JP2002273834A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film developing antistatic properties of a high level regardless of a humidity change, excellent in ink adhesiveness and shaving resistance, not containing heavy metal elements such as antimony or the like and friendly to environment. SOLUTION: The laminated film is constituted by providing a laminating film containing 10-90 wt.% of amorphous stannic oxide with a mean particle size of 1-12 nm and 90-10 wt.% of a binder resin on at least the single surface of a thermoplastic resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film, and more particularly to a laminated film which exhibits a high level of antistatic properties regardless of changes in humidity, and has excellent ink adhesion and abrasion resistance. The present invention relates to an environmentally friendly laminated film containing no heavy metal element.

[0002]

2. Description of the Related Art Thermoplastic resin films represented by polyolefin films, polyester films, polyamide films, polyphenylene sulfide films, etc. are used for industrial materials because of their lightness, thinness and mechanical properties.
It has been widely used as a base film for various applications such as magnetic material applications and packaging applications, and is expected to grow in various fields in the future of lighter, thinner and shorter sizes.

[0003] Above all, biaxially oriented polyester films have excellent properties such as dimensional stability, mechanical properties, heat resistance, and electrical properties, and are used as VHS tapes, audio tapes, backup tapes for computer data, and the like. Representative magnetic tapes, prepaid cards,
It is widely used as a base film for many applications such as magnetic recording materials including cards such as IC cards and optical recording cards, packaging materials, electric insulating materials, various photographic materials, graphic arts materials, and label materials.

However, in general, a biaxially oriented polyester film has a high degree of crystal orientation on its surface, has poor adhesion to various paints and inks, and has no antistatic properties because it is an insulating resin. There is a disadvantage that there is no. For this reason, conventionally, studies have been made to impart adhesion and antistatic properties to the polyester film surface by various methods.

[0005] For example, as a method of kneading an antistatic agent into a base film and imparting an antistatic property to the surface of the base film, for example, a method of adding an antistatic agent to a polyester resin and applying it (Japanese Patent Laid-Open No. No. 141525), a method of applying a styrene sulfonic acid copolymer (Japanese Unexamined Patent Publication No.
No. 204240), a method of providing a polyaniline-based conductive agent by coating or the like (JP-A-7-101016), and a method of providing an antimony-doped tin oxide-based conductive agent by coating or the like (JP-A-9-152723; JP-A-11-278858, JP-A-7-32
No. 9250) has been proposed.

[0006]

However, the above-mentioned prior art has the following problems. When an ion conductive type is used as an antistatic agent, there is a considerable degree of humidity dependency, particularly when a low molecular weight type is used. This is a major problem in product quality, such as not being obtained.

On the other hand, the electron conduction type antistatic agent does not have the above-mentioned humidity dependence due to its conduction mechanism. However, for example, a polyaniline type antistatic agent has a problem of coloring such as green color and is not preferable in terms of product appearance. The tin oxide antistatic agent doped with antimony does not have a problem of coloring, but a doping agent is essential to exhibit conductivity.
Tin oxide itself is a metal that has been oxidized, but the doping agent uses antimony metal, and the heavy metal-based element has a high possibility of polluting the environment during handling, and above all, Doping is a necessary condition for developing conductivity.

The object of the present invention is to eliminate these drawbacks, to achieve a high level of antistatic properties irrespective of environmental changes, to provide excellent ink adhesion and abrasion resistance, and to provide an environmentally friendly laminated film. To provide.

[0009]

In order to solve the above problems, the laminated film of the present invention comprises an amorphous stannic oxide having an average particle diameter of 1 nm or more and 12 nm or less on at least one surface of a thermoplastic resin film. 10-90% by weight,
A laminated film containing 90 to 10% by weight of a binder resin is provided.

The above laminated film has an average particle size of 1 on at least one surface of the thermoplastic resin film before the completion of the crystal orientation.
nm or more, after applying an aqueous coating solution containing amorphous stannic oxide of 12 nm or less, stretched in at least one direction,
It is preferably made of a material formed by performing a heat treatment.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with preferred embodiments. The thermoplastic resin film referred to in the present invention is a general term for a film that is melted or softened by heat and is not particularly limited, but typical examples include a polyester film,
Acrylic films such as polycarbonate films, polymethyl methacrylate films and polystyrene films, polyolefin films such as polypropylene films and polyethylene films, polyamide films such as nylon, polyvinyl chloride films, polyurethane films, and fluorine-based films can be used.

These may be homopolymers or copolymers. Of these, polyester films, polycarbonate films, acrylic films, polyamide films, and the like are preferable in terms of mechanical properties, dimensional stability, transparency, and the like.Furthermore, in terms of mechanical strength and versatility, polyester films are preferable. Is preferred.

Hereinafter, a polyester film will be described as a typical example, but the present invention is not limited to this.

In the polyester film according to the laminated film of the present invention, polyester is a generic term for polymers having an ester bond as a main bonding chain, and preferred polyesters include ethylene terephthalate, propylene terephthalate and ethylene. -2,6-naphthalate, butylene terephthalate, propylene-
2,6-naphthalate, ethylene-α, β-bis (2-
A material containing at least one component selected from chlorophenoxy) ethane-4,4'-dicarboxylate and the like as a main component can be used. These constituents may be used alone or in combination of two or more. Among them, it is particularly preferable to use a polyester having ethylene terephthalate as a main constituent when quality, economy and the like are comprehensively judged. . Further, when used for applications such as heat and shrinkage stress acting on the substrate, for example, when applying a printing ink or the like, or when accompanied by resin shrinkage such as providing an ultraviolet-curable resin layer, Polyethylene-2,6-naphthalate which is excellent in heat resistance and rigidity is more preferable.

[0015] These polyesters may further contain some other dicarboxylic acid component or diol component, preferably 2 or more.
0 mol% or less may be copolymerized.

Further, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, and fillers are contained in the polyester. , An antistatic agent, a nucleating agent and the like may be added to such an extent that their properties are not deteriorated.

The intrinsic viscosity of the above-mentioned polyester (25 ° C.
Measured in o-chlorophenol) is 0.4-1.2.
dl / g is preferable, and more preferably 0.5 to 0.8 d
Those in the range of 1 / g are suitable for practicing the present invention.

The polyester film using the above polyester is preferably biaxially oriented when the laminated film is provided. The biaxially oriented polyester film generally means an unstretched polyester sheet or film in the longitudinal direction and the width direction.
It is stretched about 5 to 5 times, and then heat-treated to complete crystal orientation, and indicates a biaxially oriented pattern by wide-angle X-ray diffraction.

The thickness of the polyester film is not particularly limited, and is appropriately selected depending on the use in which the laminated film of the present invention is used. However, it is usually preferable from the viewpoint of mechanical strength, handleability and the like. Is 1-500μ
m, more preferably 5 to 300 μm, most preferably 9
２１０210 μm. Further, the obtained films can be used by being bonded by various methods.

In addition, a white polyester film can be suitably used as a base film in image receiving sheet applications, label applications, recording card applications, and the like.

The white polyester film is not particularly limited as long as it is a polyester film colored white, but the whiteness is preferably 65 to 150%, more preferably 80 to 120%, and the optical density Is 0.5 to 5, more preferably 1 to 3 in terms of 100 μm.
Is the case. For example, when a substrate film having a small optical density is used, the concealing property is inferior.For example, in a label or the like, the appearance of the printed layer on the surface is easily impaired by the transmission of coloring such as the sticking surface, while the whiteness is small. In this case, whiteness tends to decrease when viewed with the naked eye, which is not preferable as a white polyester film.

The method for obtaining such whiteness and optical density is not particularly limited, but can usually be obtained by adding a resin incompatible with inorganic particles or polyester. The amount to be added is not particularly limited, but is preferably 5 to 35% by weight, more preferably 8 to 2% in the case of inorganic particles.
5% by weight. On the other hand, when an incompatible resin is added, it is preferably 3 to 35% by volume, more preferably 6 to 2% by volume.
5% by volume.

The inorganic particles are not particularly limited, but preferably have an average particle size of 0.1 to 4 μm, more preferably 0.3 to 4 μm.
1.5 μm inorganic particles and the like can be used as typical examples. Specifically, barium sulfate, calcium carbonate, calcium sulfate, titanium oxide, silica, alumina, talc, clay and the like or a mixture thereof can be used.These inorganic particles are other inorganic compounds, for example,
It may be used in combination with calcium phosphate, titanium oxide, mica, zirconia, and the like.

The resin incompatible with the above-mentioned polyester is not particularly limited. For example, in the case of mixing with polyethylene terephthalate or polyethylene-2,6-naphthalate, acrylic resin, polyethylene, polypropylene, modified olefin resin , Polybutylene terephthalate resin, phenoxy resin, polyphenylene oxide, and the like may be used, and may be used in combination with the above-described inorganic particles. For example, in particular, a white polyester film having a specific gravity of 0.5 to 1.3, which has a cavity inside, is mixed with a resin incompatible with inorganic particles or polyester and biaxially stretched, and the base film itself is reduced in weight When it is used for an image receiving sheet, it has advantages such as improved printing characteristics.

The white polyester film may be a film colored in another color (the coloring method is not particularly limited, but usually, coloring by pigment or dyeing is used),
Alternatively, a laminate of two or more layers with a transparent film may be used.

In the present invention, the laminated film refers to a film-like film which is formed in a laminated structure on the surface of a thermoplastic resin film as a substrate. The film itself may be a single layer or a multilayer.

The stannic oxide according to the present invention needs to be amorphous stannic oxide. Generally, stannic oxide is disclosed in JP-A-11-2785.
No. 82 and Japanese Unexamined Patent Publication No. 9-152723, a crystalline state represented by a needle-like state,
Although there is an amorphous state (so-called amorphous state), the present invention refers to the latter stannic oxide in an amorphous state. Conventionally, crystalline stannic oxide requires the use of a doping agent in order to exhibit antistatic properties, for example, whereas amorphous stannic oxide according to the present invention does not use a doping agent. It is characterized by exhibiting antistatic properties.

Thus, for example, antimony conventionally used for crystalline stannic oxide is not required, which is advantageous not only in terms of production cost but also in terms of environment in which antimony which is a heavy metal element is not used. It is a thing.

Further, by setting the average particle size of the amorphous stannic oxide to 1 to 12 nm, the compatibility with the binder resin is improved, the conductive path of electron conduction is uniformly exhibited, and the antistatic property is improved. In addition, the particles have a smaller particle diameter than conventional ones, so that a close-packed structure can be easily obtained, the conductivity is further improved by increasing the contact points between the particles, and the transparency of the coating film is improved. The average particle size is preferably 1 to 10 nm, more preferably 1 to 8 nm. When the thickness exceeds 12 nm, the transparency of the coating film is poor or the antistatic property is poor. On the other hand, if it is less than 1 nm, problems such as poor antistatic properties occur. Regarding this point, although the reason is not clear, it is considered that if the stannic oxide particles are excessively finely dispersed in the binder resin used in combination, the contact points between the particles are reduced and the antistatic property is deteriorated. . In addition, even if the binder resin has a particle diameter of less than 1 nm, when the binder resin is not used, the antistatic property is extremely excellent.

The laminated film according to the present invention comprises amorphous stannic oxide and a binder resin as main constituent components. Examples of the binder resin include an acrylic resin, a polyester resin, a urethane resin,
Epoxy resins, alkyd resins, phenol resins, polyolefin resins, and the like can be used. For example, when a polyester film is used as the thermoplastic resin film, a polyester resin, an acrylic resin, and a urethane resin are preferable in terms of adhesiveness to the base film as the binder resin, and a polyolefin film is used as the thermoplastic resin film. In this case, an acrylic resin, a urethane resin, or a polyolefin resin is preferable as the binder resin from the viewpoint of adhesiveness to the base film, but is not limited thereto.

Each of the above binder resins may be used alone, or two different resins, for example,
Polyester resin and urethane resin, polyester resin and acrylic resin, or urethane resin and acrylic resin may be used in combination. Of course, three or more types may be used in combination. It is often preferable to do so.

In the laminated film of the present invention, the polyester resin used as a component of the laminated film has an ester bond in a main chain or a side chain, and is obtained by polycondensing a dicarboxylic acid and a diol.

As the carboxylic acid component constituting the polyester resin, aromatic, aliphatic and alicyclic dicarboxylic acids and trivalent or higher polycarboxylic acids can be used. As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 −
Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid and the like can be used.
These aromatic dicarboxylic acids are preferably at least 30 mol%, more preferably at least 35 mol%, most preferably at least 4 mol% of the total dicarboxylic acid components in view of the strength and heat resistance of the laminated film.
It is preferable to use one having 0 mol% or more. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid,
Sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, and ester-forming derivatives thereof can be used.

As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, 2,
4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3 -Methyl-1,5
-Pentanediol, 2,2,4-trimethyl-1,6
-Hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-
Cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiphenol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2 -Norbornylidene)
Diphenol, 4,4′-dihydroxybiphenol,
o-, m-, and p-dihydroxybenzene, 4,
4′-isopropylidenephenol, 4,4′-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and the like can be used.

When the polyester resin is used as a coating liquid containing an aqueous resin, a compound containing a sulfonate group or a compound containing a carboxylate group is used in order to make the polyester resin water-soluble or water-dispersible. Is preferably copolymerized.

Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, ,
2,3,4-butanetetracarboxylic acid, 1,2,3,4
-Pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-
1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitate, 2,2 ', 3,3'
-Diphenyltetracarboxylic acid, thiophene-2,3
4,5-Tetracarboxylic acid, ethylenetetracarboxylic acid and the like, or alkali metal salts, alkaline earth metal salts and ammonium salts thereof can be used, but are not limited thereto.

Examples of the compound containing a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid,
4-sulfoisophthalic acid, 4-sulfonaphthalene-2,
7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo-1,4-bis (hydroxyethoxy)
Benzene or the like, or an alkali metal salt, an alkaline earth metal salt, or an ammonium salt thereof can be used, but is not limited thereto.

In the present invention, as the polyester resin that can be used, a modified polyester copolymer, for example, a block copolymer or a graft copolymer modified with acryl, urethane, epoxy or the like is also possible.

Preferred polyester resins include terephthalic acid, isophthalic acid, sebacic acid,
-Sodium sulfoisophthalic acid, ethylene glycol as a glycol component, diethylene glycol, 1,4
-A copolymer selected from butanediol and neopentyl glycol. If water resistance is required,
A copolymer using trimellitic acid as a copolymer component instead of 5-sodium sulfoisophthalic acid can also be suitably used.

In the laminated film of the present invention, the polyester resin used for the laminated film can be produced by the following production method. For example, as a dicarboxylic acid component, terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, a glycol component ethylene glycol, a polyester resin consisting of neopentyl glycol, terephthalic acid, isophthalic acid,
First step of directly esterifying 5-sodium sulfoisophthalic acid with ethylene glycol and neopentyl glycol or transesterifying terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, ethylene glycol, and neopentyl glycol And a second step in which the reaction product of the first step is subjected to a polycondensation reaction.

At this time, as a reaction catalyst, for example, an alkali metal, an alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, a titanium compound and the like can be used.

As a method for obtaining a polyester resin having a large amount of carboxylic acid at the terminal and / or side chain,
JP-A-54-46294, JP-A-60-2090
No. 73, JP-A-62-240318, JP-A-53-26828, JP-A-53-26829, JP-A-53-98336, JP-A-56-11
No. 6,718, JP-A-61-124684, JP-A-62-240318, etc. can be produced with a resin obtained by copolymerizing a trivalent or higher polycarboxylic acid. It may be a method.

Further, the intrinsic viscosity of the polyester resin used for the laminated film according to the present invention is not particularly limited.
It is preferably at least 0.3 dl / g, more preferably at least 0.35 dl / g, most preferably at least 0.4 dl / g in terms of adhesiveness. Glass transition point of polyester resin (hereinafter abbreviated as "Tg")
Is preferably 0 to 130 ° C, more preferably 10 to 85 ° C. If the Tg is less than 0 ° C., for example, the heat resistance is poor, and if it exceeds 130 ° C., the stability and water dispersibility of the resin may be poor.

In the laminated film of the present invention, the urethane resin used as a component of the laminated film is not particularly limited as long as it is a water-soluble or water-dispersible urethane resin having an anionic group. Is obtained by copolymerizing a polyol and a polyisocyanate.

As the urethane resin, those whose affinity for water is increased by a carboxylic acid group, a sulfonic acid group, or a sulfuric acid half ester base can be used. The content of a carboxylate group, a sulfonate group, a sulfuric acid half ester base or the like is preferably 0.5 to 15% by weight.

Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, hexamethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, and triethylene glycol. , Polycaprolactone, polyhexamethylene adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin,
An acrylic polyol or the like can be used.

As the polyisocyanate compound, for example, tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate with trimethylolpropane, or an adduct of hexamethylene diisocyanate with trimethylolethane Can be.

Here, the main constituent components of the urethane resin may contain a chain extender, a crosslinking agent and the like in addition to the polyol compound and the polyisocyanate compound.
As a chain extender or a crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine and the like can be used.

The urethane resin having an anionic group is prepared by, for example, a method using a compound having an anionic group as a polyol, a polyisocyanate, a chain extender, or the like. It can be produced by a method of reacting a compound, a method of reacting a group having an active hydrogen of a urethane resin with a specific compound, and the like, but is not particularly limited.

Further, a resin comprising a polyol having a molecular weight of 300 to 20,000, a polyisocyanate, a chain extender having a reactive hydrogen atom, a compound having a group which reacts with an isocyanate group, and a compound having at least one anionic group is preferable.

The anionic group in the urethane resin is preferably used as a sulfonic acid group, a carboxylic acid group, or an ammonium salt, a lithium salt, a sodium salt, a potassium salt or a magnesium salt thereof.
It is a sulfonate group.

The amount of the anionic group in the polyurethane resin is preferably 0.05% by weight to 8% by weight. If the amount is less than 0.05% by weight, the water dispersibility of the urethane resin tends to deteriorate, and if it exceeds 8% by weight, the water resistance and the blocking resistance of the resin tend to deteriorate.

In the laminated film of the present invention, the acrylic resin used as a component of the laminated film may be, for example, an alkyl acrylate or an alkyl methacrylate (the alkyl group may be a methyl group or an ethyl group). , N-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, phenylethyl, etc.), 2- Hydroxy group-containing monomers such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylate Ruamido, N- methylolacrylamide, N- methylolmethacrylamide, N, N
-Dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide,
Amide group-containing monomers such as N-phenylacrylamide, N, N-diethylaminoethyl acrylate,
Amino group-containing monomers such as N-diethylaminoethyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; and carboxyl groups such as acrylic acid, methacrylic acid and salts thereof (lithium salts, sodium salts, potassium salts, etc.) or the like. Salt-containing monomers and the like can be used, and these are copolymerized using one kind or two or more kinds. Further, they can be used in combination with other types of monomers.

Other types of monomers include, for example, epoxy group-containing monomers such as allyl glycidyl ether, and sulfones such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.). Monomers containing acid groups or salts thereof, crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salts, sodium salts,
Monomers containing a carboxyl group or a salt thereof, such as potassium salts and ammonium salts), maleic anhydride,
Monomers containing acid anhydrides such as itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, acrylonitrile, methacryloyl Nitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride, and the like can be used.

As the acrylic resin that can be used in the present invention, a modified acrylic copolymer, for example, a block copolymer or a graft copolymer modified with polyester, urethane, epoxy or the like is also possible.

The glass transition point (Tg) of the acrylic resin used in the present invention is not particularly limited, but is preferably -10 to 90 ° C, more preferably 0 to 5 ° C.
0 ° C, most preferably 10 to 40 ° C. When an acrylic resin having a low Tg is used, heat-resistant adhesiveness tends to be inferior or blocking tends to occur. On the other hand, when it is too high, adhesiveness deteriorates and film-forming properties deteriorate, which is not preferable. The molecular weight of the acrylic resin is preferably 50,000 or more, more preferably 300,000 or more, from the viewpoint of adhesiveness.

Preferred acrylic resins used in the present invention include copolymers selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylolacrylamide, and acrylic acid.

It is preferable to dissolve, emulsify, or suspend the acrylic resin in water and use it as a water-based acrylic resin from the viewpoint of environmental pollution and explosion-proof property during coating. Such an aqueous acrylic resin may be copolymerized with a monomer having a hydrophilic group (such as acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid, or a salt thereof), emulsion-polymerized using a reactive emulsifier or a surfactant, and suspended. It can be prepared by a method such as turbid polymerization or soap-free polymerization.

In the laminated film according to the present invention, various crosslinking agents can be added. The crosslinking agent used is
The functional group present in the binder resin described above, for example, a hydroxyl group, a carboxyl group, a methylol group, is not particularly limited as long as it can be cross-linked with an amide group, for example, melamine-based crosslinking agent, oxazoline-based Crosslinkers, isocyanate crosslinkers, aziridine crosslinkers, epoxy crosslinkers, methylolated or alkylolated urea, acrylamide, polyamide resins, amide epoxy compounds, various silane coupling agents, various titanate couplings Agents and the like can be used. In particular, a melamine-based cross-linking agent and an oxazoline-based cross-linking agent can be suitably used in terms of compatibility with a resin, adhesiveness, and the like.

In the laminated film according to the present invention, the amorphous stannic oxide and the binder resin are 10 to 90% by weight of amorphous stannic oxide and 90 to 10% by weight of the binder resin in terms of the solid content weight ratio. %. 10% by weight amorphous stannic oxide
If the amount is less than 90%, the antistatic property is poor. If the amount exceeds 90% by weight, the adhesion to the base film and the coating is deteriorated, and the abrasion resistance of the laminated film is poor. According to the study of the present inventors, the amorphous stannic oxide contained 30 to 90% by weight,
The content of the binder resin is preferably 70 to 10% by weight, more preferably 50 to 50% by weight of amorphous stannic oxide.
It is preferable that the content is 80 to 80% by weight and the content of the binder resin is 50 to 20% by weight in terms of adhesion to a coating material, for example, ink, and abrasion resistance.

In the laminated film according to the present invention, the cross-linking agent may be added in any amount within a range that does not impair the effects of the present invention. It is preferable to add 1 to 50 parts by weight of a crosslinking agent to 100 parts by weight, more preferably 3 to 25 parts by weight.

Further, various additives such as an antioxidant may be contained in the laminated film as long as the effects of the present invention are not impaired.
Heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, and the like may be added.

In the production of the laminated film of the present invention, as a preferable method for providing the laminated film, the laminated film may be provided by a so-called off-line coating method in which a biaxially oriented polyester film is coated. The laminated film may be provided by the so-called in-line coating method, which is provided on the base film during the manufacturing process of the film and stretched together with the base film, but the offline coating is performed according to the desired thickness of the laminated film and the content of the organic solvent in the coating solution. It is common to use different types of coating and in-line coating. In consideration of productivity, the in-line coating method applied during the film forming process is preferable.

For example, in the in-line coating method,
The melt-extruded polyester film before crystal orientation is stretched about 2.5 to 5 times in the longitudinal direction, and a coating liquid is continuously applied to the uniaxially stretched film. The applied film is dried while passing through a stepwise heated zone,
It is stretched about 2.5 to 5 times in the width direction. Further, a method in which the crystal orientation is completed by being continuously guided to a heating zone at 150 to 250 ° C. can be used.

In the present invention, before applying the coating liquid,
The surface of the base film (in the case of the above example, a uniaxially stretched film) is subjected to a corona discharge treatment or the like, and the wet tension of the base film surface is preferably at least 47 mN / m, more preferably at least 50 mN / m. This is preferable because the adhesiveness and applicability of the laminated film to the base film can be improved.

The thickness of the laminated film is not particularly limited, but is usually preferably in the range of 0.01 to 10 μm, more preferably 0.02 to 5 μm, and most preferably 0.05 μm to
1 μm. If the thickness of the laminated film is too thin, poor antistatic properties and poor adhesion may occur.

The coating method on the substrate film uses various coating methods, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Meyer bar coating method, a die coating method, a spray coating method and the like. be able to.

Next, a method for producing a laminated film of the present invention will be described with reference to polyethylene terephthalate (hereinafter referred to as “PE”).
T ") is used as the base film, but the present invention is not limited to this.

The above-described environment-friendly laminated film which is excellent in high levels of antistatic properties and ink adhesion and does not contain a heavy metal element such as antimony, has an average particle size of at least one surface of a thermoplastic resin film. 1 nm in diameter
As described above, the amorphous stannic oxide of 12 nm or less
It can be manufactured by providing a laminated film containing 0 to 90% by weight and 90 to 10% by weight of a binder resin.

More specifically, for example, the limiting viscosity is 0.5
After vacuum drying of ~ 0.8 dl / g PET pellets,
It is supplied to an extruder, melted at 260 to 300 ° C., extruded from a T-shaped die into a sheet, wound around a mirror casting drum having a surface temperature of 10 to 60 ° C. using an electrostatic application casting method, and cooled and solidified. Create an unstretched PET film. This unstretched film is stretched 2.5 to 5 times in the longitudinal direction (the direction of film movement) between rolls heated to 70 to 120 ° C. At least one surface of the film is subjected to a corona discharge treatment, and the wetting tension of the surface is set to 47 mN.
/ M or more, and the coating liquid for forming a laminated film according to the present invention is applied to the treated surface. The coated film is gripped with a clip and guided to a hot air zone heated to 70 to 150 ° C., dried, stretched 2.5 to 5 times in the width direction, and subsequently guided to a heat treatment zone at 160 to 250 ° C. For 1 to 30 seconds to complete the crystal orientation. During this heat treatment step, a 1 to 10% relaxation treatment may be performed in the width direction or the longitudinal direction as necessary. Biaxial stretching is
Any of longitudinal and transverse sequential stretching or simultaneous biaxial stretching may be used, and after stretching in the longitudinal and transverse directions, re-stretching in any of the longitudinal and transverse directions may be performed. The thickness of the polyester film is not particularly limited, but is preferably 1 to 500 μm.

In the above examples, the base film on which the laminated film is provided may contain at least one selected from the composition for forming a laminated film and the reaction products thereof. In this case, there are effects that the adhesiveness between the laminated film and the base film is improved, and the lubricity of the laminated polyester film is improved. Regarding the addition amount of one kind or plural kinds, the total amount of addition is 5 ppm or more.
Less than 0% by weight is preferred in terms of adhesiveness and lubricity. Considering environmental protection and productivity, a method using a regenerated pellet containing the laminated film forming composition is preferable as a method for containing the pellet.

The thus obtained laminated film of the present invention can be provided with various coatings such as various printing inks and ultraviolet curable resins on the laminated film. It can be widely used as various base films for insulating materials, insulating tapes, optics, graphics, cards, ribbons, vapor deposition, packaging, capacitors, etc.

[Method of Measuring Characteristics and Method of Evaluating Effects]
The method for measuring characteristics and the method for evaluating effects in the present invention are as follows. (1) Thickness of laminated film The thickness was determined from a photograph obtained by observing a cross section of a laminated polyester film provided with a laminated film using a transmission electron microscope HU-12 manufactured by Hitachi, Ltd. The thickness was an average value of 30 pieces in the measurement visual field.

(2) Transparency As a parameter of transparency, haze is used in the present invention. Haze measurement is normal (23 ° C, 65% relative humidity)
After leaving the laminated film for 2 hours, a fully automatic direct reading haze computer “HGM-” manufactured by Suga Test Instruments Co., Ltd.
2DP ". The average value measured three times was defined as the haze value of the sample.

(3) Adhesiveness UV-curable ink (Best Cure 161 ink)
It was applied to a thickness of about 1.5 μm on the laminated film by roll coating using (T & K Toka). afterwards,
Irradiation was performed for 5 seconds at an irradiation distance (distance between the lamp and the ink surface) of 9 cm using an ultraviolet lamp having an irradiation intensity of 80 W / cm to cure the ultraviolet curable ink. The evaluation of adhesion was performed by the following method. 1 mm ² cross cut 100
The pieces were put on each other, and a cellophane tape manufactured by Nichiban Co., Ltd. was adhered thereon, and reciprocated three times with a load of 19.6 N using a rubber roller. To give a 4-grade rating (（: 100,
○: 80 to 99, Δ: 50 to 79, ×: 0 to 49). (A) and (B) were evaluated as having good adhesiveness.

(4) Antistatic Property In the present invention, surface resistivity was used as a parameter of antistatic property. The surface resistivity was measured in a normal state (23 ° C., 65% relative humidity) for 24 hours, and in that atmosphere, using a digital ultra-high resistance / micro ammeter R8340A (manufactured by Advantest Co., Ltd.) at an applied voltage of 100 V After applying for 10 seconds, the measurement was performed. The unit is Ω / □. Incidentally, a level surface resistivity is no practical problem as long as the 1 × 10 ¹² Ω / □ or less, it can be said to exhibit excellent antistatic properties 1 × ¹⁰ 10 Ω / □ or less. Furthermore, in the present invention, the same evaluation as described above was performed at a relative humidity of 35%, and the evaluation of the humidity dependency was also performed.

(5) Abrasion resistance The laminated film provided on the thermoplastic resin film was scratched with a nail, and the degree of scratches was visually judged as follows. In addition, (（) and (）) were determined to have good abrasion resistance. (◎): No scraping at all (○): Scratched trace on the laminated film (△): Laminated film is cleaved along with the scratched nail (×): Powdered

[0078]

Next, the present invention will be described with reference to examples, but is not necessarily limited thereto. Example 1 As a biaxially stretched polyester film, a substrate thickness of 12 μm made of “Lumirror” P51 (packaging grade, one-sided easy-adhesion product) manufactured by Toray Industries, Inc. was used. The following laminated film forming coating liquid is applied on the treated surface, and dried at 120 ° C. for 1 minute,
Further, heat treatment was performed at 135 ° C. for 20 seconds to obtain a laminated film having a coating thickness of 0.5 μm after drying. The results are shown in Table 1. The results were excellent in transparency, antistatic property, ink adhesion and abrasion resistance.

"Laminated film forming coating liquid" Coating liquid 1: amorphous stannic oxide (average particle diameter: 1)
0 nm) is dispersed in water and has a solid content of 8% by weight. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-Sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol%

A mixture of the above-mentioned coating liquid 1 and coating liquid 2 in a solid content weight ratio of coating liquid 1 / coating liquid 2 = 90/10 was used as a coating liquid for forming a laminated film.

Example 2 A laminated film was obtained in the same manner as in Example 1, except that the weight ratio of the solid content of the coating liquid 1 and the coating liquid 2 was changed to 40/60. . The results are shown in Table 1.
It was also excellent in antistatic properties, ink adhesion properties and abrasion resistance.

Example 3 0.015% by weight of colloidal silica having an average particle size of 0.4 μm and 0.05% by weight of colloidal silica having an average particle size of 1.5 μm
PET pellets containing 0.05% by weight (intrinsic viscosity 0.6
3dl / g) is sufficiently dried in vacuum, fed to an extruder, melted at 285 ° C, extruded into a sheet from a T-shaped die, and applied to a mirror-surface casting drum having a surface temperature of 25 ° C using an electrostatic application casting method. It was wound and cooled and solidified. This unstretched film was heated to 92 ° C. and stretched 3.8 times in the longitudinal direction to obtain a uniaxially stretched film. The film was subjected to a corona discharge treatment in air, the wet tension of the substrate film was set to 52 mN / m, and the following coating liquid for forming a laminated film was applied to the treated surface. The coated uniaxially stretched film is guided to a preheating zone while being gripped with a clip, dried at 90 ° C., and continuously continuously heated in a 90 ° C. heating zone in the width direction.
The film was double-stretched and heat-treated in a heating zone at 235 ° C. to obtain a laminated PET film in which crystal orientation was completed. At this time, the thickness of the base PET film was 38 μm, and the thickness of the laminated film was 0.3 μm. The results are shown in Table 1. The results were excellent in transparency, antistatic property, ink adhesion and abrasion resistance.

"Laminated film forming coating liquid" Coating liquid 1: amorphous stannic oxide (average particle diameter: 1)
0 nm) is dispersed in water and has a solid content of 8% by weight. Coating liquid 3: An aqueous coating liquid having a solid content of 30% by weight of an acrylic resin (glass transition temperature: 42 ° C.) emulsion having the following copolymer composition. -Copolymerization component Methyl methacrylate 62 mol% Ethyl acrylate 35 mol% Acrylic acid 1 mol% N-methylolacrylamide 2 mol%-Additive: 50% by weight aqueous solution of glycerin dissolved in water.

A mixture obtained by mixing the above-mentioned coating liquid 1 and coating liquid 3 at a solid content weight ratio of coating liquid 1 / coating liquid 3 = 50/50, and further adding an additive at 10% by weight in solid content weight ratio. Was used as a coating liquid for forming a laminated film.

At this time, the glycerin component evaporates in the heat treatment zone (235 ° C.) in the polyester film forming step, and does not substantially remain in the laminated film. Although the boiling point of glycerin is 290 ° C., since the vapor pressure and the coating film of the substance are very thin at 0.3 μm,
It was confirmed by heat loss analysis that the water had evaporated even at 235 ° C. in the heat treatment zone.

Example 4 A laminated PET film was obtained in the same manner as in Example 3, except that the average particle diameter of the amorphous stannic oxide in the coating liquid 1 was 5 nm. Was. Table 1 shows the results
As shown in Table 1, it was excellent in transparency, antistatic property, ink adhesion property and abrasion resistance.

Example 5 In the coating liquid for forming a laminated film of Example 3, the average particle diameter of the amorphous stannic oxide of the coating liquid 1 was 5 nm, and the coating liquid 1 and the coating liquid 3 were 80/20 (solid). (Weight ratio by weight), and a laminated PET film was obtained in the same manner as in Example 3 except that the components were mixed. The results are shown in Table 1. The results were excellent in transparency, antistatic property, ink adhesion and abrasion resistance.

Example 6 In the laminated film forming coating liquid of Example 3, the average particle diameter of the amorphous stannic oxide of the coating liquid 1 was 5 nm, and the coating liquid 1 and the coating liquid 3 were 30/70 (solid (Weight ratio by weight), and a laminated PET film was obtained in the same manner as in Example 3 except that the components were mixed. The results are shown in Table 1. The results were excellent in transparency, antistatic property, ink adhesion and abrasion resistance.

Example 7 A laminated PET film was obtained in the same manner as in Example 3, except that the coating liquid for forming a laminated film in Example 3 was changed to the following coating liquid for forming a laminated film. The results are shown in Table 1. The results were excellent in transparency, antistatic property, ink adhesion and abrasion resistance.

[Coating liquid for forming a laminated film] Coating liquid 1: amorphous stannic oxide (average particle size: 5)
An aqueous coating liquid having a solid content concentration of 8% by weight in which water is dispersed in water. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol% ・ Additive: Glycerin dissolved in water 50% by weight aqueous solution.

A mixture obtained by mixing the above-mentioned coating liquid 1 and coating liquid 2 at a coating weight ratio of coating liquid 1 / coating liquid 2 = 60/40, and further adding an additive of 10% by weight in solid weight ratio. Was used as a coating liquid for forming a laminated film.

Example 8 As a biaxially stretched polypropylene film, a base material having a thickness of 15 μm from “Torayfan” manufactured by Toray Industries, Inc. was used. Surface tension of 50 mN by corona discharge treatment in nitrogen atmosphere
/ M, the following coating liquid for forming a laminated film is applied on the treated surface, dried at 120 ° C. for 1 minute, and further heat-treated at 135 ° C. for 20 seconds. Obtained. The results are shown in Table 1. The transparency, antistatic property,
The ink adhesion and the abrasion resistance were also excellent.

"Laminated film forming coating liquid" Coating liquid 1: amorphous stannic oxide (average particle diameter: 1)
0 nm) is dispersed in water and has a solid content of 8% by weight. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-Sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol%

A mixture of the above-mentioned coating liquid 1 and coating liquid 2 at a solid content weight ratio of coating liquid 1 / coating liquid 2 = 80/20 was used as a coating liquid for forming a laminated film.

Comparative Example 1 A laminated PET film was obtained in the same manner as in Example 1, except that the following coating liquid for forming a laminated film was used. The results are shown in Table 1. The antistatic properties were extremely poor.

"Laminated film forming coating liquid" Coating liquid 4: stannic oxide having a needle-like crystal structure was dissolved in water /
An aqueous coating liquid having a solid content of 8% by weight dispersed in an isopropyl alcohol mixed solvent (mixed at a weight ratio of 80/20). Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-Sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol%

A mixture of the above-mentioned coating liquid 4 and coating liquid 2 at a coating weight ratio of coating liquid 4 / coating liquid 2 = 60/40 was used as a coating liquid for forming a laminated film.

Comparative Example 2 A laminated PET film was obtained in the same manner as in Example 3, except that the coating liquid for forming a laminated film of Example 3 was changed to the following coating liquid for forming a laminated film. The results are shown in Table 1. As a result, the product was inferior in antistatic properties and ink adhesion, and was extremely inferior in product appearance due to blackish brown coloring.

"Coating solution for forming a laminated film" Coating solution 5: An aqueous coating solution having a solid content of 6% by weight in which sulfonated polyaniline (a counter ion of a sulfonated portion is an ammonium salt) is dispersed in water. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water. Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-sodium sulfoisophthalic acid 12 mol% Diol component ethylene glycol 5 mol% diethylene glycol 75 mol% neopentyl glycol 20 mol% Additive: glycerin dissolved in water 50% by weight aqueous solution.

A mixture obtained by mixing the above-mentioned coating liquid 5 and coating liquid 2 at a solid content weight ratio of coating liquid 5 / coating liquid 2 = 60/40, and further adding 10% by weight of an additive at a solid content weight ratio. Was used as a coating liquid for forming a laminated film.

Comparative Example 3 A laminated PET film was obtained in the same manner as in Example 3, except that the following coating liquid for forming a laminated film was used. The results are shown in Table 1, which was inferior in transparency and antistatic property.

"Coating solution for forming a laminated film" Coating solution 6: amorphous stannic oxide (average particle size: 1)
(5 nm) dispersed in water and having a solid content of 8% by weight. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol% ・ Additive: Glycerin dissolved in water 50% by weight aqueous solution.

A mixture obtained by mixing the above-mentioned coating liquid 6 and coating liquid 2 at a solid content weight ratio of coating liquid 6 / coating liquid 2 = 60/40, and further adding 10% by weight of an additive at a solid content weight ratio. Was used as a coating liquid for forming a laminated film.

Comparative Example 4 A laminated PET film was obtained in the same manner as in Example 3, except that the coating liquid for forming a laminated film of Example 3 was changed to the following coating liquid for forming a laminated film. The results are shown in Table 1. The antistatic properties were extremely poor.

"Laminated film forming coating liquid" Coating liquid 7: amorphous stannic oxide (average particle diameter:
(0.5 nm) dispersed in water and having a solid content of 6% by weight. Coating liquid 2: An aqueous coating liquid having a solid content of 16% by weight, in which a polyester resin (glass transition temperature: 21 ° C.) having the following copolymer composition is dispersed in water.・ Acid component Terephthalic acid 10 mol% Isophthalic acid 78 mol% 5-sodium sulfoisophthalic acid 12 mol% ・ Diol component Ethylene glycol 5 mol% Diethylene glycol 75 mol% Neopentyl glycol 20 mol% ・ Additive: Glycerin dissolved in water 50% by weight aqueous solution.

A mixture obtained by mixing the above-mentioned coating liquid 7 and coating liquid 2 at a solid content weight ratio of coating liquid 7 / coating liquid 2 = 60/40, and further adding an additive by 10% by weight in solid content weight ratio. Was used as a coating liquid for forming a laminated film.

Comparative Example 5 A laminated PET film was obtained in the same manner as in Example 3, except that the following coating liquid for forming a laminated film was used. The results are shown in Table 1. The antistatic properties under low humidity were extremely poor, and the humidity dependence was very large. Such a laminated film, for example, has a serious problem such as being damaged at a low humidity when used for packaging or the like, although discharge due to electrification of a computer electronic component or the like greatly affects the discharge.

"Coating solution for forming a laminated film" Coating solution 8: Lithium polystyrenesulfonate (weight average molecular weight: 65000) dissolved in water has a solid concentration of 1
6% by weight aqueous coating liquid. Coating liquid 3: The acrylic resin (glass transition temperature: 42 ° C.) having the following copolymer composition has a solid concentration of 3
0% by weight aqueous coating liquid. -Copolymerization component Methyl methacrylate 62 mol% Ethyl acrylate 35 mol% Acrylic acid 1 mol% N-methylolacrylamide 2 mol%

A mixture of the above coating liquid 8 and coating liquid 3 at a coating weight ratio of coating liquid 8 / coating liquid 3 = 25/75 was used as a coating liquid for forming a laminated film.

[0110]

[Table 1]

[0111]

According to the laminated film of the present invention, at least one surface of the thermoplastic resin film has an average particle size of 1 nm.
As described above, the amorphous stannic oxide of 12 nm or less
By providing a laminated film containing 0 to 90% by weight and a binder resin of 90 to 10% by weight, a high level of antistatic property is exhibited irrespective of humidity change, and ink adhesion and abrasion resistance are excellent. Also, an effect excellent in environmental resistance such as not containing a heavy metal element such as antimony can be exhibited.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/36 B32B 27/36 // B32B 7/02 104 B32B 7/02 104 B29K 67:00 B29K 67: 00 101: 12 101: 12 B29L 7:00 B29L 7:00 9:00 9:00 (72) Inventor Takashi Mimura 1-1-1 Sonoyama, Otsu City, Shiga Prefecture F-term in the Shiga Plant of Toray Co., Ltd. ) 4D075 BB05Z BB35Z CA02 CA22 CA35 DA04 DB31 DB48 DC27 DC28 EA06 EC02 EC53 4F100 AA28B AK01A AK01B AK41B AK42A BA02 CC00B DE01B EH46 EJ38 EJ38A JA12B JB16A JG03 JL11 4G01 QAQAAGQAAGQ

Claims (3)

[Claims] 1. A laminated film containing 10 to 90% by weight of amorphous stannic oxide having an average particle diameter of 1 nm or more and 12 nm or less and 90 to 10% by weight of a binder resin is provided on at least one surface of a thermoplastic resin film. A laminated film characterized by being made. 2. A laminated film having an average particle diameter of 1 n on at least one surface of a thermoplastic resin film before completion of crystal orientation.
2. The laminated film according to claim 1, wherein the laminated film is formed by applying an aqueous coating liquid containing amorphous stannic oxide having a size of m or more and 12 nm or less, followed by stretching in at least one direction and performing heat treatment. 3. The thermoplastic resin film is a polyethylene terephthalate film or polyethylene-2,6-
The laminated film according to claim 1, comprising a naphthalate film.