JP2001026086A - Laminating film of antibacterial resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide film, excellent in antibacterial properties and durability. SOLUTION: In the laminating film of an antibacterial resin, an antibacterial resin composition is laminated on a base material film, in which polyamide resin is a main body. The antibacterial resin composition contains polyester resin and ionization radiation polymerizable curing type resin. Polyester resin is formed as a constituent component mainly containing a dicarboxylic acid component and a glycol component or hydroxycarboxylic acid. The constitutional component contains a compound shown by a formula. (in formula, A is aromatic group and X1 and X2 are ester formable functional group and R1, R2, R3 and R4 are alkyl group and at least one of R1, R2, R3 and R4 is (10-20) C alkyl group.) Herein, furthermore, the antibacterial resin component contains hydrophilic substance or the hydrophilic substance is bonded to polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester resin containing a phosphonium base, an ionizing radiation-curable resin, an antibacterial composition containing a hydrophilic substance, and a laminate. These have excellent antibacterial properties and practical resin properties, and are particularly suitable for producing antibacterial binders, antibacterial molded products, antibacterial sheets, antibacterial films and the like.

[0002]

2. Description of the Related Art Polyamide resins and molded articles using the same, particularly films, have excellent transparency, moldability, and mechanical properties, and are used for packaging fresh foods, processed foods, pharmaceuticals, medical equipment, electronic components, and the like. It is used as an industrial film for industrial films, building materials, home appliances and the like. Gas barrier properties, moisture resistance, as a food packaging film required transparency, for example, laminated metal foil such as aluminum,
Those coated with vinylidene chloride or ethylene vinyl alcohol copolymer are known. Further, as a device using an inorganic thin film, a device in which a deposited film of silicon oxide, aluminum oxide, or the like is laminated is also known. Also, for packaging seasonings such as miso or soy sauce, moisture-containing foods such as soups and retort foods, and chemicals, a sealant layer is provided by a dry lamination method, or a polyamide film is provided by providing a sealant layer by an extrusion lamination method. Is known. More recently, in order to prevent the destruction of the laminated structure due to dimensional change due to boiling or retort treatment, a laminated film in which an aromatic polyamide is mixed with an aliphatic polyamide or an aromatic polyamide or polyethylene terephthalate is extruded in a multilayer is proposed. .

[0003] In recent years, the packaging of foods has changed drastically due to changes in the distribution of foods and dietary habits, and the required characteristics of packaging films have become increasingly severe. Deterioration of product quality due to the effects of temperature, moisture, oxygen, ultraviolet rays, and microorganisms such as bacteria and mold in the distribution and sales process is a serious problem not only in terms of sales but also in terms of food hygiene. As a method of preventing such quality deterioration, antioxidants and preservatives have been added directly to foods in the past, but in recent years, regulations on food additives have become stricter from the standpoint of consumer protection. In such a situation, there is an increasing demand for a packaging film that does not cause deterioration in quality under such circumstances.

Recently, as one of the solutions to such a problem, an antibacterial product in which an inorganic or organic antibacterial agent is filled or applied to a packaging film has been devised. For example, natural products such as chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract antibacterial agent, inorganic materials such as photooxidation catalyst titanium oxide particles, zinc oxide ultrafine particles, silver-containing zeolite, and silver-containing zirconium phosphate. Packaging films to which compound products and synthetic products such as organic ammonium salt-based compounds and organic phosphonium salt-based compounds are added.

[0005] Inorganic antibacterial agents typified by natural or synthetic silver are safe in terms of toxicity and have recently received attention, and the following inventions have already been disclosed.

For example, Japanese Patent Publication No. 63-54013 discloses an example in which an antibacterial zeolite ion-exchanged with silver ions or copper ions is blended. JP-A-3-8390
5. JP-A-3-83906 discloses a phosphate-based antibacterial agent containing silver ions. JP-A-3-161409 discloses an antibacterial agent in which a certain amount of ions in a zeolite having a specific ion exchange capacity are replaced with silver ions.

When these antimicrobial agents are added to a polyamide resin film, the antimicrobial activity is insufficient if the addition amount is relatively low, while if the addition amount is large, the transparency must be sacrificed, and It is difficult to achieve both antibacterial and antibacterial properties, and there is room for improvement in practical use.

On the other hand, antibacterial agents of organic synthetic products generally have better antibacterial activity against fungi and the like than natural products and inorganic products. However, when these antibacterial agents are surface-coated or filled on a substrate such as a film, the antibacterial agent has a low molecular weight, so that it is easily volatilized, desorbed and separated from the substrate such as a film, and the antibacterial property does not last for a long time. Moreover, it is not preferable in terms of safety to the human body. Therefore, when using an antibacterial agent in a film or the like,
It is preferable that the antibacterial agent does not dissolve in water, an organic solvent, or the like, and is hardly released, detached, peeled, or dropped off from the film surface from the viewpoint of long-term stability of the antibacterial performance and safety to the human body.

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

Japanese Unexamined Patent Publication (Kokai) 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.

Japanese Patent Application Laid-Open No. 61-245378 describes 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, 63-609
Nos. 03, 62-114903, JP-A-1-93596, JP-A-2-240090, etc., like various nitrogen-containing compounds, phosphonium salt compounds have a broad activity spectrum against bacteria as a biologically active chemical substance. Is described as having.

An invention has been disclosed 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 of a phosphonium salt-based vinyl polymer, and further discloses JP-A-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, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed.

The present inventors have disclosed JP-A-4-266912,
Japanese Patent Application Laid-Open No. 5-310820 was studied diligently, and a laminate was formed by synthesizing a phosphonium base-containing vinyl copolymer and a copolymerized polyester according to the example and applying the same on a polyamide film, and the antibacterial property was evaluated. Antibacterial activity was insufficient. Furthermore, in order to improve the antibacterial properties, a polyester was synthesized in which trinormal butyldodecylphosphonium base was bonded at 50 mol% or more, and a film was prepared from the polyester. However, the mechanical properties of the polymer decreased due to the coloring of the polymer and the decrease of the glass transition point. In addition, the antibacterial properties were insufficient.

Further, the above-mentioned organic antibacterial agent was mixed with a polyamide resin to form a film, a sheet, and the like, and the antibacterial properties against Staphylococcus aureus, Escherichia coli and the like were evaluated. .

[0016]

SUMMARY OF THE INVENTION The present invention provides a laminated film having high antibacterial activity after solving the above-mentioned conventional problems. Specifically, the present invention provides an antibacterial composition that can improve antibacterial activity by laminating on a polyamide film substrate even with a small amount of antibacterial agent, and furthermore, practically provides a polyamide film laminated with the antibacterial composition. It is intended to provide durability that can withstand the use of the.

[0017]

Accordingly, the present inventors have intensively studied measures for improving the antibacterial property without unnecessarily increasing the amount of phosphonium base, which is an antibacterial component, and imparting practically necessary durability. As a result, the present invention has been achieved. According to the present invention, the following films are provided.

1) The present invention is a laminated film of an antimicrobial resin comprising an antimicrobial resin composition laminated on a base film mainly composed of a polyamide resin, wherein the antimicrobial resin composition comprises a polyester resin and ionizing radiation. A polymerizable curable resin, wherein the polyester resin is formed mainly from an ester-forming component containing a dicarboxylic acid component and a glycol component, and the ester-forming component contains a compound represented by the following formula (I):

[0019]

Embedded image

Wherein A is an aromatic group, X₁, And X_TwoIs
Ester-forming functional group, R₁, R_Two, R _Three, And R_FourIs
A alkyl group;₁, R_Two, R_Three, And R_FourSmall of
At least one is an alkyl group having 10 to 20 carbon atoms.
is there. Here, the antibacterial resin composition further comprises a hydrophilic substance
Or a hydrophilic substance is contained in the polyester resin.
It is bound to fat.

2) The film according to 1), wherein the polyester resin is a copolymerized polyester obtained by copolymerizing the compound of the general formula (I) with 1 to 50 mol% based on all acid components.

3) The film according to 1) or 2), wherein the compound of the formula (I) is derived from a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid.

4) The film according to any one of 1) to 3), wherein the hydrophilic substance is a polyalkylene oxide and / or a derivative thereof.

5) The film according to any one of 1) to 3), wherein the hydrophilic substance is a vinyl polymer having a hydrophilic group in a side chain, and the vinyl polymer is graft-polymerized to the polyester.

6) The hydrophilic substance is a high molecular substance, and a main chain of the high molecular substance is copolymerized with a compound capable of forming an ester containing a metal sulfonate group.
3) The film of any one of the above.

7) The ionizing radiation-polymerizable curable resin contains an ionizing radiation-polymerization initiator, an ionizing radiation-polymerizable prepolymer and / or an ionizing radiation-polymerizable monomer.
The film according to any one of 1) to 6).

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antimicrobial resin laminated film of the present invention will be described in detail.

As used herein, the term "antibacterial" refers to the ability to kill bacteria and / or molds or inhibit their growth. The antibacterial resin composition refers to a resin composition having antibacterial properties.

The polyamide resin, which is a main component of the base film of the antibacterial laminated film of the present invention, is a high molecular compound having an amide bond (-CONH-) as a repeating unit. By ring-opening polymerization, 2) by polycondensation of aminocarboxylic acid,
3) Polycondensation of diamine and dibasic acid.

As specific examples, nylon 6, nylon 6
-6, nylon 11, nylon 12, nylon 4-6,
Aliphatic polyamide resins such as nylon 6-10 and nylon 6-12, poly (hexamethylene terephthalamide),
Examples thereof include aliphatic-aromatic polyamide resins such as poly (hexamethylene isophthalamide) and poly (meta-xylene adipamide), and copolymers and mixtures thereof. Among these, the polyamide resins used in the present invention include nylon 6, nylon 6-6, and nylon 6.6-6.
An aromatic ring-containing polyamide resin composed of a copolymer, a hexamethylene terephthalamide unit, a hexamethylene isophthalamide unit, and a hexamethylene adipamide unit is preferred.

The substrate film may be composed of only one kind of polyamide resin, or a plurality of kinds of polyamide resins may be blended.

The polyamide resin used in the present invention can be produced by a known method. Although the molecular weight of the polyamide resin used in the present invention is not particularly limited, the relative viscosity at a temperature of 25 ° C. and a concentration of 1 g / dl in 98% by weight sulfuric acid is preferably 1.5 to 4. The polyamide resin used in the present invention preferably has a ratio of the terminal carboxyl group concentration to the terminal amino group concentration in the range of 1.0 to 6.0, more preferably 1.0 to 5.0.
When the ratio is in the range of 0, and the ratio is too large or too small, the thermal stability is apt to decrease, and it is difficult to obtain a good film.

The base film mainly composed of the polyamide resin of the present invention may be composed of a single layer composed of the above-mentioned polyamide resin, or composed of a multilayer structure in which two or more resins are laminated. Is also good. The film having a laminated structure can be manufactured by a known method.

For example, a method in which the resin constituting each layer is melted in a separate extruder and co-extrusion is carried out, a method in which a plurality of films are formed and then laminated by lamination, a method in which these are combined, and the like. Can be taken. As an example of the laminated film, a laminated polyamide film having a layer configuration of A / B or A / B / A can be given. Here, the polyamide resin used for the layer represented by A is represented by the following X and Y of 50 to 100 and 50, respectively.
~ 0 parts by weight. More preferably, X, Y
(X): an aromatic polyamide resin component (a) composed of terephthalic acid or isophthalic acid and an aliphatic diamine, and an aliphatic polyamide-based resin. A mixture / copolymer of (b),
A resin composition containing at least 10 mol% of the aromatic polyamide resin component (a), (Y): an aliphatic polyamide resin.

The resin used for the layer B is, for example, nylon 6, nylon 6-6, nylon 1
2 and the like.

Further, the polyamide base film of the present invention may be used as an unstretched film or as a stretched film. In order to improve the processability of the film, it is desirable to use the film after stretching it uniaxially or biaxially. As the stretching method, a known method such as a tenter-type sequential biaxial stretching method, a tenter-type simultaneous biaxial stretching method, and a tubular method can be used.

In the polyamide film of the present invention, if necessary, an antioxidant, an ultraviolet absorber, a heat stabilizer, a light stabilizer, a dye, and the like which are added to a usual polyamide resin within a range not to impair the object of the present invention. , A coloring agent such as a pigment, a plasticizer, a lubricant, a release agent, a nucleating agent, a flame retardant, and the like may be added, or another thermoplastic resin may be blended.

As used herein, the term "ester-forming component" refers to a component capable of participating in an ester bond in the polyester, and specifically includes, for example, dicarboxylic acid, glycol,
And hydroxycarboxylic acids.

As the dicarboxylic acid, any of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid and heterocyclic dicarboxylic acid can be used. Aromatic dicarboxylic acids are preferred. Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. When an aromatic dicarboxylic acid is used, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, a heterocyclic dicarboxylic acid, or the like may be used in combination, if necessary. Examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
And cyclohexanedicarboxylic acid. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, eicosandicarboxylic acid, dimer acid and derivatives thereof. As the heterocyclic dicarboxylic acid,
Pyridinecarboxylic acid and its derivatives are exemplified. If necessary, a hydroxycarboxylic acid such as p-hydroxybenzoic acid or a polyvalent carboxylic acid such as trimellitic anhydride or pyromellitic anhydride may be used in combination as long as the content of the invention is not impaired.

Of these, aromatic dicarboxylic acid was added in an amount of 70 mol% for practical durability when laminated on a substrate film.
It is preferable to include the above. As the other dicarboxylic acid used in combination with the aromatic dicarboxylic acid, 1,4-dicarboxylic acid, adipic acid, and sebacic acid are particularly preferable.

The glycol components include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, neopentyl glycol, , 6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,9-nonanediol, 1,10 -Alkylene glycols such as -decanediol; alicyclic glycols such as 1,2-cyclohexanedimethanol; alkylene oxide adducts of bisphenol A or F; diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

In addition, a small amount of amide bond, urethane bond,
Glycols containing an ether bond or a carbonate bond can also be used.

Among these, ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,5-hexane are more preferable for practical durability when formed into a laminated film. Pentanediol, 3-methyl-1,5-pentanediol, 1,
4-cyclohexanedimethanol.

The above-mentioned glycol may be optionally used,
Polyhydric polyols such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination.

Examples of the hydroxycarboxylic acid component that can be used in the polyester resin in the present invention include salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, α-hydroxynaphthalenecarboxylic acid, β-hydroxynaphthalenecarboxylic acid and the like. .

In a preferred embodiment, the polyester resin used in the film of the present invention is a polyester resin obtained by copolymerizing a compound represented by the following general formula (I) in an amount of 1 to 50 mol% based on all acid components:

[0047]

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 or aryl groups, at least one of which is carbon Number 10
And 20 or less alkyl groups).

The compound represented by the general formula (I) which is an ester-forming component used in the polyester resin of the present invention includes a dicarboxylic acid wherein X ₁ and X ₂ are both carboxyl groups, and X ₁ and X ₂ are Glycols, both of which are hydroxyl groups, and hydroxycarboxylic acids, in which one of X ₁ and X ₂ is a carboxyl group and the other is a hydroxyl group, are mentioned.

Examples of the phosphonium salt of the aromatic dicarboxylic acid having a sulfonic acid group of the above formula (I) include tri-n-butyldecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, and sulfoisophthalic acid. Tri-n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, sulfoisophthalic acid-n
-Butyldodecylphosphonium 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-
Butylhexadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-
Tri-n-butyldodecylphosphonium dicarboxylate, etc .; from the viewpoint of antibacterial activity, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, sulfoisophthalate Tri-n-butyldodecylphosphonium salts 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, Tri-n-
It is obtained by reacting a phosphonium salt such as butyldodecylphosphonium bromide. The reaction solvent at this time is not particularly limited, but water is most preferable.

The method for producing the polyester resin 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 method in which a dimethyl ester of dicarboxylic acid and a glycol are esterified. Polycondensation after exchange reaction, so-called transesterification method, method of polycondensing oligomer obtained by directly reacting hydroxycarboxylic acid, preparing methyl ester of hydroxycarboxylic acid, and after transesterification A polycondensation method, a combination thereof, and the like can be given, and an arbitrary production method can be applied.

In producing the polyester, a polymerization catalyst such as antimony oxide, germanium oxide, or a titanium compound may be added for the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation. In addition to these polymerization catalysts, magnesium acetate, Mg salts such as magnesium chloride, calcium acetate, Ca salts such as calcium chloride, manganese acetate, Mn salts such as manganese chloride, zinc chloride, Zn salts such as zinc acetate, cobalt chloride, A Co salt such as cobalt acetate may be added. The metal ions are added in an amount of 300 ppm or less.
It is also possible to add phosphoric acid or phosphoric acid ester derivatives such as phosphoric acid trimethyl ester and phosphoric acid triethyl ester. In this case, it is preferably added in an amount of 200 ppm or less as a P element content.

When the total amount of the metal ions other than the polymerization catalyst is too large or the P content is too large, the polymer is liable to be colored, and the heat resistance and the hydrolysis resistance of the polymer are liable to decrease.

At this time, in terms of heat resistance, hydrolysis resistance, etc., the total P element content (P) and the total metal ion content (M)
Is preferably 0.4 to 1.0.

[0056]

(Equation 1)

If the molar ratio (P / M) is too small or too large, coloring of the composition or generation of coarse particles tends to be remarkable.

The timing of addition of the above metal ions and phosphoric acid and its derivatives is not particularly limited. Generally, metal ions are added at the time of charging raw materials, that is, before transesterification or esterification, and the addition of phosphoric acids is carried out by polycondensation. It is preferably added before the reaction.

In the radically polymerizable prepolymer, the ionizing radiation polymerization initiator is added to start the reaction of the acryloyl group in a short time and promote the reaction, and acts as a catalyst. Photoinitiators include those that undergo radical polymerization by self-cleavage and those that undergo radical polymerization by abstracting hydrogen. The former include benzoin ethers, dialkoxyacetophenones,
Hydroxyacetophenones, morpholinoacetophenones and the like are used, and the latter include benzophenones, cyclic benzophenones, benzyl and the like, and one or more of these can be used. In the ionic polymerizable prepolymer, the ionizing radiation polymerization initiator is a compound that releases a catalyst component that initiates cationic polymerization by absorbing ionizing radiation energy, and includes an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, A metallocene compound or the like is used. The compounding amount of the ionizing radiation polymerization initiator is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the total solid content of the ionizing radiation polymerizable prepolymer and the ionizing radiation polymerizable monomer. To use. Here, the solid content includes, by weight, those which become solid by ionizing radiation polymerization.

The ionizing radiation-polymerizable curable resin contains, as necessary, an ionizing radiation-polymerizable monomer in addition to the ionizing radiation-polymerizable prepolymer and the ionizing radiation polymerization initiator. In particular, a radical polymerizable prepolymer is effective for diluting a high-viscosity ionizing radiation polymerizable prepolymer to lower the viscosity and improve workability, and for imparting coating strength as a crosslinking agent. Examples of the ionizing radiation polymerizable monomer for radical polymerization include monofunctional acrylic monomers such as 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, and 1,6.
One or more of a bifunctional acrylic monomer such as hexanediol diacrylate and a polyfunctional acrylic monomer such as trimethylolpropane triacrylate may be used.

In the present invention, the antibacterial resin composition contains a hydrophilic substance, or the hydrophilic substance is bonded to the polyester resin. The presence of a hydrophilic substance significantly improves antibacterial properties.

The hydrophilic substance in the present invention is a substance having an excellent affinity for water, and is dissolved, dispersed or retained in water, moisturized,
Or a swellable substance, generally having one molecule of a hydrophilic group such as 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, or a derivative thereof, or an ether bond. Is an organic compound or a polymer compound containing two or more of them.
Specific examples thereof include polyvinyl alcohol, starch, a homopolymer or copolymer of polyacrylic acid, a homopolymer or copolymer of polymethacrylic acid, and a homopolymer or copolymer of maleic anhydride (for example, maleic anhydride- Styrene copolymer), polyvinyl sulfonic acid or its copolymer or an alkali metal salt thereof, polyalkylene glycol such as polyethylene glycol (also known as polyethylene oxide) polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, glycerin, polyglycerin Or a polymer thereof, or a water-soluble modified cellulose (eg, hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, sodium carboxycellulose) , Cellulose nitrate carboxyl methyl ether) and the like. These are mixed and used in the polyester resin containing the phosphonium base.

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 amount of the hydrophilic substance added or copolymerized is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total of the polyester resin and the hydrophilic substance. And more preferably 1 to
5% by weight. If the amount is too small, the effect of increasing the antibacterial activity tends to be insufficient. If the amount is too large, the mechanical properties, heat resistance, and weather resistance of the antibacterial composition tend to decrease. The method of mixing with the hydrophilic substance is not particularly limited, and any method can be adopted depending on the method of producing the polyester resin, its chemical properties, and its physical properties. For example, a method in which both are melted by heating using an extruder or the like, or a method in which a polymer substance and a hydrophilic substance are mixed in an appropriate solvent, for example, water, a water / alcohol mixed solvent, an organic solvent such as acetone, methyl ethyl ketone, and cyclohexanone. After mixing and dissolving or dispersing in a solvent, there is a method in which the solvent is evaporated to dryness.

In addition, as a method for introducing a hydrophilic substance, a hydrophilic group such as 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 is added to a polyester resin containing a phosphonium base. Can be copolymerized with the main chain or side chain. By copolymerization, the compatibility is improved, and the appearance, storage stability, and physical properties of the laminated film are improved.

In the present specification, the hydrophilic group means
Also includes groups that can be converted to hydrophilic groups (eg, acid anhydride groups, glycidyl groups, chloro groups).

As a method of copolymerizing these copolymerizable compounds having a hydrophilic group, 5-sulfoisophthalic acid,
4-sulfonaphthalene-2,7-dicarboxylic acid, 5-
Sulfonate metal bases such as metal salts such as (4-sulfophenoxy) isophthalic acid and metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol A method of copolymerizing a dicarboxylic acid or glycol containing a polyester resin, a method of copolymerizing an alkylene glycol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol with a polyester resin, a vinyl-based monomer containing a hydrophilic group or a mixture thereof. Examples of the method include graft polymerization or graft addition of a polymer to a polyester resin.

In the present invention, the vinyl monomer having a hydrophilic group that can be grafted onto the polyester resin is changed to a vinyl monomer containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, or the like, or a hydrophilic group. Groups that can be mentioned include vinyl monomers containing acid anhydride groups, glycidyl groups, chloro groups, and the like. Among them, those having a carboxyl group are most preferred. 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-
Alkyl acrylates such as butyl acrylate and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, alkyl methacrylates such as t-butyl methacrylate, 2-hydroxyethyl acrylate, hydroxy-containing monomers such as 2-hydroxyethyl methacrylate, acrylamide Amides such as N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N, N dimethylolacrylamide, and N-phenylacrylamide Group-containing monomer, glycidyl acrylate,
Epoxy-containing monomers such as glycidyl methacrylate are exemplified.

Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, monomers containing a sulfonic acid group or a salt thereof such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof, Crotonic acid, itaconic acid, maleic acid,
Examples thereof include monomers containing a carboxyl group or a salt thereof such as fumaric acid and salts thereof, and monomers containing an acid anhydride such as maleic anhydride and itaconic anhydride.

The monomer having a hydrophilic group may be used alone or in combination with another monomer. Examples of the other monomer include vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, and vinyl chloride. Copolymerization can be performed using the type.

The ratio between the monomer having a hydrophilic group and the other monomer is preferably in the range of 30/70 to 100/0 in molar ratio. If the ratio of the monomer having a hydrophilic group is too low, the effect of enhancing antibacterial properties is not sufficiently exhibited.

As a method for grafting a monomer having a hydrophilic group to the polyester, 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 polymer of the main chain by light, heat, radiation or the like and then graft-polymerized with a monomer, or AlCl ₃ ,
There are a cation polymerization method in which cations are generated using a catalyst such as TiCl _4, and an anion polymerization method in which anions are generated using metal Na, metal Li, or the like. Another example is a method in which a radical polymerizable unsaturated double bond is previously introduced into a main chain polymer substance, and a vinyl monomer is reacted with the radical polymerizable unsaturated double bond. Examples of the monomer having a radical polymerizable unsaturated double bond used therein include fumaric acid, maleic acid, maleic anhydride, tetrahydromaleic anhydride and the like. 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 high molecular substance having a functional group introduced into a side chain is reacted with a branch polymer having a group which reacts with the above functional group at the terminal. For example the side chain -OH group, -SH group, -NH ₂ group, -COOH group, -
A polymer having a hydrogen donating group such as a CONH ₂ group, and one end having a —N ＝ C ＝ O group, a —C ＝ C ＝ O group,

[0075]

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A method of reacting with a vinyl copolymer which is a hydrogen-accepting group, or a method of reacting in a reverse combination thereof.

A preferred example of a method of grafting a vinyl monomer having a hydrophilic group onto a polyester resin containing a phosphonium base is to dissolve a hydrophobic polyester resin having a phosphonium base in an organic solvent and to form a radical initiator. And a method of reacting a mixture of radical polymerizable monomers such as vinyl monomers having a hydrophilic group. In this case, the reaction product after the completion of the grafting reaction is, in addition to the desired graft polymer between the polyester-radical polymerizable vinyl monomer mixture, the non-grafted polyester and the radical polymer not grafted to the polyester. Although it is a mixture containing a coalescence, the graft polymer in the present invention also includes such a mixture.

The preferred weight ratio of the polyester as the main chain and the vinyl monomer to be grafted is 95/5 to 40.
/ 60, more preferably 93 / 7-55.
/ 45, most preferably 90/10 to 60
/ 40 range. If the weight ratio of the main chain polymer is too small, the graft polymerizable vinyl-based monomer is likely to remain without completely reacting, so that the properties of the conventional polymer such as heat resistance, processability, water resistance, etc. are easily damaged. . On the other hand, when the weight ratio of the main chain polymer is too large, the effect of improving antimicrobial properties, which is the object of the present invention, is not sufficiently exhibited. There is no significant difference in the antibacterial effect between the case where the hydrophilic substance is mixed with the polymer substance and the case where the copolymer is copolymerized, and both have good antibacterial properties.

The present invention has one feature in blending an ionizing radiation polymerizable curable resin. Curable resins are broadly classified into thermosetting resins and ionizing radiation-curable resins, but ionizing radiation-curable resins are excellent from the viewpoints of flexibility in resin design, rapid curability, and work environment. Good film properties can be obtained by blending a curable resin. The ionizing radiation-curable resin is formed from a composition containing at least a resin that is cured by irradiation with an electron beam or ultraviolet rays. Specifically, it contains an ionizing radiation polymerization initiator and an ionizing radiation polymerizable prepolymer, and further includes an ionizing radiation polymerizable monomer, a photosensitizer, an additive such as a leveling agent, if necessary,
Contains solvents, etc.

The ionizing radiation polymerizable prepolymer undergoes radical polymerization or ionic polymerization of the reactive group inserted into the molecular skeleton by irradiation with ionizing radiation. An acrylic prepolymer having an acryloyl group is typical as the radical polymerizable prepolymer, and an epoxy prepolymer having an epoxy group is typical as the ionic polymerizable prepolymer. The acrylic prepolymer has two or more acryloyl groups in one molecule, and urethane acrylate, epoxy acrylate, polyester acrylate and the like can be used. The higher the number of functional groups, the faster the curability and the higher the hardness. As the epoxy-based prepolymer, epoxy oligomers such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, phenol novolak type and alicyclic type can be used. In the epoxy-based prepolymer, since the epoxy group cationically undergoes ring-opening polymerization, a thermal factor affects the curing reaction.
By heating to about ° C, the curing reactivity can be further increased. The preferable compounding amount of the ionizing radiation polymerizable prepolymer is 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the total of the polyester resin and the hydrophilic substance.
Department.

In the present invention, the antibacterial composition has a slip property,
In order to improve physical properties such as abrasion resistance, blocking resistance, concealing property, etc., calcium carbonate (CaC
O ₃ ), calcium phosphate, apatite, barium sulfate (BaSO ₄ ), calcium fluoride (CaF ₂ ), talc, kaolin, silicon oxide (SiO ₂ ), alumina (Al ₂
O ₃ ), titanium dioxide, zirconium oxide (ZrO ₂ ),
Inorganic particles such as iron oxide (Fe ₂ O ₃ ) and alumina / silica composite oxide, and organic particles such as polystyrene, polymethacrylate, polyacrylate, copolymers thereof, and crosslinked products thereof are added. It is also possible.

When the antimicrobial resin composition is irradiated with an ionizing radiation such as an electron beam or an ultraviolet ray, the photocurable resin reacts and cures, and good physical properties of the coating film can be obtained.

When irradiating an electron beam, a scanning type or curtain type electron beam accelerator is used,
000 keV or less, more preferably 100 to 300 ke
The irradiation can be performed by irradiation with an electron beam having an energy of V and preferably in a wavelength region of 100 nm or less. When irradiating ultraviolet rays, use a low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc, metal halide lamp, etc.
Preferably 100 to 400 nm, more preferably 200
In the wavelength region of ~ 400 nm, preferably 20 ~ 1500
Irradiation with ultraviolet light having an integrated light quantity of mj / cm ² is performed.

The antimicrobial resin composition is applied to a polyamide film sheet by a usual coating method such as bar coating, blade coating, gravure coating, spin coating, spray coating, dip coating and the like. Thereafter, after a drying step, if necessary, the layer is cured by irradiating it with an electron beam or ultraviolet rays to obtain a laminated film having a curable resin layer having excellent antibacterial properties and durability.

[0085] The coating amount of the antibacterial resin composition is preferably 0.005~10g / m ² as solid content, more preferably 0.02~2g / m ^2. If the coating amount is too small, it is difficult to obtain sufficient antibacterial activity. If the amount is too large, blocking tends to occur, and a problem tends to occur in practical use.

When applied on a biaxially stretched polyamide film, the polyamide film is subjected to a surface treatment such as a corona treatment, a flame treatment, or electron beam irradiation in order to further improve the adhesion between the polyamide film and the antibacterial resin composition layer. You may do. Even when the film is stretched after coating as described below, an effect can be obtained by the same treatment.

When the above antibacterial resin composition is applied to an unstretched or uniaxially stretched polyamide film substrate, and then dried and stretched, the drying temperature after application is within a range not affecting the subsequent stretching. In the case of a polyamide substrate, it is necessary to stretch the film so that the water content is 2% or less, and then heat-fix at 200 ° C. or more to make the coating film strong, and the antibacterial resin composition layer and the polyamide film substrate Adhesion with the material is dramatically improved. When the water content is 2% or more, depending on the drying temperature, crystallization is likely to occur, which may deteriorate the flatness and impair the stretchability.

The antimicrobial laminated film of the present invention may further have a gas barrier layer, a sealant layer, a printed layer or an adhesive layer for laminating them. Examples of the method of laminating the gas barrier layer include a method of laminating a metal foil such as aluminum, and a method of coating vinylidene chloride or an ethylene vinyl alcohol copolymer. As a method using an inorganic thin film, a method of depositing silicon oxide, aluminum oxide, magnesium oxide, a mixture thereof, or the like can be used.

The silicon oxide is composed of a mixture of various silicon oxides such as SiO or SiO ₂ , and the aluminum oxide is composed of a mixture of various aluminum oxides such as AlO or Al ₂ O ₃ . The amount of oxygen bonded differs depending on the production conditions.

In particular, a mixture of aluminum oxide and silicon oxide is preferable as the gas barrier layer in the present invention because of its excellent transparency and bending resistance. Further, the content of aluminum oxide in the gas barrier layer is 5% by weight or more.
A mixture of silicon oxide and aluminum oxide of 5% by weight or less is preferred.

If the amount of aluminum oxide in the silicon oxide / aluminum oxide-based vapor-deposited film is less than 5% by weight, there arises a problem that lattice defects occur in the vapor-deposited film and it is difficult to obtain a sufficient gas barrier property. When the amount of aluminum oxide in the aluminum oxide-based vapor-deposited film exceeds 45% by weight, the flexibility of the film is reduced, and the film is easily broken (cracked or peeled) due to a dimensional change during hot water treatment, and the barrier property is reduced. Easy to fall.

[0092] In a preferred embodiment, a heat seal layer made of a polyolefin resin for providing thermal adhesion is formed on the surface of the inorganic vapor deposition layer as a main purpose. The heat-sealing layer also has a function as a protective layer of the inorganic vapor-deposited layer, and in order to effectively perform the function, it is extremely effective to increase the adhesive force between the inorganic vapor-deposited layer and the heat-seal layer, As a means for that, it is extremely effective to provide an adhesive layer between the inorganic vapor deposition layer and the heat seal layer.

The heat seal layer is preferably made of a constituent polyolefin resin. The heat seal layer does not necessarily have to be a single layer and may be a multilayer.The resin constituting each layer when forming a multilayer structure, as well as a combination of the same type of resin, a copolymer of a different polymer, It may be a modified product or a blend. For example, the glass transition temperature (Tg) of the base thermoplastic polyolefin resin in order to improve the laminating property and the heat sealing property.
Alternatively, it is also possible to composite a polymer having a lower melting point or a composite having a high Tg or a higher melting point to impart heat resistance.

When a polyolefin resin is used in the heat seal layer, various additives such as a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, a filler, an antistatic agent, It is also possible to blend antibacterial agents, lubricants, antiblocking agents, other resins, and the like.

Particularly preferred as the resin constituting the adhesive layer is a resin having a glass transition temperature in the range of -10 ° C. to 40 ° C., such as a polyurethane resin, a polyester resin, an epoxy resin, a vinyl chloride resin, and acetic acid. Vinyl resins, polyethylene resins, polypropylene resins, melamine resins, acrylic resins, and the like. These can be used alone or, if necessary, in combination of two or more or by melt-mixing. Alternatively, for example, a compound having a carboxylic acid group, an acid anhydride, a (meth) acrylic acid or a (meth) acrylate skeleton as a functional group;
Epoxy compounds containing glycidyl or glycidyl ether groups; oxazoline groups, isocyanate groups, amino groups,
It is also effective to use an adhesive composition containing a curing agent or a curing accelerator having a reactive functional group such as a hydroxyl group.

The heat seal layer can be laminated on the inorganic vapor-deposited layer by a dry lamination method or a wet lamination method using an adhesive, and further by a melt extrusion lamination method or a co-extrusion lamination method.

The antibacterial resin laminated film of the present invention thus obtained can take advantage of its excellent antibacterial properties and the durability and secondary processing characteristics by boiling or retorting.
Packaging materials include miso, pickles, side dishes, baby food, boiled tsukudani, konjac, chikuwa, kamaboko, fishery products, meatballs, hamburgers, genghis khan, ham, sausage,
Other processed meat products, tea, coffee, black tea, dried bonito, kelp, potato chips, oil confectionery such as butter peanuts,
It can be effectively used for packaging rice crackers, biscuits, cookies, cakes, buns, castella, cheese, butter, cut rice cakes, soups, sauces, ramen, wasabi, toothpaste, etc., and furthermore, pet foods, pesticides, It can also be used effectively for industrial materials such as fertilizer, infusion packs, medical, electronic, chemical and mechanical such as semiconductor and precision material packaging. The form of the packaging material is not particularly limited, and can be widely applied to bags, lid materials, cups, tubes, standing packs, and the like.

[0098]

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.

The methods for measuring the physical properties of the antibacterial compositions obtained in Examples and Comparative Examples are described below.

1. Antibacterial test S.I. diluted with 1/500 broth aureus (Staphylococcus aureus) bacterial solution (concentration: 10 ⁶ cells / ml) 0.1
ml was dropped on a previously sterilized 5 cm × 5 cm sample film, and a sterilized polyethylene film was adhered to the film. The test piece was transferred to a sterile petri dish and cultured in an incubator at 37 ° C. and 90% RH for 24 hours.
Then, the bacteria on the film were washed with 10 ml of SCDLP medium, diluted 10-fold, and plated on an ordinary agar plate. After 24 hours, the number of remaining bacteria was counted. The antibacterial activity was evaluated by the bacteriostatic activity value according to the following formula. If the bacteriostatic activity value is 2.0 or more,
The antibacterial properties were judged to be good.

Bacteriostatic activity value = logA-logB A: 2 in polyester film having no antibacterial layer
B: Number of bacteria measured after culturing for 4 hours B: Number of bacteria measured after culturing for 24 hours in antibacterial film

2. Hot water resistance A sample having a size of 10 cm × 10 cm was immersed in 1 L of distilled water controlled at 95 ° C. ± 2 ° C. for 2 hours, and then taken out.
The change in the appearance of the coating film was evaluated.

：: No change in appearance Δ: Slight whitening observed X: Remarkable whitening observed

(Production Example 1 of Polyester Resin) Stirrer,
Dimethyl terephthalate 485 in a stainless steel autoclave with thermometer and partial reflux condenser
Parts, 388 parts of dimethyl isophthalate, 161 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 443.3 parts of ethylene glycol, 400.4 parts of neopentyl glycol, and tetra-n-
0.52 parts of butyl titanate was charged, and 160 to 220
The transesterification reaction was performed over 4 hours up to ° C. Then, 29 parts of fumaric acid was added, the temperature was raised to 200 to 220 ° C over 1 hour, and the pressure of the reaction system was gradually reduced.
1 hour and 30 minutes under reduced pressure of polyester (A-
1) was obtained. The composition of the polyester is as shown below.

Dicarboxylic acid component Terephthalic acid 40 mol% Isophthalic acid 50 mol% C12 phosphonium salt 5 mol% Fumaric acid 5 mol% Diol component Ethylene glycol 70 mol% Neopentyl glycol 30 mol%

In the same manner, various polyesters (A-2, A-3) shown in Table 1 were produced.

(Production Example 1 of Graft Polymer) In a reactor equipped with a stirrer, a thermometer, a reflux device and a fixed-rate dropping device, 300 parts of polyester (A-1), methyl ethyl ketone 3
60 parts and 120 parts of isopropyl alcohol were added, heated and stirred to dissolve the resin in a reflux state. After the resin is completely dissolved, 65 parts of acrylic acid and 35 parts of ethyl acrylate
Parts, a mixture of 1.5 parts of octyl mercaptan, 6 parts of azobisisobutyronitrile, and 90 parts of methyl ethyl ketone.
And a solution dissolved in a mixture of 30 parts of isopropyl alcohol were 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 (B-1).

The polyester (A-2,
A-3) is graft-polymerized to form a graft polymer (B-2,
B-3) was obtained.

(Production Example 2 of Graft Polymer) Same as Production Example 1 except that the amount of acrylic acid was changed to 20 parts and the amount of ethyl acrylate was changed to 10 parts in Production Example 1 of the graft polymer. The graft polymer solution (B-4) was obtained by the following method.

(Production Example 3 of Graft Polymer) In Production Example 1 of the graft polymer, 35 parts of N-methylacrylamide and 65 parts of acrylamide
Except that part was used, a graft polymer solution (B-5) was obtained in the same manner as in Production Example 1. (B-1) to (B
Table 2 shows the composition of -5).

Example 1 40 parts by weight of nylon 6, 60 parts by weight of a mixture of nylon 6T / nylon 6 copolymer (copolymerization ratio 50/50) as layer A, and 100 parts as layer B
A part by weight of nylon 6 is melt-extruded while being laminated from a T-die, and cooled on a rotating drum at 20 ° C. to a thickness of 150 μm.
Was obtained. This unstretched film was stretched 3.1 times in the machine direction at 50 ° C. Then 12
The film was stretched 3.3 times in the transverse direction at 5 ° C. and heat-set at 215 ° C. to obtain a biaxially stretched polyamide film having a thickness of 15 μm.

Graft polymer solution (B-1) solid content 10
Acrylic ionizing radiation polymerizable prepolymer (C-1: beam set 700; manufactured by Arakawa Chemical Co., Ltd.) for 0 parts
5 parts and 2.5 parts of a photoinitiator (D-1: Irgacure 907; manufactured by Ciba Geigy Co., Ltd.) are added, and the mixture is diluted with methyl ethyl ketone so that the total solid concentration becomes 17% by weight. And Then, a coating solution was applied to the surface of the layer A of the biaxially stretched polyamide film with a bar coater so that the coating amount was 3.0 g / m ^2, and the coating solution was dried in a hot air oven at 70 ° C. for 3 minutes, and then exposed to ultraviolet light. Ultraviolet rays having an integrated irradiation light amount of 800 mj / cm ² were irradiated by an irradiation device to be cured to form a laminate having a cured coating film on the surface layer. Table 3 shows the properties of the laminated film.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polyester (A-1) was dissolved in a mixture of methyl ethyl ketone and isopropyl alcohol in place of the graft polymer solution. A coating liquid is prepared, and then a biaxially stretched polyamide film A
A laminate having a cured coating film on the surface layer was formed. Table 3 shows the properties of the laminated film.

(Examples 2 to 4) Coating solutions were prepared in the same manner as in Example 1 except that the graft polymer solutions (B-2, 4, 5) were used. A laminate having a cured coating film on the surface layer A of the axially stretched polyamide film was formed. Table 3 shows the properties of the laminated film.

Comparative Example 2 A coating solution was prepared in the same manner as in Example 1 except that the graft polymer solution (B-3) was used. A laminate having a cured coating film on the surface layer A was formed. Table 3 shows the properties of the laminated film.

(Production Example 2 of Polyester Resin) Stirrer,
Dimethyl terephthalate 43 in a stainless steel autoclave with thermometer and partial reflux condenser
6.5 parts, 436.5 parts of dimethyl isophthalate, 5-
322 parts of tri-n-butyl dodecylphosphonium salt of sulfodimethylisophthalate, ethylene glycol 682
Parts, and 0.55 part of zinc acetate.
The transesterification reaction was carried out over 4 hours while evaporating the methanol generated by heating to 0 ° C. to the outside of the system. After completion of the transesterification reaction, polyethylene glycol having a molecular weight of 1,000 (manufactured by Nacalai Tesque, Inc.)
And 0.48 parts of antimony oxide and 0.28 part of trimethyl phosphate were added and stirred for 15 minutes. After the reaction system was gradually reduced in pressure, the mixture was reacted for 1 hour and 30 minutes under a reduced pressure of 0.2 mmHg to obtain a polyester ( A-4) was obtained. The composition of the polyester (A-4) is as shown below.

Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 45 mol% C12 phosphonium salt 10 mol% Diol component Ethylene glycol 98.9 mol% Polyethylene glycol 1.1 mol%

(Example 5) A one-pack type epoxy ionizing radiation polymerizable prepolymer containing a photoinitiator (C-2: Adeka KR566; Asahi Denka) After adding 33 parts (manufactured by Co., Ltd.), the mixture was diluted with methyl ethyl ketone so that the total solid concentration became 17% by weight to obtain a coating liquid. Then, after applying a coating solution to the surface of the layer A of the biaxially stretched polyamide film with a bar coater so that the coating amount becomes 3.0 g / m ² , the coating solution was dried in a hot air oven at 70 ° C. for 3 minutes,
Thereafter, ultraviolet rays having an integrated irradiation light amount of 900 mj / cm ² were irradiated with an ultraviolet irradiation device to be cured to form a laminate having a cured coating film on the surface layer. Table 3 shows the properties of the laminated film.

(Production Example 3 of Polyester Resin) Stirrer,
Dimethyl terephthalate 43 in a stainless steel autoclave with thermometer and partial reflux condenser
6.5 parts, 388 parts of dimethylisophthalate, 322 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 74 parts of sodium 5-sulfodimethylisophthalate, 443.3 parts of ethylene glycol,
400.4 parts of neopentyl glycol and 0.55 parts of zinc acetate were charged, and transesterification was carried out for 4 hours while heating the temperature to 160 to 220 ° C. and distilling off generated methanol outside the system. After completion of the transesterification reaction, 0.44 part of antimony and 0.28 part of trimethyl phosphate were added, and the mixture was stirred for 15 minutes. After gradually reducing the pressure of the reaction system, the mixture was reacted for 1 hour and 30 minutes under a reduced pressure of 0.2 mmHg to obtain an intrinsic viscosity. η = 0.50 dl / g polyester (A-
5) was obtained. The composition of the polyester (A-5) is as shown below.

Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 40 mol% C12 phosphonium salt 10 mol% 5-Sulfodimethyl sodium isophthalate 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol%

(Example 6) Acrylic ionizing radiation polymerizable prepolymer (C-3: M7100; manufactured by Toagosei Co., Ltd.) 35 based on 100 parts of solid content of polyester (A-5)
And 2.5 parts of a photoinitiator (D-1: Irgacure 907; manufactured by Ciba-Geigy Co., Ltd.), and then diluted with methyl ethyl ketone so that the total solid concentration becomes 17% by weight. did. Then, a coating solution was applied to the surface of the layer A of the biaxially stretched polyamide film with a bar coater so that the coating amount was 3.0 g / m ² , dried in a hot air oven at 70 ° C. for 3 minutes, and then irradiated with ultraviolet light. Ultraviolet rays having an integrated irradiation light amount of 800 mj / cm ² were irradiated by an irradiation device to be cured to form a laminate having a cured coating film on the surface layer. Table 3 shows the properties of the laminated film.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

[0125]

The polyamide film laminated with the antibacterial resin composition of the present invention has excellent antibacterial activity with a small amount of antibacterial component and has practically sufficient coating durability. It is suitable for packaging.

Continuation of the front page (72) Inventor Shigetsugu Konagaya 2-1-1 Katata, Otsu-shi, Shiga F-term in TOYOBO RESEARCH CO., LTD. EJ542 EJ862 GB15 GB23 GB66 JB14B JC00B 4J002 AB023 AB043 BE023 BG013 BG052 BH013 BH023 BN171 CF151 CH023 CH051 GF00 GG02 4J029 AA03 AB04 AB07 AC02 AE03 BA02 BA03 BA04 BA05 BA05 BA05 CA05 CD06 DA14 DB02 DC08 EA02 EB05A EC05A FC03 FC04 FC05 FC08 FC35 FC36 GA22 HA01 HB01 HB06 JA061 JA091 JB161 JC583 JE182 JF131 JF141 JF181 JF321 JF361 JF471 JF541 JF571 KB04 KB05 KE02 KE03 KE05 KH08

Claims (7)

[Claims] 1. An antimicrobial resin laminated film comprising an antimicrobial resin composition laminated on a base film mainly composed of a polyamide resin, wherein the antimicrobial resin composition comprises a polyester resin and an ionizing radiation polymerizable curable film. The polyester resin is mainly formed from an ester-forming component containing a dicarboxylic acid component and a glycol component, and the ester-forming component contains a compound represented by the following formula (I): (Where 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, and R ₁ and R ₂ , R ₃ , and R ₄ are at least one alkyl group having 10 to 20 carbon atoms.) Here, the antimicrobial resin composition further contains a hydrophilic substance, or Is bonded to the polyester resin. 2. The film according to claim 1, wherein the polyester resin is a copolymerized polyester obtained by copolymerizing the compound of the general formula (I) in an amount of 1 to 50 mol% based on all acid components. 3. The film according to claim 1, wherein the compound of the general formula (I) is derived from the phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid. 4. The film according to claim 1, wherein the hydrophilic substance is a polyalkylene oxide and / or a derivative thereof. 5. The method according to claim 1, wherein the hydrophilic substance is a vinyl polymer containing a hydrophilic group in a side chain, and the vinyl polymer is graft-polymerized to the polyester. the film. 6. The method according to claim 1, wherein the hydrophilic substance is a polymer substance,
2. The polymer according to claim 1, wherein an ester-forming compound containing a metal sulfonate group is copolymerized in the main chain of the polymer substance.
A film according to any one of claims 1 to 3. 7. The ionizing radiation polymerizable curable resin according to claim 1, wherein the resin comprises an ionizing radiation polymerization initiator and an ionizing radiation polymerizable prepolymer and / or an ionizing radiation polymerizable monomer. the film.