JP2000119348A - Production of antibacterial/antifungal resin and water dispersion of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition to which an antibacterial/antifungal agent was applied, which activity can be enhanced without enhancing the amount of the organic antibacterial/antifungal agent in a base substance or on the surface of the base substance. SOLUTION: This method comprises the steps of dissolving, into an organic solvent, a polyester A having at least one antibacterial/antifungal moiety selected from ammonium salt, pyridinium salt, and phosphonium salt in its main chain or its side chain and a vinyl-binding moiety, and graft polymerizing therewith a hydrophilic group-containing vinyl-based monomer in the presence of an azobisnitrile-based initiator selected from azobisisobutylonitrile, azobispropionitrile, and azobisvaleronitrile and a polymerization modifier, wherein the polyester A is a substantially amorphous copolymerized polyester having a glass transition temperature at 30 deg.C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial resin solution comprising a polymer resin having antibacterial properties and hydrophilicity, and is suitable as a processing material for antibacterial films, antibacterial sheets, antibacterial fibers and the like.

[0002]

2. Description of the Related Art Conventionally, antibacterial materials have been added to impart antibacterial properties to films, sheets, fibers, fabrics, papers, plastic molded products, metal plates, etc. in various fields such as industrial, agricultural, food and the like. Resin coating materials have been developed and used. At present, antibacterial agents mainly studied or used are chitin, chitosan, wasabi extract, mustard extract, hinokitiol, natural products such as polyphenol extracted from tea, ultrafine zinc oxide particles, photooxidation catalyst titanium oxide particles, silver. There are inorganic products such as zeolite containing silver and zirconium phosphate containing silver, and various synthetic products such as organic ammonium salts. Natural products and inorganic products represented by silver have recently been receiving attention as being safe in terms of toxicity. For example, a zeolite carrying a gold ion having an antibacterial action (Japanese Patent Laid-Open No. 60-202162, etc.)
Also, many paints containing inorganic antibacterial materials such as phosphate compounds having similar metal ions (for example, JP-A-5-59308) have been proposed. However, silver ions, which are the mainstream of inorganic antibacterial materials, are supported on inorganic compound carriers, and silver ions are eluted and antibacterial properties decrease in many cases. Especially in places exposed to water, antibacterial properties are relatively short. However, there is a problem that the resin disappears, and when it is mixed with a resin, it often becomes colored or discolored, which significantly impairs the design of the product.

On the other hand, organic synthetic products generally have better antibacterial and antifungal properties than natural products and inorganic products, but antibacterial components tend to volatilize and separate easily, and are apt to be avoided because of their toxicity. This is because the antibacterial component is easily dissolved in water, an organic solvent, or the like. Recently, an insoluble, nontoxic, immobilized antibacterial agent has been developed. There is the following disclosure example as this improvement method. 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. Has been described. JP-A-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 group. JP-A-57-204286, 63-60
9030, 62-114903, JP-A-1-9359
6. According to Japanese Unexamined Patent Publication No. 24090/1990, phosphonium salt compounds, as well as various nitrogen-containing compounds, are known as biologically active chemicals having a broad spectrum of activity against bacteria. There is disclosed an invention in which the above phosphonium salt is immobilized on a polymer substance to attempt to expand its use. JP-A-4-266912 discloses an antibacterial agent for phosphonium salt-based vinyl polymers.
No. 65 discloses a vinylbenzylphosphonium salt-based vinyl polymer antibacterial agent. Further, JP-A-5-310820 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.

The present inventors have disclosed Japanese Patent Application Laid-Open No. 4-266912,
Examining Japanese Patent Application Laid-Open No. 4-814365 and Japanese Patent Application Laid-Open No. 5-310820, synthesizing a phosphonium base-containing vinyl polymer and a copolyester and a coating agent using the same in accordance with the examples thereof, and then synthesizing the structure of a fiber or a film. The antibacterial activity was insufficient, and the antibacterial activity was insufficient, and it was necessary to improve the antibacterial material.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have studied an organic antibacterial material which does not elute the antibacterial component and has excellent antibacterial properties and antibacterial durability. As a result, the present inventors have arrived at the antibacterial material of the present invention.

[0006]

An object of the present invention is to dissolve a specific polyester A having an antibacterial site and a vinyl binding site in a main chain or a side chain in an organic solvent, and then dissolve the azobisisobutyronitrile and azobisisobutyronitrile, Graft polymerization of a hydrophilic group-containing vinyl monomer onto the polyester A in the presence of an azobisnitrile-based initiator selected from bispropionitrile and azobisvaleronitrile and 3-t-butyl-4-hydroxyanisole This is achieved by an antibacterial resin characterized by being obtained. The above antibacterial resin is characterized in that the polyester A has an antibacterial site selected from ammonium salts, pyridinium salts, and phosphonium salts. The antibacterial resin of the present invention having the above constitution is particularly excellent in antibacterial properties.

The above antibacterial resin is characterized in that the polyester A is a substantially amorphous copolymer polyester having a glass transition point of 30 ° C. or higher. The antibacterial resin of the present invention having the above-mentioned constitution easily undergoes a graft polymerization reaction to the polyester, and the obtained antibacterial resin has excellent antibacterial properties and physical properties. In this case, the polyester A is at least one or more dicarboxylic acid components selected from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and ethylene glycol, diethylene glycol, 1,3-propanediol, and 1,4-butanediol. And at least 1% by mole of a phosphonium salt of a sulfonic acid group-containing bifunctional aromatic compound represented by the following chemical formula, which contains at least one or more glycol components selected from neopentyl glycol and cyclohexanedimethanol. It can be a copolymerized polyester copolymerized in an amount of not more than mol%. The antibacterial material of the present invention having the above configuration is particularly excellent in antibacterial properties and durability. In this case, the hydrophilic group-containing vinyl monomer may be one or more selected from acrylic acid, methacrylic acid and esters thereof, maleic acid and anhydrides thereof. The antibacterial material of the present invention having the above constitution is characterized in that a hydrophilic group-containing vinyl-based monomer can be effectively graft-added to an antibacterial polyester A containing a vinyl binding site, and its antibacterial activity is markedly enhanced. There is.

In this case, the polymerization reaction modifier is a primary or tertiary alkyl mercaptan having 8 to 16 carbon atoms,
One or two or more selected from 3-t-butyl-4-hydroxyanisole can be used. The antibacterial material of the present invention having the above constitution is characterized in that a hydrophilic group-containing vinyl monomer can be effectively graft-polymerized to polyester A, and the antibacterial resin has particularly excellent antibacterial properties and durability. . Further, an object of the present invention is to obtain a polyester A by dissolving it in an organic solvent, then graft-polymerizing a hydrophilic group-containing vinyl monomer onto the polyester A, then adding an amine and water, and distilling off the organic solvent. Achieved by the aqueous dispersion provided.

Next, the present invention will be described in detail. The polyester A of the present invention is preferably a specific polyester having at least one antibacterial site and a vinyl binding site selected from an ammonium salt, a pyridinium salt, and a phosphonium salt in a main chain or a side chain. The antimicrobial moiety of the present invention refers to a chemical structure which has an antimicrobial property by itself chemically bonded to the main chain or side chain of polyester A, and is one or two of the monomers constituting polyester A.
It is obtained by polymerizing a polyester using a monomer having a chemical structure having antibacterial performance more than at least one kind.
As a monomer having a chemical structure having antibacterial performance, a monomer having an ammonium salt, a pyridinium salt, or a phosphonium salt is preferable. In particular, a monomer having a phosphonium salt is particularly preferable in terms of antibacterial properties and heat resistance. Typical examples of the polyester A of the present invention include a dicarboxylic acid component and a glycol component as main components, and 1 mol of a phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid.
% Or less and 30 mol% or less.

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. As aromatic dicarboxylic acids, terephthalic acid,
There are isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane and derivatives thereof, and the alicyclic dicarboxylic acid is cyclohexane-
There are 1,4-dicarboxylic acids and derivatives thereof, and the like, and examples of the aliphatic dicarboxylic acids include adipic acid, sebacic acid, dodecanedioic acid, eicosandioic acid, dimer acid, and derivatives thereof, and a heterocyclic dicarboxylic acid. Include pyridinecarboxylic 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. As the glycol component, ethylene glycol,
1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, Examples include 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.

The phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid includes tri-n-sulfoisophthalic acid.
Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n-sulfoisophthalate Butyl dodecyl phosphonium salt, tri-n-sulfoterephthalate
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n sulfoterephthalate -Butyl dodecyl phosphonium salt, 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-butylhexa Decylphosphonium salt, 4-sulfonaphthalene-
2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and the like. In terms of antibacterial activity, trisulfoisophthalate is preferred. −
n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate,
Tri-n-butyldodecylphosphonium sulfoisophthalate is particularly preferred.

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

The reaction solvent is not particularly limited, but water is most preferred. 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 and manganese chloride are used for the purpose of improving heat resistance such as coloring degree and gel formation. 20 ppm as each metal ion
It is also possible to add phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester and phosphoric acid triethyl ester as P in an amount of from 20 ppm to 200 ppm. The above metal ion is 300pp
If it exceeds m, the coloring of the polymer becomes remarkable. Also 20p
If it is less than pm, no improvement in the heat resistance of the polymer is observed. Further, from the viewpoint of heat resistance and the like, the molar ratio of P to the metal ion is 0.1.
It is preferably from 4 to 1.0.

[0014]

(Equation 1)

When the molar ratio is less than 0.4 or more than 1.0, coloring of the polymer and generation of coarse particles become remarkable, and it becomes difficult to apply the polymer to molded articles such as fibers, films and plastics. As a method for producing the polyester, any production method such as a so-called direct polymerization method in which an aromatic dicarboxylic acid and a glycol are directly reacted, a transesterification reaction between a dimethyl ester of an aromatic dicarboxylic acid and a glycol, a so-called transesterification method, and the like. Can be applied. The timing of adding the metal ion, phosphoric acid and its derivative is not particularly limited, but it is preferable that the metal ion is added at the time of charging the raw materials and that the phosphoric acid is added before the polymerization reaction.

It is preferable that the copolyester A of the present invention is substantially amorphous. The term "substantially non-crystalline" means that the copolymerized polyester does not crystallize even when left at a temperature equal to or higher than the glass transition temperature for a long time, and does not show a low-temperature crystallization peak and a melting peak of DSC. When the polyester is substantially crystalline, when dissolved in an organic solvent, the solubility becomes poor with a normal solvent, and productivity,
There is a quality problem. The copolyester A of the present invention preferably has a glass transition temperature of 30 ° C. or higher. When the glass transition point of the copolymerized polyester is lower than 30 ° C., problems occur in physical properties such as scratch resistance and blocking resistance of the obtained antibacterial resin. In order to obtain more sufficient physical properties, it is more preferable that the glass transition temperature of the polyester A of the present invention is 40 ° C. or higher.

The vinyl monomer having a hydrophilic group which can be grafted onto the polyester A in the present invention includes a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, an amide group, and a quaternary ammonium. Examples include those containing a base and the like, and those containing an acid anhydride group, a glycidyl group, a chloro group, and the like as the group that can be converted into a hydrophilic group. Among them, those having a carboxyl group are most preferable from the viewpoint of hydrophilicity. For example, monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-
Alkyl acrylates such as butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, alkyl methacrylates such as t-butyl methacrylate, hydroxy-containing such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate Monomer, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N, N-dimethylolacrylamide, Amide group-containing monomers such as N-phenylacrylamide, glycidyl acrylate, glycidyl methax Epoxy group-containing monomers such rate and the like. Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, styrene sulfonic acid, monomers containing a sulfonic acid group or a salt thereof such as vinyl sulfonic acid and salts thereof, crotonic acid, Monomers containing a carboxyl group or a salt thereof such as itaconic acid, maleic acid, fumaric acid and salts thereof, and monomers containing an acid anhydride such as maleic anhydride and itaconic anhydride are exemplified. These can be used in combination with other monomers. Other monomers, for example, vinyl isocyanate,
Allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride and the like can be mentioned, and copolymerization using one or more of these can be used. it can. The ratio of the monomer having a hydrophilic group to the other monomer is 30 by mole.
The range of / 70 to 100/0 is preferred. If the ratio of the monomer having a hydrophilic group is less than 30 mol%, the effect of enhancing the antibacterial property is not sufficiently exhibited.

As a method for grafting a vinyl-based monomer having a hydrophilic group to the polyester A of the present invention, a known graft polymerization method can be used. The following method is mentioned as a typical example. For example, a radical polymerization method in which radicals are generated in a main chain polymer substance by light, heat, radiation, or the like and then graft-polymerized with a monomer, or a cationic polymerization method in which cations are generated using a catalyst such as AlCl ₄ or TiCl ₄ Or metal Na, metal L
There is an anion polymerization method of generating an anion using i or the like. Further, as another method of grafting a vinyl-based monomer having a hydrophilic group to the polyester A of the present invention, a polymerizable unsaturated double bond is previously introduced into the polyester of the main chain, and the vinyl-based monomer is reacted therewith. There is a method. Monomers having a polymerizable unsaturated double bond used for this include fumaric acid, maleic acid,
Maleic anhydride, itaconic acid, citraconic acid, 2,5-
Norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like can be mentioned. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid. Further, there is a method in which a main chain polymer substance having a functional group introduced into a side chain is reacted with a branch polymer having a group that reacts with the functional group at the terminal.
For example, -OH group, -SH group, -NH2 group, -CO
A polymer substance having a hydrogen donating group such as an OH group-CONH2 group, one end of which is -N = C = O group, -C = C = O group, -C
H-CH ₂

[0019]

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[0020]

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And the like, and a reaction in the reverse combination. The above method will be described in more detail. As the organic solvent used for dissolving the polyester A of the present invention, methyl ethyl ketone, isopropyl alcohol, tetrahydrofuran, and a mixed solvent thereof are used. Among them, a mixed solvent of methyl ethyl ketone and isopropyl alcohol is most preferable. As a polymerization initiator for graft-polymerizing a vinyl monomer to polyester A, benzoyl peroxide, acetyl peroxide,
Lauroyl peroxide, ketone peroxide, cumene peroxide,
organic peroxides such as t-butyl peroxide, hydrogen peroxide, potassium persulfate, inorganic peroxides such as ammonium persulfate,
Examples thereof include sulfinic acids, azobisnitrile such as azobisisobutyronitrile, azobispropionitrile, and azobisvaleronitrile, diazoaminobenzene, and nitrosoacyl allylamine. In addition, a dialkylaniline, sodium sulfite, sodium thiosulfate, various amines, iron,
Nickel, cobalt, or the like can be added and used. In the case of the antibacterial resin of the present invention, when azobisisobutyronitrile is used as a reaction initiator for graft polymerization, an antibacterial material having the highest reactivity and excellent properties can be effectively produced.

If necessary, primary mercaptans such as octyl mercaptan and n-dodecyl mercaptan, tertiary mercaptans such as t-decyl mercaptan, t-tetradecyl mercaptan, t-hexadecyl mercaptan, dialkyl disulfide, Polymerization modifiers such as diacyl disulfide and 3-t-butyl-4-hydroxyanisole can also be used. In the case of the antibacterial resin of the present invention, when 3-t-butyl-4-hydroxyanisole is used as a polymerization reaction modifier, the antibacterial properties, durability and the like are the best.

The weight ratio of the polyester A as the main chain of the present invention and the vinyl monomer to be grafted is 40 / 60-9.
5/5, more preferably 55 / 45-9.
3/7, most preferably in the range of 60/40 to 90/10. If the weight ratio of the polyester A is less than 40%, the graft-polymerizable vinyl-based monomer remains without completely reacting, and the properties of the conventional polyester, such as heat resistance and processability, are impaired. When the weight ratio of the polyester A in the main chain exceeds 95%, the effect of improving antibacterial properties, which is the object of the present invention, cannot be sufficiently exhibited. The antimicrobial resin of the present invention can be neutralized by adding an amine and water, and can be dispersed in water by heating to remove the solvent. Ammonia, triethylamine,
And triethanolamine.

The antibacterial resin of the present invention has a further antibacterial activity.
Other organic antibacterial agents or silver
/ Zeolite particles, silver / zirconium phosphate particles, oxidation
Zinc fine particles, titanium oxide fine particles having photooxidation catalytic function
It is also possible to add an inorganic antibacterial agent such as Ma
In addition, the surface of a molded article obtained from the antibacterial resin of the present invention has a smooth surface.
Physical properties such as wear resistance, abrasion resistance, blocking resistance, concealment
In order to improve the properties, calcium carbonate (CaC
O_Three), Barium sulfate (BaSO)_Four), Calcium fluoride
(CaF_Two), Talc, kaolin, silicon oxide (Si
O_Two), Alumina (Al_TwoO_Three), Titanium dioxide, oxidation
Zirconium (ZrO_Two), Iron oxide (Fe_TwoO _Three), A
Inorganic particles such as lumina / silica composite oxide, cross-linked polystyrene
Len, cross-linked polymethacrylate, cross-linked polyacryl
It is also possible to add organic particles such as
You.

The above particles will be described in more detail.
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 type may be used, and the shape thereof may be spherical, cubic, spindle-shaped,
It can be arbitrarily selected such as a columnar shape, a needle shape, a spherical shape, and an egg shape. 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 columnar, plate-like, spherical, spindle-like, and egg-like. Examples of the alumina include crystalline alumina hydrates such as gibbsite, bayerite, Nordstrandite, boehmite, diaspore, and todite; amorphous gels, boehmite gels, amorphous alumina hydrates such as bayerite gels, and ρ , Γ, κ, δ, θ-type intermediate activated alumina or α-type alumina.

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 particle size is preferably 0.01 μm or more and 5 μm or less. The following is preferred. When the added amount of the particles exceeds 5% by weight, coarse particles in the polymer substance become remarkable, and coarse protrusions are conspicuous on the surface of a molded article such as a film or a fiber obtained from an antibacterial material using the same. Body quality and abrasion resistance are reduced. As a method of adding these particles to the antimicrobial resin of the present invention, a method of adding at any stage during the polymerization of polyester A, a method of adding at any stage of the graft polymerization reaction, an antimicrobial resin solution or aqueous dispersion There is a method of adding it to the body later, but any method may be used.

The antimicrobial resin of the present invention can be laminated on an inorganic substrate such as glass, an organic substrate such as a fiber, a film, a sheet, a plastic, or a metal plate by a coating method or the like. The molded body thus obtained is used, for example, for packaging films, films for magnetic tapes, industrial films, plastics, fibers and the like. The film may be an unstretched film, a uniaxially oriented film, or a biaxially oriented film, but a biaxially oriented film is particularly preferred.

(Action) Since the antibacterial resin of the present invention has a hydrophilic group on a side chain of a polyester having a specific composition having an antibacterial site, when it is applied to a substrate, the antibacterial property is remarkably improved. It is also excellent in scratch resistance and blocking resistance.

(Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but is not limited to the following Examples. Hereinafter, methods for measuring the physical properties of the antibacterial materials obtained in Examples and Comparative Examples will be described. Antibacterial test method 0.1 ml of a 1/50 broth diluted E. coli (Escherichia coli) bacterial solution was dropped onto a 5 cm x 5 cm test film previously sterilized with high pressure steam, and the film was subjected to high pressure steam sterilization. The adhered polyethylene film was adhered. The test film 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
Then, the cells were washed out with ml, and the number of bacteria was counted by a dilution culture method using an ordinary agar plate. Blocking Resistance of Films Two films were superimposed, and the presence or absence of adhesion between the films after passing between two rolls with a pressure of ² kg / cm ² was evaluated. Abrasion Resistance of Films When two films were overlaid and rubbed lightly with finger pressure, the presence or absence of scratches and shavings on the coated surface was evaluated.

Production Example of Polyester A In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 388 parts of dimethyl isophthalate, 5-sulfodimethyl isophthalate tri-n-butyl dodecyl phosphonium. 161 parts of salt, ethylene glycol 443.3
Parts, neopentyl glycol 400.4 parts, and tetra-n-butyl titanate 0.52 parts,
The transesterification reaction was performed over 4 hours to 220 ° C.
Then add 29 parts of fumaric acid and add 1 to 200 to 230 ° C.
The temperature was raised over time, and the pressure of the reaction system was gradually reduced.
The reaction was carried out at a reduced pressure of 2 mmHg for 1 hour and 30 minutes to obtain a polyester (A1). The composition of the polyester (A-1) is as shown below. Dicarboxylic acid component Terephthalic acid 50 mol% Isophthalic acid 40 mol% C12 phosphonium salt 5 mol% Fumaric acid 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol% The composition as shown in Table 1 was obtained in the same manner. Different polyesters (A-2, A-3, A-4, A-5) were produced. Table 1 shows the composition and properties of each polyester.

Preparation Example 1 of Graft Polymer A reactor equipped with a stirrer, a thermometer, a reflux device and a metered addition device was charged with 300 parts of polyester (A-1), 360 parts of methyl ethyl ketone, 120 parts of isopropyl alcohol and 3-t-butyl. 5 parts of -4-hydroxyanisole were added, and the mixture was heated and stirred to dissolve the resin under reflux. After the resin is completely dissolved, a mixture of 65 parts of acrylic acid and 35 parts of ethyl acrylate, 6 parts of azobisisobutyronitrile are mixed with 90 parts of methyl ethyl ketone and 3 parts of isopropyl alcohol.
A solution dissolved in 0 parts of the mixed solution was added dropwise to the polyester solution over 1.5 hours, and the mixture was further reacted for 3 hours to obtain a graft polymer solution. After the graft polymer solution was cooled to room temperature, 59 parts of triethylamine was added and neutralized, and then 800 parts of ion-exchanged water was added and stirred for 30 minutes. Thereafter, the solvent remaining in the solvent was distilled off by heating to obtain an aqueous dispersion (B-1). The polyesters (A-2, A-3, A-5) were graft-polymerized by the same method to obtain graft polymers (B-2, B-3, B-5). However, since the solubility of the polyester (A-4) was insufficient, a uniform solution could not be obtained.

Preparation Example 2 of Graft Polymer Graft polymer was prepared in the same manner as in Preparation Example 1, except that acrylic acid (20 parts) and ethyl acrylate (10 parts) were used as the grafting monomer. A polymer aqueous dispersion (B-6) was obtained.

Production Example 3 of Graft Polymer 300 parts of polyester (A-1), 360 parts of methyl ethyl ketone, and 120 parts of isopropyl alcohol were placed in a reactor equipped with a stirrer, a thermometer, a reflux device, and a metered addition device, and heated and stirred. The resin was dissolved under reflux. After the resin is completely dissolved, a mixture of 65 parts of methyl methacrylate and 35 parts of styrene, 6 parts of azobisisobutyronitrile, 90 parts of methyl ethyl ketone,
A solution dissolved in 0 parts of the mixed solution was added dropwise to the polyester solution over 1.5 hours, and further reacted for 3 hours to obtain a graft polymer solution (B-7). Triethylamine and ion-exchanged water were added thereto, followed by heating to evaporate the solvent to obtain an aqueous dispersion. However, an aqueous dispersion could not be obtained by phase separation.

Example 1 An unstretched film having a thickness of 650 μm obtained by melt-extruding a polyester having an intrinsic viscosity of 0.62 onto a rotary cooling drum was stretched 3.5 times in the machine direction, and then stretched in the transverse direction at 120 ° C. Stretched 3.7 times, and heat-set at 220 ° C.
A μm biaxially stretched polyester film was obtained. This was used as a substrate film. The polyester aqueous dispersion (B-1) was diluted with ion-exchanged water so as to have a solid content concentration of 5%, and this was used as a coating liquid. After applying the coating liquid on the substrate film, it was dried at 150 ° C. to obtain a coated film. The average thickness of the coating layer on this film was 0.4 μm. Table 2 shows the properties of the obtained film.

Example 2 A coated film was obtained in the same manner as in Example 1, except that the polyester aqueous dispersion (B-2) was used. Table 2 shows the properties of the obtained film.

Example 3 A coated film was obtained in the same manner as in Example 1 except that the aqueous polyester dispersion (B-6) was used. Table 2 shows the properties of the obtained film.

Comparative Example 1 50 parts of polyester (A-1) was treated with methyl ethyl ketone 6
00 parts, uniformly dissolved in a mixed solvent of 350 parts of isopropyl alcohol, and coated on a base film,
It was dried at 150 ° C. to obtain a coated film. The thickness of the coating layer of this film was 0.4 μm. Table 2 shows the properties of the obtained film.

Comparative Example 2 A coated film was obtained in the same manner as in Example 1, except that the aqueous polyester dispersion (B-3) was used. Table 2 shows the properties of the obtained film.

Comparative Example 3 A polyester polymer solution (B-7) was prepared with a solid content of 5%.
This was diluted with methyl ethyl ketone to give a coating solution. After applying the coating liquid on the base film, 1
It was dried at 50 ° C. to obtain a coated film. The average thickness of the coating layer on this film was 0.4 μm. Table 2 shows the properties of the obtained film.

Comparative Example 4 A coated film was obtained in the same manner as in Example 1 except that the aqueous polyester dispersion (B-5) was used. Table 2 shows the properties of the obtained film.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

The antibacterial resin of the present invention has remarkably excellent antibacterial properties and excellent physical and mechanical properties such as abrasion resistance and blocking resistance. Therefore, it is suitable as a material for antibacterial plastics, fibers and films. is there.

Continued on front page F-term (reference) 4J027 AB02 AB03 AB06 AB07 AB08 AB29 AB34 AJ06 BA03 BA04 BA05 BA06 BA07 BA08 BA09 BA13 BA14 BA29 CA26 CA29 CB09 CC02 CD01 4J029 AA03 AB04 AC05 AD01 AD07 AD10 BA03 BA04 BA05 BA10 BD06ABD07ABF09 CH01 CH02 CH03 DA01 DA14 DB14 DC08 GA13 GA42 GA43 HB01 HB02 HB06 JB162 JB182 JC131 JC141 JD05 KB03 KH01 KH03 4J038 CP121 GA01 GA08 GA14 HA156 JB01 KA06 MA08 MA10 MA12 MA13 NA05

Claims (5)

[Claims] (1) at least one selected from an ammonium salt, a pyridinium salt, and a phosphonium salt in a main chain or a side chain;
Polyester A having various antibacterial sites and a vinyl binding site is dissolved in an organic solvent, and then an azobisnitrile-based initiator selected from azobisisobutyronitrile, azobispropionitrile, and azobisvaleronitrile, and A method for producing an antibacterial resin, comprising graft-polymerizing a hydrophilic group-containing vinyl monomer in the presence of a polymerization reaction modifier, wherein the polyester A has a substantially non-glass transition point of 30 ° C or higher. A method for producing an antibacterial resin, which is a crystalline copolyester. 2. The polyester A according to claim 1, wherein at least one or more dicarboxylic acid components selected from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and ethylene glycol, diethylene glycol, and 1,3-propane. Diol, 1,4-butanediol, neopentyl glycol, cyclohexane dimethanol and at least one glycol component selected from the group consisting of a sulfonic acid group-containing bifunctional aromatic compound represented by the following formula 1% by mole or more of phosphonium salt
A method for producing an antimicrobial resin, which is a copolymerized polyester copolymerized at 0 mol% or less. 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.) Alkyl group) 3. The hydrophilic group-containing vinyl monomer according to claim 1, which is at least one selected from acrylic acid, methacrylic acid and esters thereof, maleic acid and anhydride thereof. Method for producing antibacterial resin. 4. The polymerization reaction modifier according to claim 1, wherein the primary or tertiary alkyl mercaptan having 8 to 16 carbon atoms is used.
A method for producing an antimicrobial resin, wherein the method is one or more selected from 3-t-butyl-4-hydroxyanisole. 5. The polyester A according to claim 1, which is dissolved in an organic solvent, a vinyl monomer having a hydrophilic group is graft-polymerized to the polyester A, and an amine and water are further added. A method for producing an aqueous dispersion of an antibacterial resin, which comprises dispersing.