JP2000301669A - Antibacterial film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial film excellent in antibacterial and antifungal properties, having an excellent durability generating no appearance change while keeping antibacterial properties even after immersion in boiling water and excellent in transparency, handling characteristics and abrasion resistance. SOLUTION: In a film wherein an antibacterial compsn. is contained in the single surface of at least a surface layer, a change of the haze value of the film before and after immersion in boiling water is 1.0% or less per a film thickness of 10 μm and the fungi resistance display thereof due to an evaluation method according to JIS Z2911 6.2.2 is 2 or more before and after 100 hr- immersion in boiling water and the three-dimensional surface roughness SRa of the antibacterial surface layer of at least single surface of the film is 0.04 μm or more and the number-of-projection PCC value per a unit area is 2,000/mm2 or more and an air venting speed is 500 sea or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has both excellent antifungal properties and practical durability, and exhibits excellent antifungal sustaining effect without causing a change in appearance even after immersion in boiling water, and The present invention relates to an antibacterial film having excellent surface smoothness, excellent handling characteristics irrespective of film thickness, 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,
Used for plastics, films, sheets, adhesives, etc. 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.

[0004] Inorganic antibacterial agents typified by natural and silver are safe in terms of toxicity and have recently received attention, and the following inventions have already been disclosed. That is, JP-A-3-83905 discloses a silver-ion-containing phosphate antibacterial agent disclosed in JP-A-3-3-1905.
Japanese Patent No. 61409 discloses an antibacterial agent obtained by replacing a fixed volume of zeolite having a specific ion exchange capacity with silver ions. However, when films and sheets were prepared according to the inventions disclosed therein and their antibacterial properties against Staphylococcus aureus and Escherichia coli were evaluated, the antibacterial activity was insufficient when the amount added was relatively low, while the antibacterial activity was low. When the amount added is increased in order to improve the melting point, 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 generally have better antibacterial properties against fungi and the like than natural products and inorganic products. However, when such antibacterial agents are coated or filled on a substrate such as a film. Since the antibacterial agent has a low molecular weight, it is easy to volatilize, desorb and separate from a substrate such as a film, which is not preferable from the viewpoint of long-term stability of antibacterial properties and safety to the human body. When an antibacterial agent is used in films, etc., the antibacterial agent does not dissolve in water or organic solvents, and is unlikely to be released, detached, peeled off, or dropped off from the film surface. It is preferable from the viewpoint of safety.

Under such circumstances, recently, an immobilized antibacterial agent has been disclosed in which an organic antibacterial agent is bonded to a polymer material as a raw material of a film, a sheet or the like by ionic or covalent bonding. 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. JP-A-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, and JP-A-62-114903.
JP-A-1-93596, JP-A-2-240090
Like various nitrogen-containing compounds, phosphonium salt compounds are known as biologically active chemicals having a broad spectrum of activity against bacteria, as described in the publications such as No. There is also disclosed an invention in which these phosphonium salts are immobilized on a polymer substance to attempt to expand applications. For example, Japanese Patent Application Laid-Open No. 4-266912 discloses an antibacterial agent of a phosphonium salt-based vinyl polymer as disclosed in WO 92/143.
No. 65 discloses a vinylbenzylphosphonium salt-based vinyl polymer antibacterial agent, respectively. Further, JP-A-5-310820 discloses 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 the examples, polyesters using a phosphonium salt of sulfoisophthalic acid are disclosed.

Japanese Patent Application Laid-Open No. 6-41408 does not mention any antibacterial action, but it is useful for photographic supports, packaging, general industrial use, magnetic tapes, and the like for copolyesters of sulfonium phosphonium salts. And polyalkylene glycols are disclosed. The alkyl group bonded to the phosphonium salt described in this patent specification is disclosed in JP-A-5-31.
Unlike the type disclosed in Japanese Patent Application Laid-Open No. 0820, it is a type having a relatively short carbon number such as a butyl group, a phenyl group, and a benzyl group.

The present inventors have disclosed Japanese Patent Application Laid-Open Nos. 4-266912, WO92 / 14365, and 5-310.
Based on the description of JP 820 and the like, a phosphonium base-containing vinyl copolymer and a copolymerized polyester are synthesized according to the examples to form a film, a sheet, or the like,
A laminate was formed by applying the antibacterial polymer on the film sheet surface. However, their antibacterial and fungicidal properties, sustained effects after immersion in boiling water and changes in appearance before and after, and the handling properties as a film were evaluated, but the antibacterial and antifungal properties were insufficient, and after immersion in boiling water Poor practicality such as whitening phenomenon, poor handling characteristics during film formation and processing, and poor slippage due to contact with guide rolls etc. during film running, causing scratches etc. Was something.

In particular, recently, decorative steel sheets around bathrooms have also been required to have antibacterial and antifungal properties. In such applications, the surface does not deteriorate even when exposed to hot water, and the antibacterial and antifungal properties are high. It is necessary to have durability such that the effect of the tire is maintained. However, the conventional techniques described above are insufficient in not only antibacterial properties but also durability.

Also, various films such as nylon, polystyrene, polyethylene terephthalate, and polyester have excellent heat resistance and transparency, especially when formed into a biaxially stretched film, and are suitable for packaging, magnetic tape, capacitors, and the like.
It is used in various applications such as photoengraving, building materials and 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 also 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, when an organic low molecular weight antibacterial agent is added to impart an antibacterial active ingredient, brittleness increases and abrasion resistance during film running decreases. In order to improve the slipperiness of the film, a known technique in which inorganic particles are added to limit the surface roughness Ra (JP-A-3-74437)
No. 1). However, in the above-described known technique, although good handling characteristics can be obtained when the film feeding speed is low, the handling characteristics rapidly deteriorate when the film feeding speed is increased to increase productivity. There was a problem. Also,
When the thickness of the film is reduced, the handling characteristics tend to be deteriorated.
A similar tendency was found in the film in which the range of a and the static friction coefficient were defined.

[0012]

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 Sufficient durability to withstand, especially excellent properties that exerts the effect of sustaining mold resistance even after immersion in boiling water and does not cause a change in appearance, as well as transparency, heat resistance and smoothness of the film surface It is an object of the present invention to provide an antibacterial film which is excellent, has good handling characteristics irrespective of the thickness of the film, and has good abrasion resistance on the film surface.

[0013]

That is, the object of the present invention can be achieved by the following means.

A. A film containing an antimicrobial composition on at least one surface of a surface layer, wherein a 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 of film thickness, and JIS Z
In each case, the mold resistance was evaluated to be 2 or more before and after immersion in boiling water for 100 hours, and the three-dimensional surface roughness SRa of the antibacterial surface layer on at least one side of the film was 0.2. 04 μm or more, and the number of protrusions per unit area PCC value is 2,000 / m
m ² or more and an air bleeding speed of 500 seconds or less.

B. An antibacterial film, wherein the antibacterial composition according to A is a polymer in which a residue of an organic antibacterial agent is bonded to a main chain or a side chain.

C. An antibacterial film, wherein the residue of the organic antibacterial agent according to B is at least one of an ammonium base, a phosphonium base, and a sulfonium base.

D. The antibacterial film according to B or C, wherein the polymer substance mainly comprises a polyester composition.

F. The antibacterial film according to any one of A to D, wherein the film is a biaxially stretched film.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial film of the present invention will be described below. The antimicrobial film of the present invention contains an antimicrobial composition. Here, the antimicrobial composition refers to a composition capable of killing bacteria and / or molds or suppressing their growth.

The antimicrobial composition used in the present invention is preferably a high molecular substance in which a residue of an organic antimicrobial agent is bonded to a main chain or a 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. Therefore, by binding the residue of the organic antibacterial agent to the main chain or side chain of the polymer substance, elution can be prevented, and as a result, the antibacterial and antifungal effect can be maintained. .

The organic antibacterial agent 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, natural extracts include chitin, chitosan,
Wasabi extract, mustard extract, hinokitiol, tea extract, etc., as low molecular weight compounds, allyl isothiocyanate, polyoxyalkylene trialkyl ammonium,
Quaternary ammonium salts such as benzalkonium chloride, organic silicon quaternary ammonium salts, tri-n-butylhexadecyldecylphosphonium chloride, tri-n-butyltetradecyldecylphosphonium chloride, tri-n-butyltetradodecyldecylphosphonium chloride, etc. , Phenylamides, biguanides, sulfoisophthalic acid tetraalkylphosphonium salts or diesters thereof, but are not limited thereto.

Among these organic antibacterial agents, onium salts such as ammonium bases, phosphonium bases and sulfonium bases, and antibacterial active groups such as phenylamide group and biguanide group are selected because of their ease of binding to polymer substances. Is preferred, and a phosphonium salt-based polymer compound having high antibacterial properties and a broad antibacterial spectrum is particularly preferable.

Preferred is a polymer substance containing an acidic group and a phosphonium base ionically bonded to the acidic group, and more preferably a dicarboxylic acid component and a glycol component as main components and represented by the following general formula: It is a polyester resin in which a phosphonium base of a sulfonic acid group-containing aromatic dicarboxylic acid is copolymerized in an amount of 1 to 50 mol% based on all acid components.

[0024]

Embedded image

In the formula, 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 to 20 carbon atoms. These are the following alkyl groups.

In addition, as one of the high molecular substances, there is a phosphonium salt vinyl polymer represented by the following general formula.

[0027]

Embedded image In the formula, B is an aromatic group, R ₅ , R ₆ , and R ₇ are each substituted with a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxy group, or an alkoxy group. It represents an alkyl group, an aryl group or an aralkyl group, X ^-
Represents an anion, and n represents an integer of 2 or more.

Specific examples of the above R ₅ , R ₆ and R ₇ include those having 1 to 1 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl and the like.
8, an aryl group such as phenyl, tolyl, and xylyl; an aralkyl group such as benzyl and phenyl;
An alkyl group or an aryl group having a hydroxyl group, an alkoxy group, or the like as a substituent is particularly preferred. R ₅ ,
R ₆ and R ₇ may be the same group or different groups. X ⁻ is an anion, for example, a halogen ion such as a fluorine ion, a chloride ion, a bromine ion or an iodine ion, a sulfate ion, a phosphate ion, a perchlorate ion and the like. Of these, halogen ions are preferred. n is preferably 2 to 500, and 10 to 3
00 is particularly preferred.

The dicarboxylic acid component used in the polyester resin includes terephthalic acid, isophthalic acid,
Examples thereof include 6-naphthalenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. If necessary, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, a heterocyclic dicarboxylic acid, or the like may be used in combination. As the alicyclic dicarboxylic acid, 1,2-
Examples thereof include cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the aliphatic dicarboxylic acid 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, if necessary.

Of these, 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.
As other dicarboxylic acids, 1,4-dicarboxylic acid, adipic acid and sebacic acid are preferred.

The glycol component includes 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, neopentyl glycol (HPN) of hydroxypivalic acid, polypropylene glycol Le, 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, preferred main constituent components are ethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,5-hexane, because of the boiling water resistance when formed into a film. They are pentanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanedimethanol, and it is particularly preferable to contain at least 70 mol% of ethylene glycol.

If necessary, a polyhydric polyol 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-sulfoisophthalic acid.
Butyldecylphosphonium salt, tri-n-butyldodecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-sulfoisophthalate Butyl octadecyl phosphonium salt, tri-n-sulfoterephthalate
Butyldecylphosphonium salt, tri-n-butyldodecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-sulfoterephthalate Butyl octadecyl phosphonium salt, 4-sulfonaphthalene-2,7
Tri-n-butyldecylphosphonium dicarboxylate, tri-n-butyloctadecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate, tri-n-butylhexadecyl 4-sulfonaphthalene-2,7-dicarboxylate Phosphonium salt, 4-sulfonaphthalene-
Tri-n-butyltetradecylphosphonium 2,7-dicarboxylate; tri-n-butyldodecylphosphonium 4-sulfonaphthalene-2,7-dicarboxylate; and the like. From the viewpoint of antibacterial activity, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, and tri-n-butyldodecylphosphonium sulfoisophthalate are particularly preferred.

The phosphonium salt of an aromatic dicarboxylic acid may be a sulfoaromatic dicarboxylic acid or its sodium salt, potassium salt, ammonium salt, etc., such as tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide or tri-n-butyltetradecylphosphonium bromide. -N-
It is obtained by reacting a phosphonium salt such as butyl dodecylphosphonium 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, antimony oxide,
In addition to polymerization catalysts such as germanium oxide and titanium compounds,
Mg salts such as magnesium acetate and magnesium chloride; Ca salts such as calcium acetate and calcium chloride; Mn salts such as manganese acetate and manganese chloride; Zn salts such as zinc chloride and zinc acetate; Co salts such as cobalt chloride and cobalt acetate. , 300 pp as metal ions for the resulting polyester
It is also possible to add phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester or phosphoric acid triethyl ester in an amount of 200 ppm or less in terms of phosphorus (P).

The total amount of metal ions other than the above polymerization catalyst was 300 ppm based on the produced polyester, and the P amount was 200 ppm.
If it exceeds 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 atomic ratio (P / M) between the total P amount (P) and the total metal ion amount (M) is 0.4 to 1. It is preferably 0. If the molar atomic ratio (P / M) 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, and a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed,
A so-called transesterification method in which a dimethyl ester of a dicarboxylic acid and a glycol are subjected to transesterification and then polycondensation, and the like, may be used, and an arbitrary production method can be applied.

The timing of adding the metal ions and phosphoric acid and derivatives thereof is not particularly limited. Generally, the metal ions are charged at the time of charging the raw materials, that is, before ester exchange or esterification, and the phosphoric acid is added before the polycondensation reaction. Is preferably added.

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

The composition other than the antibacterial composition constituting the antibacterial film of the present invention includes polyethylene, polypropylene, polyvinyl chloride, nylon, polyester, polycarbonate, polystyrene, polyurethane, and the like.
Polyamide, polyimide, polyamide imide, or the like is applied. Among them, polyester, polyvinyl chloride, polystyrene and the like are preferable from the viewpoint of boiling water resistance.

In addition, the antibacterial film of the present invention has the following properties in order to improve the abrasion resistance and handleability of the film.
It is important to contain inert particles such as inorganic particles, crosslinked polymer particles and heat-resistant organic particles.

Examples of the inorganic particles include 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, and the like. Examples thereof include metal salts such as barium sulfate and calcium fluoride.

As the organic particles, polystyrene,
Polymethacrylate, polyacrylate,
Examples include particles that are inert to film compositions such as silicone resins, benzoguanamine-formaldehyde condensates, melamine-formaldehyde condensates, benzoguanamine-melamine-formaldehyde condensates, copolymers thereof, or cross-linked products thereof. .

One of the above lubricant particles may be used alone, or two or more thereof may be used in combination. Further, in order to further improve the abrasion resistance of the antibacterial film of the present invention, a silane coupling agent, a titanate coupling agent, and an aluminum-based coupling agent capable of improving adhesion and wettability with a resin and dispersibility. The surface of the particles can also be modified using a coupling agent or the like.

The average particle size of the lubricant particles is from 0.01 to 2.
0 μm is preferred, and particularly preferably 0.05 to 1.5 μm
m. Further, it is preferable from the viewpoint of handleability that the degree of dispersion of the particle diameter (the ratio between the standard deviation of the particle diameter and the average particle diameter) is 25% or less. The amount of lubricant particles added is
0.005 to 100% by weight of the film composition.
The content is preferably 0% by weight, particularly preferably 0.1% by weight.
1 to 1.0% by weight. The shape of the lubricant particles preferably includes one or more types having an area shape factor of 60% or more determined by the following equation (1) from the viewpoint of handling properties. As described above, the inert particles having a nearly uniform particle diameter and a nearly spherical shape include spherical monodisperse silica particles, spherical monodisperse polystyrene particles, spherical monodisperse polymethyl methacrylate particles, spherical monodisperse silicon resin particles, and spherical monodisperse silicon resin particles. And cubic calcium carbonate particles.

Area shape factor (%) = (projected cross-sectional area of particle / area of circle circumscribing particle) × 100 (1)

The film composition used in the present invention may contain a known antioxidant, antistatic agent, colorant,
An appropriate amount of an ultraviolet absorber, a light stabilizer and the like can be blended. The blending amount is based on 100% by weight of the film composition.
It is desirably 10% by weight or less. If the amount is more than 10% by weight, the film tends to be broken when the film is stretched, resulting in poor production stability.

The method for forming the antibacterial film of the present invention includes, but is not limited to, the following methods.

A method in which the antibacterial composition is used alone or mixed with another composition and extruded into a sheet by a melt extruder to form an unstretched film, or the unstretched film is uniaxially or biaxially stretched. By doing, 1
A method of forming an axially stretched film or a biaxially stretched film may be mentioned, but a film forming method of biaxially stretching is preferable in terms 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, the film contains an antibacterial composition at least on one surface of the surface layer. Need to be. As the laminating method, a method of co-extruding and laminating with a melt extruder,
A method of laminating by extruding on another substrate film directly or via an adhesive layer by a melt extruder and the like can be mentioned. Among them, a laminated biaxially stretched film in which at least one outermost surface layer is an antibacterial agent layer by a coextrusion method is preferable. Further, the thickness of the outermost antibacterial agent layer is 1 to 5 μm.
m, the amount of the antibacterial agent with respect to the entire film can be reduced while maintaining a high antibacterial activity,
Further, a laminated biaxially stretched film having excellent film strength and heat shrinkage can be obtained, so that it is more preferable. Also, a coating solution obtained by mixing and dissolving or dispersing the antimicrobial composition in a solvent such as water, a water / alcohol mixed solvent, acetone, methyl ethyl ketone, or cyclohexanone is applied to at least one surface of the film surface, and the solvent is dried. A coating method can also be adopted.

A known method can be used for stretching the film. For example, in the case of the uniaxial stretching method, there is a method in which the film is uniaxially stretched vertically or horizontally. In the case of the biaxial stretching method, a sequential biaxial stretching method in which the film is biaxially stretched in the longitudinal / horizontal or transverse / longitudinal order, or a simultaneous biaxial stretching method can be used. In addition,
Multi-stage stretching methods such as longitudinal / longitudinal stretching, longitudinal / horizontal / longitudinal stretching, and longitudinal / longitudinal / horizontal stretching can also be adopted, and are selected according to various properties such as required strength and dimensional stability. You. In order to improve the dimensional stability, it is also effective to perform a heat setting treatment, a longitudinal relaxation treatment, and a horizontal relaxation treatment.

In the present invention, the change in the haze value of the film before and after immersion in boiling water for 100 hours is 1.0% or less per 10 μm of the film thickness, and JIS Z2911 6.
It is necessary that the mold resistance display by an evaluation method according to 2.2 is 2 or more, and that the mold resistance display after immersing the film in boiling water for 100 hours is 2 or more. If the change in the haze value of the film before and after immersion in boiling water for 100 hours exceeds 1.0% per 10 μm of the film thickness, for example, when used under high temperature and high humidity such as a wall material in a bathroom, the appearance is deteriorated. In addition, when the film is immersed in boiling water for 100 hours, if the mold resistance display is not 2 or more, mold is generated under the same environment. They are,
This can be achieved by selecting the composition constituting the above-mentioned film.

According to the present invention, in addition to the contents described above, the three-dimensional surface roughness (SRa) of at least one antibacterial surface layer of the film is 0.04 μm or more, and the number of protrusions per unit area PCC is 2,000. / Mm ² or more, and the air bleeding speed needs to be 500 seconds or less.

Here, the “three-dimensional surface roughness SRa” is
It means the average roughness on the center plane when the surface roughness curve is approximated by a sine curve. Here, the central plane is a plane in which the total area on the convex side and the total area on the concave side in the sine curve are the same.

Specifically, the height of a predetermined number of measurement points (points) spaced at a constant pitch is measured by a stylus type three-dimensional surface roughness meter [SE-3AK, manufactured by Kosaka Laboratories Ltd.] Measured values are converted into a three-dimensional surface roughness analyzer [SPA, manufactured by Kosaka Laboratories.
−11] and automatically analyzed.

The automatic analysis is performed in the following procedure.
The surface roughness curve is obtained by approximating a sine curve based on the measured values (heights) of the respective measurement points on the film surface (FIG. 1). L is the measurement length (mm) on the measurement surface.

Input ZC-device 0.02 μm and set the slice width to 0.0 μm at 5 points
It is set to 125 or 0.025 μm. When the measurement point in the longitudinal direction of the film is i (data is taken at intervals of 2 μm over a reference length of 1 mm) and the measurement point in the lateral direction of the film is j (150 times at intervals of 2 μm), the data in the height direction is h (I, j) [i = 1 to 500, j = 1 to
150]. The three-dimensional surface roughness SRa is defined by the following equation and is expressed in μm.

[0060]

(Equation 1)

[0061]

(Equation 2)

When SRa is less than 0.04 μm, handling characteristics and running characteristics are likely to be poor. Also, SRa
The upper limit of is not particularly defined, but if it exceeds 0.2 μm,
Depending on the inert particles used, transparency may decrease, which may not be preferable. SRa is 0.045 to 0.10
It is preferably in the range of 0 μm, particularly preferably 0.050 to
It is in the range of 0.080 μm.

"PCC value of the number of protrusions per unit area"
Is the number of projections having a height of 0.00625 μm or more from the reference plane (center plane) having the reference height at the time of calculating the three-dimensional surface roughness SRa per 1 mm ² (number / mm ² ) It is.

If the PCC value is less than 2000 pieces / mm ² , the running characteristics become poor. The upper limit of the PCC value is not particularly defined, but when it is 10,000 or more / mm ² , the overlap of the projections increases, and the handling characteristics and the running characteristics are liable to deteriorate. The PCC value is preferably in the range of 2,000 to 7000 / mm ² , and particularly preferably in the range of 3,000 to 6,000 / mm ² .

Further, the term “air bleeding speed” as used in the present invention refers to the film / air speed when the film is wound up into a roll.
It is a measure of how easily the entrained flow of air entrained between the films escapes. The low air bleeding speed means that less air is caught between the film and the film when the film is wound into a roll, and there is less wrinkling and uneven roll ends due to air remaining in the winding roll. Become. The air bleeding speed is determined by the stiffness of the film (E * t ³ ; here, E
Has a negative correlation with Young's modulus and t indicates the film thickness). Experiments show that even if the films have the same surface roughness, as the film thickness decreases, the air bleeding index increases and the winding properties deteriorate. Is known. In the antibacterial film of the present invention, in order to obtain an antibacterial film having good handling characteristics irrespective of the thickness and strength of the film, it is necessary that the air bleeding speed of the film be 500 seconds or less. Preferably, it is 450 seconds or less, particularly preferably 400 seconds or less.

That is, the air bleed speed is 500 seconds or less,
By setting the time to preferably 400 seconds or less, particularly preferably 300 seconds or less, an antibacterial film having good handling properties can be obtained at high speed operation regardless of the thickness and strength of the film. Conversely, if the air bleed speed exceeds 500 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 will be trapped between the film and the take-up roll. Wrinkles are likely to occur and the winding appearance is poor, or 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.

The antibacterial film of the present invention having the above characteristics has excellent surface smoothness, excellent handling characteristics irrespective of the thickness of the film, and good abrasion resistance of the film surface. The three-dimensional surface roughness SRa, the PCC value of the number of protrusions per unit area, and the air bleeding speed are determined based on film forming conditions and lubricant particles (type, shape, average particle size, particle size) contained in the film. Distribution and the amount of addition) can be achieved.

[0068]

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 films obtained in Examples and Comparative Examples are shown below.

1. Mold resistance test A sample film having a size of 5 cm x 5 cm was stuck on an inorganic salt agar medium plate by a method according to JIS Z29116.2.2, and sucrose 5 was added to a spore suspension of the following 5 mold strains: Spray 0.2 ml of the mixed solution containing
After 28 days of cultivation at ℃, the growth status of the mold was evaluated. (Test strain) Aspergillus niger ATCC 6275 Penicillium citrinum ATCC 98
49 ChaetomiumglobosumATCC620
5 Rhipuspustoloneifer ATCC104
04 Aureobasidiumpullulans 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 A sample film of 10 cm × 10 cm size is 97 ° C. ± 1
After immersion in 1 L of distilled water controlled at 100 ° C. for 100 hours, it was taken out and various characteristics were evaluated.

3. Film haze The total haze was determined using a Voick integral type HTR meter SEP-H2D manufactured by Nippon Seimitsu Kogaku Co., Ltd. in accordance with JIS K6714.

4. Three-dimensional center plane average surface roughness (SRa) Using a stylus type three-dimensional surface roughness meter (SE-3AK, manufactured by Kosaka Laboratory Co., Ltd.), the radius of the needle is 2 μm and the load is 30 mg. A cutoff value of 0.25 in the longitudinal direction of the film.
mm, the measurement was performed over a measurement length of 1 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 an interval of 2 μm in the width direction of the film.
Each time, that is, over 0.3 mm in the width direction of the film, data was taken into the analyzer. Next, SRa was determined using an analyzer.

5. PCC value 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 the SRa is 1 mm.
^{2 is shown} .

6. Vent Speed The measurement device shown in FIG. 2 is prepared. That is, a circular hole 1a is provided on the upper surface of the base 1, and a glass flat plate 2 having a diameter of 70 mm is fixed in the hole 1a.
And a ring-shaped slot 1c surrounding the hole 1b is made. The slot 1c is made to pass through a groove on the outer periphery of the glass plate 2 through the pipe 3 through the pipe 3. To connect the suction port of the vacuum pump 4. And on the upper surface of the base 1,
A film sample 5 large enough to cover the glass plate 2 is superimposed, and the outer periphery thereof is hermetically fixed on the base plate 1 with an adhesive tape 6, and the vacuum pump 4 is driven so that interference fringes appear on the outer periphery of the glass plate 2. After that, the time (sec) until the interference fringes spread over the entire surface of the glass plate 2 and the movement stopped was measured, and this time (sec) was defined as the air bleeding speed.

7. Film handling characteristics When slitting a wide slit roll at high speed and rewinding it into a small width roll, the roll edge at the roll end is not displaced, and it is evaluated whether or not a slit roll without any wrinkles can be obtained. The following ranking was used for evaluation. 1st grade: It is extremely difficult to obtain a slit roll with no problem 2nd grade: A slit roll with no problem is obtained at low speed (150 m / min) 3rd grade: A slit roll with no problem is obtained at medium speed (200 m / min) Grade 4: Grade-free slit rolls can be obtained at high speed (250 m / min)

8. Abrasion Resistance of Film Under an atmosphere of 23 ° C. and 65 RH%, a tape-shaped film roll slit to a イ ン チ inch width is inserted into a metal fixed guide pin (Rt: 0.15 μm, Ra: 0.08 μm).
While contacting at an angle of 35 ° and applying a tension of 50 g, 2
Run 90 m at a speed of 00 cm / min. After evaporating the contact surface of the film after running with the fixing pins with aluminum, abrasion on the film surface is evaluated in five stages while irradiating light from obliquely above the sample surface, and is expressed by the following ranking. Grade 1; Very many scratches 2nd; Many abrasions 3rd; Some abrasions 4th grade; Little abrasions 5th grade; No abrasions

9. Average particle diameter and degree of dispersion of particle diameter The lubricant particles were observed with a S-510 scanning electron microscope manufactured by Hitachi, Ltd., and a photograph was enlarged and copied.
The contours of the lubricant particles were traced and optionally 200 particles were painted black. This image was measured for the horizontal Feret diameter of each particle using an image analyzer (Luex IID manufactured by Nireco Co., Ltd.), and the average was used to calculate the average particle diameter (μ).
m). Further, the degree of dispersion of the particle diameter was calculated by the following equation. Variation (%) = (standard deviation of particle diameter / average particle diameter)
× 100

10. Area shape factor Twenty particles were arbitrarily selected from the trace image used for the measurement of the average particle diameter, and the projected cross-sectional area of each particle was measured using the above-mentioned image analyzer. Further, the area of a circle circumscribing the particles was calculated, and calculated by the following equation. Area shape factor (%) = (projected cross-sectional area of particle / area of circle circumscribing particle) × 100

(Production Example 1 of Polyester Resin) Stirrer,
Dimethyl terephthalate in a stainless steel autoclave equipped with a thermometer and a partial reflux condenser.
5 parts, 48.4 parts of dimethyltri-n-butyldodecylphosphonium salt of 5-sulfoisophthalic acid, 204.6 parts of ethylene glycol, and 0.25 part of tetra-n-butyltitanate are charged and heated to 160 to 220 ° C. for 4 hours. The transesterification reaction was carried out while distilling off the methanol produced by the distillation out of the system. After the transesterification was completed, the reaction system was gradually reduced in pressure at 250 ° C., and then reacted under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester (A-1). The composition of the polyester is as shown in Table 1. In the same manner, various polyesters (A-
2, A-3, A-4).

Example 1 Crosslinked poly (methyl methacrylate) particles having an average particle size of 0.5 μm, a degree of variation of 5%, and an area shape coefficient of 95% were used as lubricant particles as polyester (A-A).
1) Polyester (A-1) comprising polymer chips in which 3.0% by weight is added to 100% by weight and crosslinked polymethyl methacrylate particles having an average particle size of 1.5 μm, a degree of variation of 5%, and an area shape factor of 95%. The polyester chip (A-1) to which 2.0% by weight was added to 100% by weight and the polyester chip (A-1) to which no lubricant particles were added were added in a weight ratio of 1%.
After mixing at a ratio of 1: 8, the mixture was dried. These three types of mixed polyester chips are extruded at 290 ° C.
And then extruded from a T-die, adhered and cooled and solidified on a cooling roll at 40 ° C by an electrostatic application method, and the thickness was 100 μm.
Was obtained. The unstretched sheet is preheated to 85 ° C. by a roll, and 3.5 infrared rays are heated at a surface temperature of 130 ° C. by 3.5 using four infrared heaters having a surface temperature of 780 ° C.
After stretching the film twice and then re-stretching 1.2 times in the machine direction with a roll at 120 ° C., the film was preheated to 90 ° C. with a tenter,
The film was stretched 3.6 times in the transverse direction, and further heat-set at 220 ° C. for 10 seconds. The thickness of the obtained film was 7 μm.
The properties of this film were measured by the method described above. Table 2 shows the results.

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 7 μm. The characteristics of this film
It was measured by the method described above. Table 2 shows the results.

(Example 3) Three kinds of mixed polyester chips (a) described in Example 1 and polyethylene terephthalate A-4 containing no lubricant particles and an antibacterial composition
(B) was separately dried, and then 290
° C and the thickness ratio is a / b / a = 20/60/20
A film was produced in the same manner as in Example 1 except that the film was co-extruded from a T-die so as to obtain a laminated film in which the thickness of the antibacterial composition layer was 1.4 μm and the thickness of the entire film was 7 μm. . The properties of this film were measured by the method described above. The laminated film of the third embodiment is the same as that of the first embodiment.
The thickness of the antimicrobial composition layer is 7 μm
Although the thickness was reduced to 1.4 μm, the obtained result was the same as that of Example 1.

Comparative Example 1 Crosslinked poly (methyl methacrylate) particles having an average particle size of 0.5 μm, a degree of variation of 5%, and an area shape coefficient of 95% were used as lubricant particles as polyester (A-A).
3) 100% by weight of a polyester chip added to 3.0% by weight, an average particle size of 1.5 μm, and a degree of dispersion of 5
% Of polyester (A-3) and 2.0% by weight with respect to 100% by weight of polyester (A-3), and a polymer chip (A- 3) was mixed at a weight ratio of 1: 1, 8 and dried. The obtained mixed polyester chip was melted at 290 ° C. by an extruder, extruded from a T-die, and adhered and cooled and solidified on a cooling roll at 40 ° C. by an electrostatic application method to obtain an unstretched sheet having a thickness of 100 μm. . The unstretched sheet is rolled to 65
C., and stretched 3.6 times in the machine direction at a surface temperature of 115.degree. C. using three infrared heaters having a surface temperature of 780.degree.
After re-stretching 2 times, the film was preheated to 80 ° C with a tenter, stretched 3.6 times in the transverse direction, and further heat-set at 190 ° C for 10 seconds. The thickness of the obtained film was 7 μm. The properties of this film were measured by the method described above. Table 2 shows the results.

Comparative Example 2 Crosslinked poly (methyl methacrylate) particles having an average particle size of 2.0 μm, a degree of variation of 5%, and an area shape factor of 95% were used as lubricant particles as polyester (A-
1) A polyester chip added 3.0% by weight to 100% by weight and a polyester chip (A-1) to which no lubricant particles are added are mixed at a weight ratio of 1: 9, and then dried, It is melted at 290 ° C with an extruder, extruded from a T-die while changing the discharge amount from the example, and adhered and cooled and solidified by an electrostatic application method on a cooling roll at 40 ° C to obtain an unstretched sheet having a thickness of 90 µm. Obtained. The unstretched sheet is preheated to 85 ° C by a roll, stretched 3.5 times in the machine direction at a surface temperature of 130 ° C using three infrared heaters having a surface temperature of 780 ° C, and then rolled at a surface temperature of 120 ° C. After stretching 1.2 times in the machine direction in the longitudinal direction, the film was preheated to 90 ° C. with a tenter, stretched 3.6 times in the transverse direction, and further stretched 22 times.
Heat set at 0 ° C. for 10 seconds. The thickness of the obtained film was 6 μm. The properties of this film were measured by the method described above. Table 2 shows the results.

Comparative Example 3 Crosslinked polymethyl methacrylate particles having an average particle size of 1.5 μm, a degree of variation of 5%, and an area shape factor of 95% were used as the lubricant particles as polyester (A-
4) A polyester chip added at 3.0% by weight to 100% by weight, and a silver-based antibacterial agent Novalon (Toa Gosei Co., Ltd.)
Of polyester (A-4) was added in an amount of 1.8% by weight to 100% by weight of polyester (A-4).
After mixing at a ratio of 9 and drying, it is melted at 290 ° C. by an extruder, extruded from a T-die, adhered and cooled and solidified by an electrostatic application method on a cooling roll at 40 ° C., and a 100 μm thick unstretched sheet I got The unstretched sheet is rolled to 8
Preheated to 5 ° C., stretched 3.5 times in the machine direction at a surface temperature of 130 ° C. using three infrared heaters having a surface temperature of 780 ° C., and then 1.2 mm in a machine direction with a roll having a surface temperature of 120 ° C. After re-stretching, the film was preheated to 90 ° C. with a tenter, stretched 3.6 times in the transverse direction, and
Heat set for 0 seconds. The thickness of the obtained film was 7 μm. The properties of this film were measured by the method described above. Table 2 shows the results. However, other evaluations were not performed because the mold resistance was already poor before the boiling water test.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

The antibacterial film of the present invention has a sufficiently high antibacterial property that satisfies practicality, in particular, has a high antifungal property, and has excellent durability that can withstand practical use. It has excellent properties that it does not change its appearance while maintaining its mold-preventing effect even after being immersed in water, and has excellent transparency, heat resistance and smoothness of the film surface, and can be handled regardless of the film thickness Since the film has good properties and good abrasion resistance on the film surface, it can be used as a film alone or as a laminate with other films / sheets or molded products, a laminate with a metal plate, a laminate with a polyvinyl chloride steel plate, etc. In the form of magnetic tape, packaging for food and medical supplies, etc., walls, wallpapers, floors and ceilings, window frames and doorknobs for hospitals, medical facilities, public facilities, general houses, etc., for building materials such as handrails,
For example, cooking appliances such as microwave ovens and rice cookers, household appliances such as refrigerators, washing machines, telephones, and vacuum cleaners, canned beverage cans,
Metal containers such as pails and drums, system kitchens
Water supplies such as sinks, furniture such as desks, shelves and tables,
It is suitable as a constituent material for decorative panels, interior / exterior panels, structures, accessories, parts, etc. in general medical equipment, stationery, trains, automobiles, ships, aircrafts, etc.

[Brief description of the drawings]

FIG. 1 is a diagram showing a three-dimensional surface roughness SRa and a surface roughness curve of a film obtained by approximating a sine curve by a three-dimensional surface roughness analyzer.

FIG. 2 is an explanatory diagram of an apparatus for measuring an air bleed speed.

[Explanation of symbols]

 SRa Three-dimensional surface roughness 1 Board 2 Glass plate 3 Suction pipe 4 Vacuum pump 5 Film sample 6 Adhesive tape

Continued on front page F term (reference) 4F100 AK41B AK41J AK41K AL06B AT00A BA02 BA10A BA10B GB08 GB15 GB23 GB31 GB33 GB48 GB66 GB71 JC00B JD02B JK09 JK15B JL05 JN01B YY00B 4F210 AA24E AE10 QC06 Q07

Claims (5)

[Claims] 1. A film containing an antimicrobial composition on at least one surface of a surface layer, wherein the film contains 1 part of boiling water.
The change in haze value before and after immersion for 00 hours is 1.0% or less per 10 μm of film thickness, and JIS Z29
11 The mold resistance indicated by the evaluation method according to 6.2.2 is 2 or more before and after immersion in boiling water for 100 hours, and the three-dimensional surface roughness SRa of the antibacterial surface layer on at least one side of the film is 0.1 or more. 04 μm or more, and the number of projections per unit area PCC value is 2000 / mm.
An antibacterial film having an air release speed of ² or more and an air bleeding speed of 500 seconds or less. 2. The antibacterial film according to claim 1, wherein the antibacterial composition is a polymer in which a residue of an organic antibacterial agent is bonded to a main chain or a side chain. 3. The residue of the organic antibacterial agent according to claim 2,
An antibacterial film characterized by being at least one of an ammonium base, a phosphonium base, and a sulfonium base. 4. The antibacterial film according to claim 2, wherein the polymer substance mainly comprises a polyester composition. 5. The antibacterial film according to claim 1, wherein the film is a biaxially stretched film.