JPH11115110A - Packaging material and packaging bag made of antibacterial laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated packaging material and packaging bag applied by antibacterial agent for improving antibacterial activity without increasing antibacterial composition having high activity or more particularly inorganic and/or organic antibacterial agent amount in a base or on a surface of the base. SOLUTION: The antibacterial laminate comprises at least four or more layers of laminate packaging material having a polyester layer, polyester sealant layer and antibacterial composition-containing layer in such a manner that outermost layers of both sides of the laminate are each formed of polyester resin containing antibacterial composition made of inorganic and/or organic antibacterial agent and hydrophilic substance, a polyester layer is laminated at an inner layer side in contact with the outermost layer of one side, and a heat sealable polyester sealant is laminated at an inner layer side in contact with the outermost layer of the opposite side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a packaging material and a packaging bag comprising an antibacterial laminate containing an antibacterial composition comprising an inorganic and / or organic antibacterial agent and a hydrophilic substance.
Therefore, the present invention can be applied to all fields of application where the laminated packaging material is used, that is, industrial films and packaging films, and can impart new antibacterial properties. In particular, it is suitably used in foods, medical instruments, medical facilities, and packaging and the like in the field of pharmaceuticals that require sterilization.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene, polypropylene, polyvinylidene chloride, nylon, polyethylene terephthalate and ethylene terephthalate, have excellent physical and chemical properties, and can be used in fibers, plastics,
Used for films, sheets, adhesives, etc. Recently,
Antimicrobial products have been devised in which an inorganic or organic antibacterial agent is filled or applied. Currently, antibacterial agents mainly studied or used include chitin, chitosan, wasabi extract mustard extract, hinokitiol,
Natural products such as tea extract antibacterial agents, photo-oxidation catalyst titanium oxide particles,
Examples include inorganic compounds such as ultrafine zinc oxide particles, silver-containing zeolite, and silver-containing zirconium phosphate, and synthetic products such as organic ammonium salts and organic phosphonium salts. Inorganic antibacterial agents typified by natural and 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 an antibacterial agent obtained by replacing a certain volume of zeolite having a specific ion exchange capacity with silver ions. An agent is disclosed. Films, sheets, fibers, and plastics were prepared according to the inventions disclosed therein, and their antibacterial properties against Staphylococcus aureus, Escherichia coli, etc. were evaluated. Inadequately, in order to improve the antibacterial activity, transparency had to be sacrificed, and there was room for improvement in practical use. On the other hand, antibacterial agents of organic synthetic products generally have higher antibacterial activity against fungi and the like than natural products and inorganic products, but when these antibacterial agents are surface-coated or filled on a substrate such as a film, Since the antibacterial agent has a low molecular weight, it is easy to volatilize, desorb, and separate from a substrate such as a film, which is not preferable in terms of long-term stability of antibacterial properties and safety to human bodies. When using antibacterial agents in films, etc., the antibacterial agents do not dissolve in water or organic solvents and are not easily released, detached, peeled, 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 material serving as a raw material 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 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. Is described. JP-A-61-245378 discloses a fiber comprising a polyester copolymer containing an antibacterial component having a polar group such as an amidine group or a quaternary ammonium base. JP-A-57-204286, 63-60903, 6
2-114903, JP-A-1-93596, JP-A-2-93
Japanese Patent Publication No. 24090 and the like, like various nitrogen-containing compounds,
Phosphonium salt compounds are known as biologically active chemicals with a broad spectrum of activity against bacteria.

[0005] An invention in which the above phosphonium salt is immobilized on a polymer substance to expand the use thereof has been disclosed. 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. 5-310820
Disclose 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,
Polyesters using phosphonium salts of sulfoisophthalic acid are 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 for copolyesters of phosphonium sulfonate and polyester. Modified polyesters and polyester films comprising alkylene glycols are disclosed. The alkyl group bonded to the phosphonium salt described in the specification of the above patent is disclosed in Japanese Patent Application Laid-Open No. Hei 5-3108.
Unlike 20, it is a type having a relatively short carbon number such as a butyl group, a phenyl group, and a benzyl group. JP-A-4-2669
12, JP-A-4-814365, JP-A-5-31082
0, and the phosphonium base-containing vinyl copolymer and copolyester are synthesized to form fibers, films, sheets, etc. according to the examples, and the antibacterial polymer thereof is applied to the fibers, film sheet surface. Thus, a laminate was formed, and its antibacterial activity was evaluated, but the antibacterial activity was insufficient. Further, in order to improve the antibacterial property, trinormal butyl dodecylphosphonium base is added to 50%.
A polyester having mol% or more bonded thereto was synthesized, and a film, a sheet or the like was prepared therefrom. However, not only the mechanical properties due to the coloring of the polymer and the reduction of the glass transition point but also the antibacterial properties were insufficient. Furthermore, the above-mentioned inorganic antibacterial agent and organic antibacterial agent were used alone or in combination to form fibers, fabrics, films, sheets, and the like. Insufficient for practical use.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve 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 substrate. Provided is a laminated packaging material and a packaging bag to which an antibacterial agent capable of improving the antibacterial activity without increasing the amount is provided, and the antibacterial property is easily imparted by coating and packaging with the laminated packaging material and the packaging bag. It is to provide the obtained article.

[0008]

The object of the present invention is achieved by an antibacterial composition containing an inorganic and / or organic antibacterial agent and a hydrophilic substance. In a preferred embodiment, this is achieved by an antibacterial composition in which the organic antibacterial agent and the hydrophilic substance are copolymerized. In a further preferred embodiment, the inorganic antibacterial agent is silver (Ag), zinc (Z
n), at least one kind of metal fine particles of copper (Cu) and / or an inorganic compound carrying metal ions, or titanium oxide (TiO ₂ ) and / or zinc oxide (ZnO ₂ ).

In a further preferred embodiment, the present invention is achieved by an antibacterial composition in which the organic antibacterial agent is a high molecular compound containing an ammonium base and / or a phosphonium base and / or a sulfonium base in a main chain or a side chain. In a particularly preferred embodiment, the hydrophilic substance contains at least one of a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain, and a polyamine chain. This is achieved by an antimicrobial composition that is a molecular compound. The antibacterial composition of the present invention is characterized in that its antibacterial activity is significantly enhanced by including a hydrophilic substance in an inorganic and / or organic antibacterial agent. Next, the present invention will be described in detail.

The inorganic antibacterial agent of the present invention is a general term for inorganic compounds having antibacterial activity against Staphylococcus aureus and Escherichia coli containing metals or metal ions, and may be in any form of gas, liquid and solid. Examples thereof include metal particles such as silver, zinc and copper having antibacterial activity or metal ion species such as metal oxides such as silica, zeolite, synthetic zeolite, zirconium calcium phosphate, zinc calcium phosphate, ceramic, and soluble glass. Sol-gel thin film of a metal oxide having a photo-oxidation catalytic function such as powder, alumina silicon, titanium zeolite, apatite, calcium carbonate, etc., or a metal oxide such as zinc oxide, titanium oxide, molybdenum oxide or the like. Fine particles, or sol-gel thin films or fine particles, surface-treated with an inorganic or organic compound reagent, or composite particles obtained by laminating, coating, or wrapping / embedding the surface with another inorganic oxide or composite oxide by sol-gel method or the like Is raised. It is also possible to add the above-mentioned inorganic antibacterial agent to the metal alcoholate as a raw material when forming the metal sol-gel, and use the compound 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 particles S
1, S2, S5 (manufactured by Admatech Co., Ltd.), Holon Killer (manufactured by Nikko Corporation), Zeomic (Shinagawa Fuel Co., Ltd.)
Silver-based antibacterial agents such as Amenitop (manufactured by Matsushita Electric Industrial Co., Ltd.) and Ion Pure (manufactured by Ishizuka Glass Co., Ltd.), P-25
Titanium dioxide fine particles and sol-gel bodies such as (Nippon Aerosil Co., Ltd.) and ST-135 (Ishihara Sangyo Co., Ltd.), but are not limited thereto. or,
Examples of the composite particles include fine particles obtained by coating titanium dioxide with silica, and GYT (manufactured by Goyo Paper Industries Co., Ltd.).
It is not limited to this. One of the high-molecular antibacterial agents is a phosphonium salt-based vinyl polymer represented by the following general formula [Chemical Formula 1].

[0012]

Embedded image

(R ₁ , R ₂ and R ₃ are a hydrogen atom, an alkyl group or an aryl group substituted with a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxyl group or an alkoxy group; Or an aralkyl group;
-Represents an anion, and n represents an integer of 2 or more. 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 phenyl. And an aryl group such as tolyl and xylyl, an aralkyl group such as benzyl and phenyl, a hydroxy 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 a halogen ion is preferable. n is not particularly limited, but 2 to 50
0, preferably 10 to 300. Another example of the phosphonium base-containing polymer compound is a copolymer polyester mainly comprising a phosphonium salt of a dicarboxylic acid component and a sulfonic acid group-containing aromatic dicarboxylic acid in an amount of 1 mol% to 50 mol% and a glycol component.

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 cyclohexanone-1,4-dicarboxylic acid and derivatives thereof, and aliphatic dicarboxylic acids include adipic acid, sebacic acid, dodecandioic 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 of 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-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, and tri-n-butylhexadecylphosphonium sulfoisophthalate. Tri-n-butyltetradecylphosphonium sulfoisophthalate, n-butyldodecylphosphonium sulfoisophthalate, 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, 4-
And tri-n-butyldodecylphosphonium salts of sulfonaphthalene-2,7-dicarboxylic acid. From the viewpoint of antibacterial activity, tri-n-butylhexadecylphosphonium sulfoisophthalate and tri-n-butyltetrasulfoisophthalate. Decyl phosphonium salts and tri-n-butyl dodecyl phosphonium sulfoisophthalate are particularly preferred.

The above-mentioned phosphonium salts of aromatic dicarboxylic acids include sulfo-aromatic dicarboxylic acids or their sodium, potassium, ammonium salts and the like, as well as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide and tri-n-butyltetradecylphosphonium bromide. It can be obtained by reacting a phosphonium salt such as n-butyldodecylphosphonium bromide. The reaction solvent at this time is not particularly limited, but water is most preferable. For the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation, the copolymerized polyester may contain, in addition to a polymerization catalyst such as antimony oxide, germanium oxide, or a titanium compound, magnesium salts such as magnesium acetate and magnesium chloride, calcium acetate, and calcium chloride. Etc. C
a salt, Mn salt such as manganese acetate and manganese chloride, Zn salt such as zinc chloride and zinc acetate, Co salt such as cobalt chloride and cobalt acetate are each 300 ppm or less as metal ions, phosphoric acid or trimethyl phosphate, phosphoric acid It is also possible to add a phosphoric ester derivative such as triethyl ester as P in an amount of 200 ppm or less.

The total amount of metal ions other than the polymerization catalyst is 3
If the amount exceeds 00 ppm or the amount of P exceeds 200 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, heat resistance,
From the viewpoint of hydrolysis resistance and the like, the molar ratio between the total P amount and the total metal ion amount is preferably 0.4 to 1.0.

[0018]

(Equation 1)

The molar atomic ratio is less than 0.4 or 1.0
When the ratio exceeds the above range, coloring of the composition of the present invention and generation of coarse particles become remarkable, which is not preferable. The molecular weight of the organic high-molecular-weight antibacterial agent is not particularly limited, but in the case of a copolymerized polyester, the molecular weight is from 5,000 to 50,000, preferably 1
0000 or more and 30,000 or less, more preferably 150
It is not less than 00 and not more than 25000. When the molecular weight is 5,000 or less, the mechanical strength of the antibacterial composition of the present invention is insufficient, which is not preferable for practical use. The method for producing the copolymerized polyester is not particularly limited, but a so-called direct polymerization method of directly reacting dicarboxylic acids and glycols to polycondensate an obtained oligomer, a transesterification reaction between dimethyl ester of dicarboxylic acid and glycol. A so-called transesterification method of performing polycondensation after the reaction is performed, and an arbitrary 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 by polycondensation during the preparation of raw materials, that is, before transesterification or esterification. It is preferably added before the reaction. The synthesis of the phosphonium base-containing polymer is not limited to the above method, and other synthesis methods include adding a tri-n-butyltetradecylphosphonium bromide to a sulfonic acid (or salt) group-containing polymer.
Reaction of a phosphonium salt such as tri-n-tetradecylphosphonium 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. Organic compounds or polymer compounds containing at least one of carboxyl groups or alkali metal salts thereof, sulfonic acid groups or alkali metal salts thereof, quaternary ammonium bases and amine bases, such as polyoxymethylene chains and polyoxyethylene chains And a polyoxypropylene chain. A 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, polyacrylimide, poly (N, N-dimethylaminomethylacrylamide),
Poly (N, N-dimethylaminoethyl acrylate),
Poly (N, N-dimethylaminoethyl methacrylate), polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, polyvinylimidazole, homopolymer or copolymer of polyacrylic acid, homopolymer or copolymer of polymethacrylic acid, maleic anhydride Homopolymer or copolymer (for example, maleic anhydride / styrene copolymer), polyvinyl sulfonic acid or copolymer thereof or alkali metal salt thereof, polystyrene sulfonic acid or copolymer thereof or alkali metal salt thereof, polystyrene Quaternary ammonium salt derivatives, polyvinyl imidazoline salts, polyallylamine salts, polyethylene glycol (also known as polyethylene oxide) polypropylene glycol, polyethylene propylene glycol, polytetrame Polyalkylene glycol such as tylene glycol, polyol such as glycerin, polyglycerin or a polymer thereof, alkali or ammonium salt of sulfoisophthalic acid is 1 mol% or more and 10 mol or more.
Examples thereof include polyesters copolymerized at 1% or less. In addition, these polyalkylene glycols, polyglycerols may be alcohols, alkylphenols, fatty acids, polyether derivatives blocked with amines, etc., for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide adduct, Derivatives such as fatty acid esters or fatty alcohol ethers, polyglycerin fatty fatty acid esters, polyglycerin fatty alcohol ethers, polyglycerin ricidyl ethers, and reaction products thereof can be given. Among them, polyethylene glycol, polyglycerin and derivatives thereof are preferred from the viewpoint of improving compatibility with polyester and antibacterial properties.

The molecular weight of the hydrophilic substance is not particularly limited. In the case of polyethylene glycol, the number average molecular weight is preferably 200 or more and 30,000 or less, more preferably 100 or less.
It is preferably from 0 to 25,000. The hydrophilic substance (in the case of a copolymer, it refers to a hydrophilic substance contained in the copolymer)
Although the amount of addition is not particularly limited, when polyethylene glycol is added as a hydrophilic substance, it is 0.1 to 20% by weight, preferably 0.5 to 10% by weight based on the total amount of the inorganic and organic antibacterial agents. More preferably, it is 1 to 5% by weight. If the amount 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 antimicrobial composition are undesirably reduced. The method for incorporating the hydrophilic substance into the inorganic and / or organic antibacterial agent is not particularly limited, and the method for producing the inorganic and / or organic antibacterial agent, mixing, melting and kneading depending on the chemical properties and physical properties, ion Any method such as bonding, covalent bonding, and copolymerization can be adopted.

In particular, the addition of a hydrophilic substance to an organic polymer antibacterial agent can take the form of copolymerization as well as mixing. For example, the glycols, polyols, alkali or ammonium salts of sulfoisophthalic acid,
Bonding a copolymerizable hydrophilic substance (monomer) such as vinylpyrrolidone, acrylic acid, styrene sulfonic acid or the like to the polymer main chain or side chain of the polyester, polyamide, polyolefin or the like having the antibacterial component,
It is preferable from the viewpoint of preventing 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.

Further, a method in which an inorganic and / or organic antibacterial agent and a hydrophilic substance are heated and melt-mixed using an extruder or the like; A method of adding a hydrophilic substance or a monomer to the reaction system during or after the reaction, or a method of adding an inorganic and / or organic antibacterial agent and a hydrophilic substance to a suitable solvent, for example, water, a water / alcohol mixed solvent ,
After mixing and dissolving or dispersing in an organic solvent such as acetone and methyl ethyl ketone, the solvent is dried.
The hydrophilic substance in the antibacterial composition obtained by the above process may be present in any form such as a covalent bond, an ionic bond, a copolymer, or a mixture with an inorganic antibacterial agent and an organic antibacterial agent. However, in the case of an organic antibacterial agent, it is preferable that the hydrophilic substance be present in the form of a copolymer from the viewpoint of the life of the antibacterial activity.

The antimicrobial composition of the present invention has slipperiness and abrasion resistance.
Of physical properties such as resistance, blocking resistance, concealment, etc.
For the purpose, the antibacterial composition contains calcium carbonate (C
aCO _Three), Calcium phosphate, apatite, burr sulfate
Um (BaSO_Four), Calcium fluoride (CaF_Two),
Talc, kaolin, silicon oxide (SiO_Two),alumina
(Al_TwoO_Three), Titanium dioxide, zirconium oxide (Z
rO_Two), Iron oxide (Fe_TwoO_Three), Alumina / silica double
Inorganic particles such as oxides, polystyrene, polymethacrylate
Acrylates, polyacrylates and their copolyesters
Add organic particles such as coalesced or cross-linked products thereof
It is also possible. More details about the above particles
This is as follows.

Calcium carbonate particles are classified into three crystal forms, calcite classified into trigonal or hexagonal system, aragonite classified into orthorhombic system, and vaterite classified into hexagonal or pseudo-hexagonal system. Is classified as
Any crystal type 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. Examples of the alumina include crystalline alumina hydrates such as gibbsite, bayerite, nordstrandite, boehmite, diamond bore, todite; amorphous alumina hydrates such as amorphous gel, boehmite gel, bayerite gel; , Η, γ, χ, κ, δ, θ-type intermediate activated alumina or α-type alumina. The average particle size is not particularly limited because 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.
% By weight or less is preferred. 5000 ppm of particles added
In the case of exceeding, the coarse particles in the inorganic and / or organic antibacterial agent become remarkable, coarse protrusions are conspicuous on the surface of the antibacterial film obtained therefrom, the particles easily fall off, and the quality of the film is deteriorated. . The method of filling and mixing the 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 particles in the system, and a method of synthetic polymerization of the organic antibacterial agent There are a method of adding and dispersing the fine particles in the reaction system, and a method of adding the particles to the polymer and melt-mixing, particularly when the organic antibacterial agent is a thermoplastic polymer.

When the organic antibacterial agent is polyester,
The particles are usually added to the polyester polymerization 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, 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 and / or organic antibacterial agent. For the polyester sealant layer of the antibacterial laminate of the present invention, a copolymerized polyester is used. Examples of the copolymerized polyester component include polyethylene terephthalate, acid components such as isophthalic acid, adipic acid, sebacic acid, azelaic acid, and 1,4-cyclohexanecarboxylic acid, and diethylene glycol, polytetramethylene glycol, 1,3-butanediol, and propylene. Glycol components such as glycol are exemplified, but the acid component and glycol component constituting the copolymerized polyester are not limited to these. By copolymerizing these copolymer components in an amount of 20 mol% or more, proper heat sealability as a sealant can be obtained.

As a method of laminating the antibacterial laminate of the present invention, a conventional method such as a coextrusion method, an extrusion lamination method, a hot melt lamination method, a dry lamination method, or a wet lamination method can be adopted. . In the co-extrusion method, the layers can be easily laminated by extruding from a plurality of extruders and laminating with a combining adapter or the like. In the dry lamination method and the wet lamination method, an adhesive is preferably interposed on the lamination surface. As a coating method, a method such as gravure roll coating, reverse roll coating, dip coating, doctor blade, and air knife coating is used. As a method of laminating a multilayer body of four or more layers, any of the above methods may be used alone, or a combination of any two or more methods may be used.

The structure of the antimicrobial laminate of the present invention can be selected arbitrarily within the scope of claims 1 to 7 according to the purpose of use and application. Furthermore, in order to add performance other than the above to the antibacterial laminate of the present invention, it is possible to adopt a configuration of five or more layers. For example, a packaging material having excellent gas barrier properties is constituted by an antibacterial composition resin / polyester / aluminum foil / polyester sealant / antibacterial composition resin, an antibacterial composition resin / polyester / polyvinylidene chloride / polyester sealant / antibacterial composition resin, etc. Obtainable. As a method for obtaining a packaging bag having antibacterial properties using the antibacterial laminate of the present invention, as a sealing method, a bar sealing method, a rotating roll sealing method, an impulse sealing method, a fusing sealing method, a hot melting sealing method, an ultrasonic sealing method Method, high-frequency sealing method, etc., and it is possible to select any method,
As the form of the obtained bag, an arbitrary form such as a pillow packaging bag, a three-side seal bag, a four-side seal bag, or the like can be selected according to the purpose. However, an example of a method of obtaining the above-described antibacterial laminate structure and a packaging bag made of the antibacterial laminate is merely an example, and is not limited to the above example.

(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 compositions obtained in Examples and Comparative Examples will be described. Antibacterial test S. diluted with 1/50 broth aureus (Staphylococcus aureus) bacterial solution (concentration: 10 7 cells / ml) 0.1 m
1 was dropped onto a 5 cm × 5 cm film previously sterilized by high pressure steam, 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. Then, the bacteria on the film are washed out with 10 ml of SCDLP medium, and 1
After diluting 0-fold and spreading on a normal agar plate, the number of bacteria was counted 24 hours later.

Example 1 (A) Preparation of antimicrobial composition and coating solution 5 mol of dimethyl terephthalate, 4 mol of dimethyl isophthalate, tri-n-butylhexadecylphosphonium of dimethyl 5-sulfoisophthalate 1 mol of salt, 22 mol of ethylene glycol, zinc acetate (Zn) with respect to the theoretical amount of copolyester
And the transesterification reaction was carried out while evaporating the methanol produced by elevating the temperature from 140 to 220 ° C. to the outside of the system. After transesterification, 250 ° C
0.12 mol of polyethylene glycol having a molecular weight of 10,000 (Nacalai Co., Ltd.), 250 ppm of antimony oxide as antimony (Sb) and 80 ppm of trimethylphosphonate as P based on the theoretical amount of the resulting copolymerized polyester. Stir for 15 minutes, then add 2000 ppm of spherical silica having an average particle size of 0.9 microns.
Was added. A polycondensation reaction was performed at 260 ° C. under vacuum for 60 minutes to obtain a copolymerized polyester resin having an intrinsic viscosity of 0.50. The above polymer was dissolved in commercially available special grade methyl ethyl ketone to obtain a 6 wt% solution.

(B) Preparation of Laminated Film Using terephthalic acid as an acid component and ethylene glycol as a glycol component, and further adding 30 mol% of isophthalic acid to produce a copolyester having an intrinsic viscosity of 0.60, a polyester sealant Used as layer material. On the other hand, as the material of the polyester layer, the limiting viscosity is 0.1.
60 polyethylene terephthalates were used.

For extruding the film, two extruders were used. The extruding temperature was 280 ° C. to 290 ° C., and one of the extruders contained the copolymerized polyester and the other extruded the polyethylene terephthalate. The mixture was supplied and co-extruded into a film while being laminated in a T-die to obtain a laminated film of a polyester sealant layer and a polyester layer. At this time, the extrusion amounts of both materials were adjusted, the thickness ratio of the polyester layer and the polyester sealant layer was adjusted to 5: 1, and the thickness of the laminated film was adjusted to 230 μm. This laminated film is referred to as T.I. M. Using a film stretcher manufactured by Long Co., the film was subjected to sequential biaxial stretching of 3.5 times × 3.6 times at 90 ° C. in the machine and transverse directions, and then heat-set at 220 ° C. for 15 seconds. The thickness of the obtained laminated biaxially stretched film is about 18μ.
m. The coating liquid obtained in the above (A) is applied to the polyester layer side of the obtained biaxially stretched laminated film by a bar coater method, and dried with hot air at 80 ° C., and then the above (A) is applied to the polyester sealant layer side of the laminated film. The coating solution obtained in (1) was similarly applied by a bar coater method and dried at 80 ° C. with hot air. The final coating amount of the coating agent (antibacterial composition) on the film was about 0.4 g / m ² on both film surfaces. Table 1 shows the antibacterial evaluation results of the obtained laminated film on the antibacterial composition-coated side.

(Examples 2 to 8) An antimicrobial laminated film was obtained in the same manner as in Example 1 except that the kind and amount of polyethylene glycol were changed as shown in Table 1.
The antibacterial property was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 1.

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

(Comparative Examples 1 to 3) An antibacterial laminated film was obtained in the same manner as in Examples 1, 9, and 10 except that polyethylene glycol was not added. The antibacterial properties were evaluated in the same manner as in
It was shown to.

The substances in Table 1 represent the following substances. T: Terephthalic acid I: Isophthalic acid C16: Tri-n-butylhexadecylphosphonium salt of 5-sulfoisophthalic acid C14: Tri-n-butyltetradodecylphosphonium salt of 5-sulfoisophthalic acid C12: 5-Sulfoisophthalic acid Tri-n-butyl dodecyl phosphonium salt EG: ethylene glycol PEG: polyethylene glycol

Example 11 (A) Preparation of Antibacterial Composition Coating Solution Calcium carbonate fine particles having an average particle size of 0.5 μm were 4000
1 part by weight of silver / phosphoric acid per 100 parts by weight of terephthalic acid / isophthalic acid // ethylene glycol / polyethylene glycol (molecular weight: 1000) (50/40 // 95/5 molar ratio) copolymer dispersed at a concentration of ppm Zirconium antibacterial filler, Novalon (Toa Gosei Chemical Co., Ltd.)
Was added and mixed in a commercially available reagent, methyl ethyl ketone, to give a 6% by weight solution.

(B) Preparation of Laminated Film Using terephthalic acid as an acid component and ethylene glycol as a glycol component, and further adding 30 mol% of isophthalic acid to produce a copolyester having an intrinsic viscosity of 0.60, a polyester sealant Used as layer material. On the other hand, as the material of the polyester layer, the limiting viscosity is 0.1.
60 polyethylene terephthalates were used. The extruding temperature was set to 280 ° C. to 290 ° C. using two extruders for film formation, and the copolymerized polyester was supplied to one extruder and the polyethylene terephthalate was supplied to the other extruder. A laminated film of a polyester sealant layer and a polyester layer was obtained by co-extrusion into a film while being laminated in a T die. At this time, the extrusion rates of both materials were adjusted, the thickness ratio of the polyester layer and the polyester sealant layer was 5: 1, and the thickness of the laminated film was 2
It was adjusted to 30 μm. This laminated film is referred to as T.I. M. Using a film stretcher manufactured by Long Co., the film was subjected to sequential biaxial stretching of 3.5 times × 3.6 times at 90 ° C. in the machine and transverse directions, and then heat-set at 220 ° C. for 15 seconds. The thickness of the obtained laminated biaxially stretched film was about 18 μm. The coating solution obtained in the above (A) was applied to the polyester layer side of the obtained biaxially stretched laminated film by a bar coater method.
After drying with hot air at 0 ° C., the coating liquid obtained in the above (A) was similarly applied to the polyester sealant layer side of the laminated film by a bar coater method, and dried with hot air at 80 ° C. The final coating amount of the coating agent (antibacterial composition) on the film was about 0.4 g / m ² on both film surfaces. Table 2 shows the evaluation results of the antibacterial properties of the obtained laminated film on the antibacterial composition-coated side.

(Examples 12 and 13) The same as Example 11 except that the inorganic antibacterial agents shown in Table 2 were used instead of the silver / zirconium phosphate antibacterial filler (Toagosei Co., Ltd.) in Example 11. To obtain an antimicrobial laminated film,
Table 2 shows the evaluation results of the antibacterial properties on the polyester side of the laminated film obtained in the same manner as in Example 11. In addition, P-
The antibacterial property of the 25-containing system was evaluated while illuminating black light at a distance of 40 cm.

(Comparative Examples 4 to 6) The procedure of Example 11 was repeated, except that a copolymer of terephthalic acid / isophthalic acid // ethylene glycol (60/40 // 100 molar ratio) was used instead of the copolymer. Antibacterial laminated films were obtained in exactly the same manner as in Examples 11, 12, and 13. The evaluation results of the antibacterial properties on the polyester side of the laminated films obtained in the same manner as in Example 11 are shown in Table 2.

(Example 14) (A) Preparation of sulfonic acid group-containing polyester and aqueous dispersion First, sulfonic acid group-containing polyester was prepared by the following method. Using 55 mol% of dimethyl terephthalate, 45 mol% of dimethyl isophthalate and 5 mol% of sodium 5-sulfoisophthalate as dicarboxylic acid components,
Transesterification and polycondensation were carried out by a conventional method. 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-containing polyester having a solid content of 5%.

(B) Preparation of Mixed Coating Solution 0.1 parts by weight of silver / zirconium phosphate antibacterial filler, Novalon (Toagosei Co., Ltd.) was added to 100 parts by weight of the above (A) aqueous dispersion of sulfonic acid group-containing polyester. The mixture was added, mixed and finely dispersed to obtain a coating solution. (C) Adjustment of Film A base film was prepared in the same manner as in Example 11 except that the coating liquid was changed, and then a coating liquid was applied to form a laminated film. The final coating weight of the film was 0.5 g /
m ² . Table 3 shows the results of evaluating the antibacterial properties of the coated surface of the obtained film.

(Examples 15 and 16) Same as Example 14 except that the inorganic antibacterial agents shown in Table 3 were used in place of the silver / zirconium phosphate antibacterial filler (Toagosei Co., Ltd.). To obtain an antimicrobial laminated film,
Table 3 shows the evaluation results of the antibacterial properties of the coating-coated surface of the film in the same manner as in Example 11. The antibacterial evaluation of the P-25-containing system was performed while illuminating a black light at a distance of 40 cm.

(Example 17) (A) Preparation of antimicrobial composition coating liquid 4000 fine calcium carbonate particles having an average particle size of 0.5 μm
Copolymerized polyester dispersed at a concentration of ppm (terephthalic acid / isophthalic acid // ethylene glycol / polyethylene glycol (molecular weight 20,000) = 60/40 /
After adding 2 parts by weight of a silver / zirconium phosphate-based antibacterial filler (manufactured by Toagosei Co., Ltd.) to 100 parts by weight of (/ 95/5 molar ratio), the mixture was dissolved in a commercially available special-grade reagent methyl ethyl ketone to obtain a 6% by weight solution.

(B) Preparation of Laminated Film Using terephthalic acid as an acid component and ethylene glycol as a glycol component, and further adding 30 mol% of isophthalic acid to produce a copolyester having an intrinsic viscosity of 0.60, a polyester sealant Used as layer material. On the other hand, as the material of the polyester layer, the limiting viscosity is 0.1.
60 polyethylene terephthalates were used. The extruding temperature was set to 280 ° C. to 290 ° C. using two extruders for film formation, and the copolymerized polyester was supplied to one extruder and the polyethylene terephthalate was supplied to the other extruder. A laminated film of a polyester sealant layer and a polyester layer was obtained by co-extrusion into a film while being laminated in a T die. At this time, the extrusion rates of both materials were adjusted, the thickness ratio of the polyester layer and the polyester sealant layer was 5: 1, and the thickness of the laminated film was 2
It was adjusted to 30 μm. This laminated film is referred to as T.I. M. Using a film stretcher manufactured by Long Co., the film was subjected to sequential biaxial stretching of 3.5 times × 3.6 times at 90 ° C. in the machine and transverse directions, and then heat-set at 220 ° C. for 15 seconds. The thickness of the obtained laminated biaxially stretched film was about 18 μm. The coating solution obtained in the above (A) was applied to the polyester layer side of the obtained biaxially stretched laminated film by a bar coater method.
After drying with hot air at 0 ° C., the coating liquid obtained in the above (A) was similarly applied to the polyester sealant layer side of the laminated film by a bar coater method, and dried with hot air at 80 ° C. The final coating amount of the coating agent (antibacterial composition) on the film was about 0.4 g / m ² on both film surfaces. Table 4 shows the evaluation results of the antibacterial properties of the obtained laminated film on the side on which the antibacterial composition was applied.

(Examples 18 to 19) The same as Example 17 except that the inorganic antibacterial agents shown in Table 2 were used in place of the silver / zirconium phosphate antibacterial filler (Toagosei Co., Ltd.). To obtain an antimicrobial laminated film,
Table 4 shows the evaluation results of the antibacterial properties of the coating-coated surface of the film in the same manner as in Example 17. The antibacterial evaluation of the P-25-containing system was performed while illuminating a black light at a distance of 40 cm.

(Comparative Examples 10 to 12)
Antimicrobial laminates were produced in exactly the same manner as in Examples 17, 18, and 19, except that a copolymerized polyester (terephthalic acid / isophthalic acid // ethylene glycol = 60/40 // 100 molar ratio) was used in place of the copolymer in Example 19. Preparation of the film and evaluation of antibacterial properties were performed, and the results in Table 4 were obtained.

(Embodiments 20 to 31)
In Table 19, instead of polyethylene glycol,
3 types of polyglycerin, polyglycerin # 31
0, polyglycerin # 500, polyglycerin # 750
(Sakamoto Pharmaceutical Co., Ltd.), polyvinyl alcohol (PV
Except for using A), preparation of antibacterial laminated films and evaluation of antibacterial properties were carried out in exactly the same manner as in Examples 17, 18, and 19, and the results shown in Table 5 were obtained.

Example 32 The antibacterial composition-containing layer obtained by applying the antibacterial laminated film shown in Examples 1 to 31 on a polyester sealant was used as the inner surface of the bag, and three sides were sealed by the impulse sealing method. Is filled with a methylene blue test solution, and the remaining one is similarly sealed by the impulse sealing method to form a four-side sealed bag filled with the test solution, and left in a thermostat at 45 ° C. ± 2 ° C. for 24 hours. As a result of the examination, all the results were good without any liquid leakage.
As described above, by using the packaging material and the packaging bag comprising the antibacterial laminate according to the present invention to cover and package, it is possible to impart antibacterial properties to an article originally having no antibacterial property, and to enhance the antibacterial properties according to the present invention. Various articles having antibacterial activity can be provided. Therefore, in a field that requires sterilization, it is possible to manufacture an article with added value such as maintaining its effect.

[0051]

By using the packaging material and the packaging bag comprising the antibacterial laminate of the present invention, a high antibacterial property can be imparted to an article having no antibacterial property in a retrofitted form. A package having a characteristic antimicrobial agent on the surface can be provided. In addition, by adding a photocatalytic function, it is possible to obtain a packaging material, a packaging bag, and a packaging body that exhibit stronger antibacterial properties by irradiating near-ultraviolet light in an optional step.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

Claims (7)

[Claims] Claims: 1. An at least four or more laminate packaging material comprising a polyester layer, a polyester sealant layer and an antimicrobial composition-containing layer, wherein the outermost layers on both sides of the laminate are mainly composed of an inorganic and / or organic antimicrobial agent. Consisting of a polyester resin layer containing an antibacterial composition comprising a hydrophilic substance,
An antimicrobial laminated packaging material in which a polyester layer is laminated on the inner layer side in contact with the outermost layer on one side, and a heat-sealable polyester sealant layer is laminated on the inner layer side in contact with the outermost layer on the other side. 2. The antibacterial laminated packaging material containing an antibacterial substance according to claim 1, wherein an organic antibacterial agent and a hydrophilic substance are copolymerized. 3. The method according to claim 1, wherein the inorganic antibacterial agent is an inorganic compound carrying at least one metal particle and / or metal ion of silver (Ag), zinc (Zn), and copper (Cu). The antibacterial laminated packaging material according to any one of claims 1 and 2, wherein 4. The method according to claim 1, wherein the inorganic antibacterial agent is titanium oxide (TiO.sub.2).
₂₎ and / or antimicrobial laminated packaging material containing any antimicrobial composition of claim 1, wherein comprises zinc oxide (ZnO _2). 5. The method according to claim 1, wherein the organic antibacterial agent is a polymer compound containing an ammonium base and / or a phosphonium base and / or a sulfonium base in a main chain or a side chain. Antibacterial laminated packaging material containing an antibacterial substance. 6. The method according to claim 1, wherein the hydrophilic substance comprises a hydroxyl group, an amino group,
At least one of 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, a polyether chain, and a polyamine chain.
2. A high molecular compound containing a seed.
An antibacterial laminated packaging material containing any of the antibacterial substances according to any one of claims 1 to 5. 7. A packaging bag comprising the antibacterial laminated packaging material according to claim 1.