., Ltd. titanium dioxide PES-SO ₃ Na: containing a sulfonic acid group Polyester ND: not detected

(Example 23) Polyethylene terephthalate (PET, molecular weight: 2000) in which fine particles of calcium carbonate having an average particle size of 0.5 µm were dispersed at a concentration of 4000 ppm.
0) 95 parts by weight of polyethylene glycol (molecular weight 20)
000) 2 parts by weight of 5 parts by weight of a silver / zirconium phosphate antibacterial filler (manufactured by Toagosei Co., Ltd.) were added, and
Extruded at 0 ° C and cooled with a cooling roll at 30 ° C.
An unstretched film having a thickness of about 180 μm was obtained. The unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated to 85 ° C. and having different peripheral speeds to obtain a base film. Next, 3.5 degrees in the horizontal direction at 130 ° C. by a tenter.
After stretching twice, heat-setting at 200-210 ° C, thickness 1
A 4.5 μm biaxially stretched polyester film was obtained. Table 5 shows the evaluation results of the antibacterial properties of the obtained films.

(Examples 24 to 25) The same procedures as in Example 17 were carried out except that the inorganic antibacterial agents shown in Table 3 were used instead of the silver / zirconium phosphate antibacterial filler (manufactured by Toagosei Co., Ltd.) in Example 23. An antibacterial film was obtained in the same manner, and the antibacterial property was evaluated in the same manner as in Example 17. Table 5 shows the obtained results. The antibacterial property of the P-25-containing system was evaluated while illuminating a black light at a distance of 40 cm.

(Comparative Examples 10 to 12)
In Example 25, an antibacterial film was prepared and evaluated in the same manner as in Examples 23, 24 and 25 except that polyethylene terephthalate was used instead of the copolymer.
Was obtained.

[0090]

[Table 5]

Novalon: silver-based antibacterial agent manufactured by Toagosei Co., Ltd. Z-Nove: zinc-based antibacterial agent of Mitsui Kinzoku Mining Co., Ltd. P-25: Nippon Aerosil Co., Ltd. titanium dioxide EG: ethylene glycol PEG: polyethylene glycol, later Indicates the molecular weight. ND: not detected

(Examples 26 and 37) Examples 23 and 24,
In Table 25, instead of polyethylene glycol,
3 types of polyglycerin (polyglycerin # 31
0, polyglycerin # 500, polyglycerin # 75
0) (manufactured by Sakamoto Pharmaceutical Co., Ltd.)) and Examples 23, 24 and 25 except that polyvinyl alcohol (PVA) was used.
An antibacterial film was obtained in the same manner as described above, and the antibacterial property was evaluated. Table 6 shows the obtained results.

[0093]

[Table 6]

Novalon: Silver antibacterial agent manufactured by Toagosei Co., Ltd. Z-Nove: Zinc antibacterial agent of Mitsui Kinzoku Mining Co., Ltd. P-25: Titanium dioxide of Nippon Aerosil Co., Ltd. PG: Polyglycerin ND: Not detected

[0095]

The antibacterial composition of the present invention significantly improves the original antibacterial activity of an inorganic or organic antibacterial agent even when the antibacterial component is small, and shows a sufficient antibacterial activity even at a low concentration of the antibacterial agent. . Taking advantage of this property, general packaging films, magnetic tape base films, electronic component packaging films, photographic support films, thermal paper films, wallpaper sheets and other films, fibers, plastics, polymer binders, and paper When used for wood, ceramics, etc., it can exhibit excellent antibacterial properties.

Claims (6)

[Claims] 1. An antimicrobial composition comprising an inorganic and / or organic antimicrobial agent and a hydrophilic substance. 2. The method according to claim 1, wherein the inorganic antibacterial agent is at least one metal fine particle of silver, zinc, or copper and / or an inorganic compound carrying ions of the metal and / or an organic compound bonded to the metal ion. The antibacterial composition according to claim 1, wherein 3. The antibacterial composition according to claim 1, wherein the inorganic antibacterial agent contains titanium oxide and / or zinc oxide. 4. The antibacterial according to claim 1, wherein the organic antibacterial agent is a polymer having at least one of an ammonium base, a phosphonium base or a sulfonium base in a main chain and / or a side chain. Composition. 5. The method according to claim 1, wherein the hydrophilic substance is a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain or a polyamine chain. 5. The antibacterial composition according to claim 1, wherein the composition is a polymer having at least one kind. 6. A polymer obtained by copolymerizing an organic antibacterial agent component and a hydrophilic substance component.
The antibacterial composition according to 2, 3, 4 or 5.