JP2000256482A - Antibacterial film - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a sufficiently high antibacterial property that satisfies practicality, in particular, antifungal property, and is not affected by excellent durability, transparency, heat resistance, smoothness, abrasion resistance and film thickness. To provide a film having good handling characteristics. SOLUTION: The antibacterial composition is contained in at least one surface layer of at least one surface of the film, and the change in the haze value of the film before and after immersion in boiling water for 100 hours is 1.
0% or less, mold resistance indication of 2 or more by an evaluation method according to JIS Z 2911 6.2, 2 or more of the mold resistance indication after immersing the film in boiling water for 100 hours, Dimensional surface roughness SRa is 0.
Antimicrobial film characterized by 02μm or less, projection density PCC value per unit area of roughness central plane of is not less 800 / mm ² or more and deflation speed is less than 900 seconds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent mold-proofing properties and practical durability, and exhibits excellent mold-proofing continuity without changing its appearance even after immersion in boiling water. The present invention also relates to an antibacterial film having excellent surface smoothness, excellent handling characteristics irrespective of the thickness of the film, and excellent abrasion resistance of the film surface.

[0002]

2. Description of the Related Art Thermoplastic resins, especially polyethylene, polypropylene, polyvinylidene chloride, nylon, polystyrene, polyethylene terephthalate and ethylene terephthalate, have excellent physical and chemical properties, and can be used for fibers, plastics, films, sheets and adhesives. It is used as an agent. Recently, antibacterial products in which an inorganic or organic antibacterial agent is filled or coated have been devised, and the uses thereof have been diversified.

At present, antibacterial agents mainly studied or used include natural products such as chitin, chitosan, wasabi extract mustard extract, hinokitiol, tea extract antibacterial agent, photooxidation catalyst titanium oxide particles, and zinc oxide superoxide. Examples include inorganic compounds such as fine particles, silver-containing zeolite, and silver-containing zirconium phosphate, and synthetic products such as organic ammonium salt-based and organic phosphonium salt-based compounds. Natural products and inorganic antibacterial agents typified by silver are safe in terms of toxicity and have recently received attention, and the following inventions have already been disclosed. That is, JP
JP-83905 discloses a silver ion-containing phosphate-based antibacterial agent, 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. , Respectively.

However, when films and sheets were prepared according to the inventions disclosed therein and their antibacterial properties against Staphylococcus aureus, Escherichia coli and the like were evaluated, the antibacterial activity was insufficient when the addition amount was relatively low. Therefore, when the amount added is increased in order to improve the antibacterial activity, there is a problem that discoloration due to heat at the time of melt extrusion or deterioration of weather resistance occurs.

On the other hand, antibacterial agents of organic synthetic products are generally superior in antibacterial performance to fungi and the like to natural products and inorganic products, but the antibacterial agents are coated or filled on a substrate such as a film. In this case, 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 from the viewpoint of long-term stability of antibacterial properties and safety to the human body. When using antibacterial agents for films, etc.,
It is preferable that the antibacterial agent does not dissolve in water or an organic solvent and is hardly released, detached, peeled, or dropped off from the film surface from the viewpoint of long-term stability of the antibacterial performance and safety to the human body.

Under 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 sheet, or the like by an ionic bond or a covalent bond has been disclosed. For example, JP-A-54-86584 discloses an antibacterial material mainly composed of a polymer substance containing an antibacterial agent component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid. Is described. Japanese Patent Application Laid-Open No. 61-245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a polar group such as an amidine group or a quaternary ammonium base.

Further, JP-A-57-204286,
JP-A-63-60903, JP-A-62-114903
JP-A-1-93596, JP-A-2-240090
As described in the publications such as Japanese Patent Publication No. H06-131, as well as various nitrogen-containing compounds, phosphonium salt compounds are known as biologically active chemicals having a broad activity spectrum against bacteria. Also disclosed are inventions in which these phosphonium salts are immobilized on a polymer substance to attempt to expand the use thereof. For example, Japanese Patent Application Laid-Open No. 4-266912 discloses an antibacterial agent for a phosphonium salt-based vinyl polymer.
No. 4365 discloses an antibacterial agent of vinylbenzylphosphonium salt-based vinyl polymer. Further, JP-A-5-310820 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. Among them, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed.

Japanese Patent Application Laid-Open No. 6-41408 does not mention any antibacterial action. However, it is useful as a photographic support, packaging, general industrial use, magnetic tape, or the like, as a copolymer of a sulfonium phosphonium salt copolymerized polyester. And polyalkylene glycols are disclosed. The alkyl group bonded to the phosphonium salt described in this patent specification is disclosed in
Unlike -310820, butyl and phenyl groups,
It has a benzyl group and a relatively short carbon number.

The present inventors have disclosed in Japanese Patent Laid-Open No. 4-266912
JP-A-4-814365, JP-A-5-31082
After careful study based on the description of No. 0, phosphonium base-containing vinyl copolymer and copolymerized polyester were synthesized according to the examples to form films, sheets, etc., and the antibacterial polymer thereof was applied on the film sheet surface. The antibacterial and fungicidal properties were evaluated by evaluating the antibacterial and fungicidal properties, the sustained effect after immersion in boiling water, the change in appearance before and after, and the handling properties as a film. And whitening phenomenon occurs after immersion in boiling water,
Poor handling characteristics during film formation and processing,
In addition, due to poor slipperiness due to contact with a guide roll or the like during running of the film, abrasion or the like was generated, and the utility was poor.

In addition, various films such as nylon, polystyrene, polyethylene terephthalate, and polyester are excellent in heat resistance and transparency, particularly in biaxially stretched films, and are used for packaging, magnetic tape, capacitors, photoengraving, building materials, and the like. It is deployed for various uses such as home appliances. When used for these films, their slipperiness and abrasion resistance are major factors that affect the workability of the film manufacturing process and the working process in each application, and the quality of the product. On the other hand, it is strongly required that the film surface be smooth and have good transparency, or that the film be thin from the viewpoint of cost reduction. However, if the surface is simply smoothed and made transparent and thin, poor handling characteristics during film production and processing, and poor slipperiness due to contact with guide rolls etc. during film running may cause abrasion or chipping. Occurs and the wear resistance becomes poor. In addition, particularly when an organic low-molecular-weight antibacterial agent is added to impart an antibacterial active ingredient, the brittleness increases and the abrasion resistance during running of the film decreases. As a film having a good sliding property, a film having a limited surface roughness Ra by adding inorganic particles (JP-A-3-744)
37), etc., these films having good slip properties can provide good handling characteristics at low-speed operation, but have a problem that the handling characteristics rapidly deteriorate at high-speed operation. Also, when the thickness of the film is reduced, the handling characteristics tend to deteriorate. However, the same tendency is also observed in a film in which the above-described inorganic particles are added and the surface roughness Ra and the range of the static friction coefficient are defined. Even if good handling characteristics are obtained, there is a problem that desired handling characteristics cannot be obtained if the thickness changes.

[0011]

The object of the present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide a sufficiently high antibacterial property which satisfies practicality, especially high fungicide resistance against fungi, and To provide a film having excellent properties that does not cause a change in appearance while exhibiting a long-lasting effect of mold resistance even after being immersed in boiling water, and having sufficient durability to withstand,
And excellent in transparency, heat resistance and smoothness of the film surface,
Good handling characteristics irrespective of film thickness,
Another object of the present invention is to provide an antimicrobial film having good abrasion resistance on the film surface.

[0012]

According to the antibacterial film of the present invention, the change in haze value of the film before and after immersion in boiling water for 100 hours is 1.0% or less per 10 μm, and JIS Z
2911 The mold resistance display by the evaluation method according to 6.2 is 2 or more, and the mold resistance display after immersing the film in boiling water for 100 hours is 2 or more, and at least one surface of the film has a three-dimensional surface. Roughness SRa is 0.02 μm
A sufficiently high antibacterial property, characterized in that the number of projections per unit area on the center surface of the roughness is not less than 800 / mm ² and the air bleeding speed is not more than 900 seconds, Among them, it has high mold resistance against mold,
Furthermore, it provides a film having excellent properties enough to withstand practical use, in particular, a film having excellent properties that does not cause a change in appearance while exhibiting a sustaining effect of mold resistance even after immersion in boiling water, and transparency, heat resistance and film. It is intended to provide an antibacterial film having excellent surface smoothness, good handling characteristics irrespective of the thickness of the film, and good abrasion resistance of the film surface. A preferred embodiment of the present invention is an antibacterial film containing a polymer substance having an organic antibacterial agent component bound to a main chain or a side chain.In a preferred example, the organic antibacterial agent component has a main chain or a side chain. The polymer substance bonded to the chain is a polymer having at least one of an ammonium base, a phosphonium base and a sulfonium base in a main chain and / or a side chain. In an even more preferred example, the antibacterial film is an antibacterial film mainly composed of a polyester-based composition, and particularly preferably a biaxially stretched film.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antibacterial film of the present invention will be described in more detail. The antibacterial film of the present invention contains an antibacterial composition. Here, the “antibacterial composition” refers to a composition capable of killing bacteria and / or molds or suppressing their growth, and the antibacterial composition in the present invention comprises an organic antibacterial agent component. It is a polymer substance bonded to the main chain or side chain.

Some of the organic antibacterial agents have relatively high antibacterial and antifungal properties, but are generally easily eluted and do not maintain their antibacterial and antifungal effects. In particular, the tendency becomes more remarkable in hot water and boiling water. In the present invention, elution can be prevented by binding an organic antibacterial agent component to the main chain or side chain of the polymer substance,
Therefore, it was possible to maintain the antibacterial and antifungal effects.

The organic antimicrobial component is a general term for natural extracts, low molecular weight organic compounds and polymers having antibacterial properties, and generally refers to compounds containing elements such as nitrogen, sulfur and phosphorus. For example, as natural extracts, chitin, chitosan, wasabi extract, mustard extract, hinokitiol, tea extract, etc., as low molecular weight compounds, allyl isothiocyanate, polyoxyalkylene trialkyl ammonium, benzalkonium chloride, hexa Quaternary ammonium salts such as methylene biguanide hydrochloride, organic silicon quaternary
Quaternary phosphonium salts such as quaternary ammonium salts, tri-n-butylhexadecyldecylphosphonium chloride, tri-n-butyltetradecyldecylphosphonium chloride, tri-n-butyltetradodecyldecylphosphonium chloride, phenylamides and biguanides , Sulfoisophthalic acid tetraalkylphosphonium salt or diethyl thereof, imidazole / thiazole compound, thiocarbide compound, pyridine / quinoline compound and the like, but are not limited thereto.

Among these organic antibacterial agents, ammonium base,
Onium salts such as phosphonium bases and sulfonium bases,
A polymer in which an antibacterial active group such as a phenylamide group or a biguanide group is bonded to a main chain or a side chain is preferable, and a phosphonium salt compound having high antibacterial properties and a wide antibacterial spectrum is particularly preferable.

A preferred example is a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group. A more preferred example is a dicarboxylic acid component and a glycol component as main components and represented by the following general formula. A polyester resin obtained by copolymerizing a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid with 1 to 50 mol% based on all acid components.

[0018]

Embedded image

Wherein A is an aromatic group, X ₁ and X ₂ are ester-forming functional groups, and R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups, at least one of which has 10 carbon atoms. The polyester resin is obtained by copolymerizing a bifunctional aromatic sulfonate phosphonium salt represented by the formula (1) with an alkyl group of not less than 20) in an amount of 1 to 50 mol% based on all acid components constituting the polyester resin.

In addition, as one of the polymer substances, the following general formula

[0021]

Embedded image

(Wherein R ₅ , R ₆ and R ₇ are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms,
An aryl group, a hydroxy group, or an alkyl group substituted with an alkoxy group, an aryl group or an aralkyl group,
X ^- is an anion, n represents an integer of 2 or more. )), And a phosphonium salt-based vinyl polymer.

Specific examples of the above R ₅ , R ₆ , and R ₇ include:
Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, alkyl groups such as dodecyl, phenyl, tolyl, aryl groups such as xylyl, benzyl,
It is substituted with an aralkyl group such as phenyl, a hydroxyl group, an alkoxy group and the like, and an alkyl group, an aryl group and the like are particularly preferable. R ₅ , R ₆ and R ₇ are the same group,
It may be a different group. Examples of the anion X ^- include a halogen ion such as fluorine, lump, bromine or iodine, a sulfate ion, a phosphate ion, a perchlorate ion and the like. Among these, a halogen ion is preferable. n is not particularly limited, but is 2 to 500, preferably 10 to 300.
It is.

As the dicarboxylic acid component used in the polyester resin, terephthalic acid, isophthalic acid, 2,2
Examples thereof include 6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Further, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, a heterocyclic dicarboxylic acid, or the like may be used in combination within a range not to impair the content of the invention. Examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid,
Dodecanedicarboxylic acid, azelaic acid, eicoic acid, dimer acid and derivatives thereof. Heterocyclic dicarboxylic acids include pyridine carboxylic acid and its derivatives. Further, an oxycarboxylic acid such as p-oxybenzoic acid and a polyvalent carboxylic acid such as trimellitic anhydride and pyromellitic anhydride may be used in combination as long as the content of the present invention is not impaired.

Among them, it is particularly preferable that terephthalic acid or 2,6-naphthalenedicarboxylic acid is contained in an amount of 70 mol% or more from the viewpoint of boiling water resistance when formed into a film. Other dicarboxylic acids include 1,4-dicarboxylic acid,
Adipic acid and sebacic acid are particularly preferred.

As the glycol component, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1, Alkylene glycols such as 3-propanediol, 1,9-nonanediol and 1,10-decanediol; alicyclic glycols such as 1,2-cyclohexanedimethanol; alkylene oxide adducts of bisphenol A or F; diethylene glycol; polyethylene Glycol, neopentyl glycol of hydroxypivalic acid (HPN), polypropylene glycol, polytetramethylene glycol and the like.

In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond, or a carbonate bond may be contained.

Among these, the main constituent components more preferable than the boiling water resistance when formed into a film are ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol, and 1,5-pentane. Diol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanedimethanol, and it is particularly preferable to contain 70 mol% or more of ethylene glycol.

[0029] In addition, as long as the content of the invention is not impaired,
Polyhydric polyols such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination.

Examples of the phosphonium salt of a sulfonic acid group-containing aromatic dicarboxylic acid include tri-n sulfoisophthalate.
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butyl sulfoisophthalate Hexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate, n-butyldodecylphosphonium sulfoisophthalate, tri-n-butyldecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, -Sulfonaphthalene-2,
7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-
Tris-n-butyltetradecylphosphonium salt of sulfonaphthalene-2,7-dicarboxylic acid, tri-n-butyldodecylphosphonium salt of 4-sulfonaphthalene-2,7-dicarboxylic acid, and the like. Tri-n-butylhexadecylphosphonium isophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, and tri-n-butyldodecylphosphonium sulfoisophthalate are particularly preferred.

The phosphonium salt of an aromatic dicarboxylic acid is a sulfo aromatic dicarboxylic acid or a sodium salt thereof,
It can be obtained by reacting a potassium salt, an ammonium salt or the like with a phosphonium salt such as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide or tri-n-butyldotesylphosphonium bromide. The reaction solvent at this time is most preferably water, but is not particularly limited.

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, an Mg salt such as magnesium acetate or magnesium chloride; Calcium, Ca salts such as calcium chloride, manganese acetate,
Mn salts such as manganese chloride, Zn such as zinc chloride and zinc acetate
Salts, cobalt salts such as cobalt chloride, cobalt acetate, etc., each being 300 ppm or less as a metal ion, and phosphoric acid or a phosphate derivative such as trimethyl phosphate or triethyl phosphate being 200 ppm or less in terms of phosphorus (P). Is also possible.

When the total amount of metal ions other than the polymerization catalyst is more than 300 ppm and 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, in terms of heat resistance, hydrolysis resistance and the like, the molar ratio between the total P amount and the total metal ion amount is 0.4 to 0.4.
It is preferably 1.0. The molar ratio (molar atomic ratio) of these additives is represented by the following formula.

[0035]

(Equation 1)

When the molar atomic ratio is less than 0.4 or more than 1.0, the composition of the present invention is not preferable because coloring and generation of coarse particles become remarkable.

The method for producing the polyester is not particularly limited, but is a direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed, a transesterification of a dimethyl ester of dicarboxylic acid with glycol. A so-called transesterification method in which polycondensation is performed after the reaction is performed, and any of these production methods can be applied.

The timing of addition of the metal ions and phosphoric acid and derivatives thereof is not particularly limited. Generally, metal ions are added at the time of charging raw materials, that is, before transesterification or esterification. It is preferable to add the acids before the polycondensation reaction.

As the composition constituting the film, the above-mentioned antibacterial composition can be used alone to form the film, or can be used by mixing with other compositions other than the antibacterial composition. The antimicrobial composition is not necessarily required to be a single one, and two or more may be used, or two or more of the other compositions constituting the film may be used in combination. When mixing the antibacterial composition and other components constituting the film, if the compatibility of both is poor, the transparency of the film may be reduced and the appearance may be impaired, so a combination of a composition having good compatibility may be used. You have to choose.

Other compositions constituting the antimicrobial film of the present invention other than the antimicrobial composition include polyethylene,
Polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene, polyurethane, polyamide, polyimide, polyamideimide, and the like are applied. Among them, polyester, polyvinyl chloride, polystyrene and the like are preferable from the viewpoint of boiling water resistance.

In the present invention, the change in the haze value of the film before and after immersion in boiling water for 100 hours is not more than 1.0% per 10 μm, and the mold has a low mold resistance indicated by an evaluation method according to JIS Z 2911 6.2. Must be 2 or more, and the mold resistance display after immersing the film in boiling water for 100 hours must be 2 or more. 100 in boiling water
If the change in the haze value of the film before and after immersion for more than 1.0% per 10 μm, the appearance will be deteriorated when the film is used under high temperature and high humidity such as a wall material for a bathroom. In addition, if the film is immersed in boiling water for 100 hours and the mold resistance is not 2 or more, mold generation occurs when the film is used in a similar environment.

These can be achieved by selecting the composition constituting the above-mentioned film. According to the present invention, in addition to the above, the three-dimensional surface roughness SRa of at least one surface of the film is 0.02 μm or less, and the number of protrusions PCC value per unit area on the central surface of the roughness is 8
00 pieces / mm ² or more and air bleeding speed is 900
The present invention provides an antibacterial film having excellent smoothness on the surface of the film, excellent handling properties irrespective of the thickness of the film, and excellent abrasion resistance on the surface of the film, which is characterized in that the film thickness is not more than seconds.

Examples of the method for forming the antibacterial film of the present invention include the following methods, but are not limited thereto.

A method of forming an unstretched film by extruding the antibacterial composition alone or mixed with another composition into a sheet with a melt extruder, or by uniaxially or biaxially stretching after extrusion. A method of forming a biaxially stretched film may be mentioned, but a film forming method of biaxially stretching is preferable from the viewpoint of mechanical strength and dimensional stability of the film.

The film may be a single layer or a laminate of two or more layers. In order to exhibit the antibacterial performance required in the present invention, an antibacterial composition is provided on at least one surface of at least one surface of the film. Must be included. Examples of the method of laminating include a method of coextruding and laminating with a melt extruder, a method of laminating by extruding on another substrate film directly or through an adhesive layer with a melt extruder, and the like. Can be When the film is stretched, a known stretching method can be adopted. In the case of uniaxial stretching, for example, a method using longitudinal uniaxial stretching, horizontal uniaxial stretching or the like, and in the case of biaxial stretching, for example, in addition to the sequential two-strength stretching method in which longitudinal stretching and transverse stretching are performed in order, horizontal / longitudinal A stretching method such as a longitudinal stretching method, a longitudinal / horizontal / longitudinal stretching method, a longitudinal / longitudinal / horizontal stretching method can be employed, and is selected according to various properties such as required strength and dimensional stability. In order to improve dimensional stability, it is also effective to perform a heat setting treatment, a longitudinal relaxation treatment, and a horizontal relaxation treatment.

The three-dimensional roughness SRa, the PCC value of the number of protrusions on the center plane of the roughness, and the air bleeding speed are adjusted by the film forming conditions and lubricant particles. The type and amount of the lubricant particles are not particularly limited as long as the three-dimensional surface roughness SRa, the number of protrusions PCC value on the center surface of the roughness, and the air bleeding speed are within a predetermined range,
As inorganic particles, silica, titanium dioxide, talc, kaolinite, zirconium oxide, iron oxide, alumina, alumina / silica composite oxide, metal oxides such as aluminum borate, calcium carbonate, magnesium carbonate, calcium phosphate, barium sulfate, Metal salts such as calcium fluoride, and organic particles include polystyrene, polymethacrylate, polyacrylate, benzoguanamine / formaldehyde condensate, melamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, and copolydensates thereof Examples include particles that are inert to the film composition such as coalesced or crosslinked products thereof. One of these lubricants may be used alone, or two or more thereof may be used in combination. Also,
In the present invention, the surface of the particles can be modified using a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, or the like in order to improve adhesion, wettability, and dispersibility with the resin.

The lubricant used has an average particle size of 0.01 μm.
m to 1.0 μm, especially 0.05 μm to 0.8 μm
m or less, and the degree of variation of the particle diameter (the ratio between the standard deviation and the average particle diameter) is preferably 25% or less, and the amount of addition is 0.005% by weight based on 100% by weight of the film composition.
The content is preferably not less than 2.0% by weight and more preferably not less than 0.1% by weight and not more than 0.8% by weight. Also,
The shape of the lubricant particles preferably includes at least one kind having an area shape factor of 60% or more. This area shape factor is obtained by the following equation.

[0048]

## EQU2 ## Area shape factor = (projected cross-sectional area of particle / area of circle circumscribing particle) × 100 (%)

As the film composition used in the present invention, a film composition in which known antioxidants, antistatic agents, coloring agents, ultraviolet absorbers, light stabilizers and the like are appropriately blended, if necessary, can be used. . The compounding amount is the film composition 100
10% by weight or less relative to the weight% is desirable. If the amount exceeds 10% by weight, when the film is stretched, breakage during stretching tends to occur, resulting in poor production stability.

The three-dimensional roughness SRa of at least one surface of the antibacterial film of the present invention needs to be within a range of 0.02 μm or less. If SRa exceeds 0.02 μm, for example, the electromagnetic conversion characteristics will be poor in magnetic tape applications, and the withstand voltage characteristics will decrease in film capacitor applications.

Further, it is necessary that the number of protrusions PCC per unit area on the central surface of the roughness is 800 / mm ² or more. If the PCC value is less than 800 pieces / mm ² , the running characteristics will be poor. Although there is no particular upper limit for the PCC value, it is difficult to increase the number to 3000 / mm ² or more when SRa is 0.02 μm, so the upper limit is naturally determined.

Further, the air bleeding speed of the antibacterial film of the present invention needs to be 900 seconds or less. More preferably, it is 700 seconds or less. That is, by setting the air bleeding speed to 900 seconds or less, more preferably 700 seconds or less,
At the time of high-speed operation, an antibacterial film having good handling characteristics can be obtained regardless of the thickness and strength of the film.
Conversely, if the air bleeding speed exceeds 900 seconds, the handling characteristics during high-speed work will be poor. For example, when the film is wound in a roll at high speed, air is taken in between the film and the take-up roll. Wrinkles are likely to occur, the winding appearance is poor, and the film meanders in the width direction due to the lubricating effect of the air layer in which the film is wound, causing irregularities in the roll end faces.

[0053]

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 these Examples.

The methods for measuring the physical properties of the antibacterial films obtained in the examples and comparative examples are described below.

<1. Mold resistance test> JIS Z 2911
A mixed solution obtained by attaching a sample film of 5 cm × 5 cm on an inorganic salt agar medium plate by a method according to 6.2.2 and adding 5% of sucrose to a spore suspension of the following five mold strains: 0.2 ml was sprayed and the growth status of the mold after 28 days of culture at 27 ± 1 ° C. was evaluated.

(Test strain) Aspergillus niger ATCC 6275 Penicillium citrinum ATCC 9849 Chaetomium globosum ATCC 6205 Rhizopus stolonifer ATCC 10404 Aureobasidium pullulans IFO 6353

(Indication of mold resistance) (1) Mold growth is 1/3 or more of sample area (2) Mold growth is less than 1/3 of sample area (3) Mold growth is not recognized

<2. Boiling water resistance test> 10cm × 10c
A sample film having a size of m was immersed in 1 L of distilled water controlled at 97 ° C. ± 1 ° C. for 100 hours and then taken out to evaluate various characteristics.

<3. Film haze> JIS K671
VOIC integral formula HT manufactured by Nippon Seimitsu Optics Co., Ltd.
The total haze was determined using an R meter SEP-H2D.

<4. Three-Dimensional Surface Roughness SRa> The film surface was measured using a stylus type three-dimensional surface roughness meter (SE-3AK, manufactured by Kosaka Laboratory Co., Ltd.) with a needle radius of 2 μm and a load of 30 m.
g, a cutoff value of 0. 0 in the longitudinal direction of the film.
It was measured over a measurement length of 1 mm at 25 mm, divided into 500 points at a pitch of 2 μm, and the height of each point was taken into a three-dimensional roughness analyzer (SPA-11). The same operation is performed continuously at intervals of 2 μm in the width direction of the film.
The analysis was carried out 50 times, that is, over 0.3 mm in the width direction of the film, and the data was taken into the analyzer. Next, SRa was determined using an analyzer.

<5. The number of protrusions having a height of 0.00625 μm or more from a reference plane having a reference height at the time of calculating PCC value> SRa, expressed per mm ² .

<6. Air bleeding speed> A measuring device shown in FIG. 1 is prepared. That is, a circular hole 1a is provided on the upper surface of the base 1,
A glass plate 2 having a diameter of 70 mm is fixed in the hole 1a to form a groove between the outer periphery of the glass plate 2 and the hole wall 1b, and a ring-shaped groove 1c surrounding the hole 1b is formed. The slot 1c is made to pass through the outer circumference of the glass plate 2 and the suction port of the vacuum pump 4 is connected to the full hole 1c via the pipe 3. Then, a film sample 5 having a size to cover the glass plate 2 is placed on the upper surface of the platen 1, and the outer periphery thereof is hermetically fixed on the platen 1 with an adhesive tape 6, and the vacuum pump 4 is driven to drive the glass plate 2. The time (sec) from the appearance of the interference fringes on the outer peripheral portion to the spread of the interference fringes on the entire surface of the glass plate 2 and the stop of the movement was measured, and this time (sec) was defined as the air bleeding speed.

<7. Handling characteristics of film> When slitting a wide slit roll at high speed and rewinding it into a small width roll, it is necessary to determine whether a slit roll with no problem can be obtained without causing roll deviation and wrinkles at the roll end.
It was evaluated on a scale and evaluated according to the following ranking. Grade 1: It is extremely difficult to obtain a slit roll without questioning. Grade 2: A slit roll with no problem is obtained at low speed. Grade 3: A slit roll with no problem is obtained at medium speed. Grade 4: High speed and no problem. Slit roll is obtained

<8. Abrasion resistance of film> When a tape-shaped roll with a narrow slit is rubbed against a metal guide roll and running, the size of the abrasion of the tape after the guide roll is rubbed against a certain supply tension is increased to 5 floors. It is evaluated and represented by the following ranking. Grade 1: Very abrasions Grade 2: Many abrasions Grade 3: Some abrasions Grade 4: Almost no abrasions Grade 5: No abrasions

<9. Average particle diameter> The lubricant particles were observed with a scanning electron microscope (S-510, manufactured by Hitachi, Ltd.), the photograph was enlarged and copied, the outer shape of the lubricant was traced, and 200 particles were arbitrarily determined. Painted black. This image was measured for the horizontal Feret diameter of each particle using a Luzex 500 type image analyzer manufactured by Nicole Co., Ltd., and the average value was defined as the average particle diameter. Further, the degree of dispersion of the particle diameter was calculated by the following equation.

[0066]

## EQU3 ## Degree of dispersion = (standard deviation of particle diameter / average particle diameter) × 100 (%)

<10. Area shape coefficient> arbitrarily select 20 particles from the trace image used for measuring the average particle diameter,
9. The projected cross-sectional area of each particle was measured using the image analyzer used in the above. Further, the area of a circle circumscribing the particles was calculated, and calculated by the following equation.

[0068]

## EQU4 ## Area shape factor = (projected cross-sectional area of particle / area of circle circumscribing particle) × 100 (%)

<Production Example 1> Production example of polyester resin In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 276.5 parts of dimethyl terephthalate and trisulfodimethylisophthalate were added.
48.4 parts of n-butyldodecylphosphonium salt, 204.6 parts of ethylene glycol, and 0.25 part of tetra-n-butyl titanate are charged and heated to 160 to 220 ° C.
The transesterification reaction was carried out while distilling off the methanol generated over time out of the system. After transesterification, 250
After the pressure of the reaction system was gradually reduced at
1 hour and 30 minutes under reduced pressure of polyester (A-
1) was obtained. The composition of the polyester is as shown in Table 1. Various polyesters (A-2, A-3, A-4) shown in Table 1 were produced in the same manner.

Example 1 As a lubricant, an average particle size of 0.2
a polymer chip in which 2.0% by weight of silica having 100 μm of polyester (A-1) was added with silica having μm, a degree of variation of 5%, and an area shape factor of 95%; ) Was mixed at a weight ratio of 1: 9, dried, melted at 290 ° C by an extruder, extruded from a T-die, and adhered and cooled and solidified by electrostatic printing on a cooling roll at 40 ° C. An unstretched sheet having a thickness of about 100 μm was obtained. The unstretched sheet was pre-ripened to 90 ° C by a roll, stretched 3.6 times in the longitudinal direction at a surface temperature of 130 ° C using three infrared heaters having a surface of 800 ° C, and then the film was heated to 90 ° C with a tenter. It was preheated, stretched 3.5 times in the transverse direction, and heat set at 220 ° C. for 10 seconds. The thickness of the obtained film was about 8 μm. The properties of this film were measured by the method described above. The results are shown in Tables 2 and 3.

<Example 2> A film was formed in the same manner as in Example 1 except that polyester (A-2) was used instead of polyester (A-1). The thickness of the obtained film was about 8 μm. The properties of this film were measured by the method described above. Tables 2 and 3 show the results.
Shown in

Comparative Example 1 An average particle size of 0.2 as a lubricant was used.
a polymer chip containing 2.0% by weight of 100% by weight of polyester (A-3) with silica having a thickness of μm, a degree of variation of 5%, and an area shape factor of 80%, and a polymer chip containing no lubricant (A-3). ) Were mixed at a weight ratio of 1: 9, dried, melted at 270 ° C. by an extruder, extruded from a T-die, adhered and cooled and solidified by electrostatic printing on a cooling roll at 40 ° C. An unstretched sheet having a thickness of about 100 μm was obtained. The unstretched sheet was pre-ripened to 68 ° C by a roll, stretched 3.6 times in the machine direction at a surface temperature of 110 ° C using three infrared heaters having a surface of 800 ° C, and then the film was heated to 80 ° C with a tenter. It was preheated, stretched 3.5 times in the transverse direction, and heat set at 190 ° C. for 10 seconds. The thickness of the obtained film was about 8 μm. The properties of this film were measured by the method described above. The ties are shown in Tables 2 and 3.

<Comparative Example 2> A lubricant having an average particle size of 0.2
a polymer chip in which 2.0% by weight of silica having 100 μm of polyester (A-1) was added with silica having a particle size of 5 μm, a degree of variation of 5% and an area shape factor of 55%; ) Was mixed at a weight ratio of 1: 9, dried, melted at 290 ° C by an extruder, extruded from a T-die, and adhered and cooled and solidified by electrostatic printing on a cooling roll at 40 ° C. A stretched sheet having a thickness of about 100 μm was obtained. The unstretched sheet was heated to 90 ° C. by a roll, stretched 3.6 times in the machine direction, preheated to 90 ° C. by a tenter, stretched 3.5 times in the transverse direction, and heat-set at 230 ° C. for 10 seconds. . The thickness of the obtained film is about 8 μm
Met. The properties of this film were measured by the method described above. The results are shown in Tables 2 and 3.

Comparative Example 3 As a lubricant, an average particle size of 0.2
a polymer chip obtained by adding 2.0% by weight of 100% by weight of polyester (A-4) with silica having a thickness of μm, a degree of variation of 5% and an area shape factor of 95%, and a silver-based antibacterial agent Novalon (manufactured by Toa Gosei Co., Ltd.) ) To polyester (A-4) 100
The polymer chips added at 1.8% by weight to the weight% were mixed at a weight ratio of 1: 9, dried, melted at 290 ° C. by an extruder, extruded from a T-die, and extruded at 40 ° C.
Adhesion, cooling and solidification by electrostatic application method on the cooling roll of
A stretched sheet having a thickness of about 100 μm was obtained. The unstretched sheet was pre-ripened to 90 ° C. by a roll, stretched 3.6 times in the machine direction at a surface temperature of 130 ° C. using three infrared heaters having a surface of 800 ° C.
Pre-ripened to 0 ° C, stretched 3.5 times in the transverse direction,
Heat fixed for 2 seconds. The thickness of the obtained film was about 8 μm. The properties of this film were measured by the method described above. Table 2 shows the results.

[0075]

[Table 1]

T: terephthalic acid, I: isophthalic acid,
EG: ethylene glycol NPG: neopentyl glycol P: 5-sulfodimethylisophthalic acid phosphonium salt (C12): 5-sulfodimethylisophthalic acid tri-n
-Butyldodecylphosphonium salt (C16): 5-sulfodimethylisophthalic acid tri-n
-Butylhexadecylphosphonium salt

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

The antibacterial film of the present invention has a sufficiently high antibacterial property that satisfies practicality, in particular, a high antifungal property, and also has excellent durability that can withstand practical use. It has excellent properties that it does not change appearance even when immersed in boiling water while maintaining its antifungal property, and has excellent transparency, heat resistance and smoothness of the film surface, and is related to the thickness of the film. And the film has good handling characteristics and good abrasion resistance on the film surface. From this, the antibacterial film of the present invention can be used for magnetic tape in the form of a film alone or a laminate with another film / sheet or molded product, a laminate with a metal plate, a laminate with a vinyl chloride steel plate, or the like. For packaging of food and medical supplies, and for building materials such as walls, wallpapers, floors and ceilings, hospitals, medical facilities, public facilities, general houses, and other window frames, doorknobs, and handrails, such as cooking microwave ovens and rice cookers Equipment, refrigerators, washing machines, telephones, vacuum cleaners, and other home appliances, cans, beverage cans, pail cans,
Metal containers such as drum cans, water supplies such as system kitchens and sinks, furniture such as desks, shelves and tables, medical equipment in general, stationery, decorative boards for trains, cars, ships, aircraft, etc. It is suitable as a constituent material for exterior plates, structures, accessories, parts, and the like.

[Brief description of the drawings]

FIG. 1 is a conceptual vertical sectional view of a device for measuring the air bleeding speed.

[Explanation of symbols]

 1: Base plate 2: Glass plate 3: Suction pipe 4: Vacuum pump 5: Film sample 6: Adhesive tape

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // C08L 67:00 (72) Inventor Shigetsugu Konagaya 2-1-1 Katada, Otsu City, Shiga Prefecture TOYOBO F-term (Reference) 4F071 AA45 AA46 AE08 AE22 AF30 AF30Y AF52 AF52Y BB08 BC01 BC14 BC16 BC17 4H011 AA02 AA03 BB04 BB07 BB17 BB19 BC19 DA08 DH04 DH19 4J002 BB031 BB121 CF03 001 GQ01 GS01

Claims (5)

[Claims] An antibacterial composition is contained in at least one surface layer of at least one surface of a film, and a change in haze value of the film before and after immersion in boiling water for 100 hours is 1.
0% or less, a mold resistance display of 2 or more by an evaluation method according to JIS Z 2911 6.2, and the mold resistance display after immersing the film in boiling water for 100 hours is 2 or more, The three-dimensional surface roughness SRa of at least one surface of the film is 0.02 μm or less, and the number of protrusions PCC per unit area on the central surface of the roughness is 800 /
An antibacterial film having a diameter of not less than ² mm and an air bleeding speed of not more than 900 seconds. 2. The antibacterial film according to claim 1, wherein the antibacterial composition is a polymer substance having an organic antibacterial component bound to a main chain or a side chain. 3. The antibacterial composition, wherein the polymer substance having an organic antibacterial agent component bound to a main chain or a side chain comprises at least one of an ammonium base, a phosphonium base, and a sulfonium base in a main chain and / or The antibacterial film according to claim 1, wherein the antibacterial film is a polymer having a side chain. 4. The antibacterial film according to claim 1, which mainly comprises a polyester composition. 5. The antibacterial film according to claim 1, wherein the film is a biaxially stretched film.