JP2001232739A - Film for vapor deposition and vapor deposited film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for vapor deposition, in which gas barrier properties for oxygen and stream are remarkably excellent, and a vapor deposited film using the same. SOLUTION: The film for vapor deposition is constituted of laminating a polyester B layer containing 0.005-1.0 wt.% hydroxyapatite partiales by 0.01-5 μm thickness on at least one side of a base film (A layer) consisting of a polyester film. Further, in the vapor deposited film. an inorganic thin film is subjected to vapor deposition on the surface of the polyester B layer of the film for vapor deposition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for vapor deposition excellent in barrier properties against oxygen and water vapor and a vapor deposited film comprising the same.

[0002]

2. Description of the Related Art Conventionally, in order to preserve foods and medicines for a long period of time, packaging that has an effect of blocking the intrusion of oxygen and water vapor from the outside air that promotes decay and deterioration is performed, that is, a package excellent in so-called gas barrier properties. There is a need. In recent years, there has been a strong demand for a film package having excellent gas barrier properties used for this purpose to have transparency in which the state of contents can be particularly confirmed.

As an opaque and highly gas-barrier package, a film package in which an aluminum foil is laminated is known, but the aluminum foil is inferior in flexibility to a polymer film, and is not easily bent in a process or the like. Therefore, it is desired to substitute a film having a gas barrier property as high as that of an aluminum foil because a pinhole is generated and the gas barrier property tends to be reduced.

[0004] As a transparent gas barrier film, a film obtained by laminating a polyvinylidene chloride resin or an ethylene-vinyl alcohol copolymer resin is known. It has been well known that a polymer film formed of a metal compound has good gas barrier properties and transparency.

[0005]

However, such a conventional transparent gas barrier film has the following problems. That is, a polyvinylidene chloride resin or an ethylene-vinyl alcohol copolymer resin laminated film is made of oxygen,
The gas barrier property of water vapor is not sufficient, and the decrease is remarkable especially in the sterilization treatment at a high temperature. In addition, polyvinylidene chloride generates chlorine gas when incinerated, and there is a concern that it will affect the global environment.

On the other hand, a film on which a silicon oxide film or an aluminum oxide film is formed by vapor deposition has a good barrier property. However, in recent years, as eating habits have become rich and various foods and confectioneries have appeared on the market, Improvement of properties such as barrier properties,
Long-term preservation of quality has become even more important. Particularly in the packaging of snacks, foods, etc., more gas barrier properties have been required in order to prevent oxidation and wetness of the contents and to ensure fresh quality for a longer period of time.

In order to solve these requirements, for example, a method of laminating low-crystalline polyesters as disclosed in JP-A-9-300589 and a specific copolymerized polyester as disclosed in JP-A-8-231836 are disclosed. There is a method of blending the components to obtain a transparent gas barrier film,
Although the gas barrier properties are certainly improved, they have not yet reached the high gas barrier properties required in recent years.

The present invention has been made in view of the background of the prior art,
An object of the present invention is to provide a film for vapor deposition having a remarkably excellent gas barrier property against oxygen and water vapor, and a vapor deposited film using the same.

[0009]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the film for vapor deposition of the present invention has a hydroxyapatite particle of 0.005 to 1.0 on at least one surface of a base film (A layer) composed of a polyester film.
The polyester film of the present invention is characterized in that a polyester B layer containing 0.01% to 5% by weight is laminated,
It is characterized in that an inorganic thin film is deposited on the layer surface.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is directed to a vapor-deposited film having excellent gas barrier properties against oxygen and water vapor. The present invention is directed to a polyester B containing a specific amount of hydroxyapatite particles in a base film.
When the layers were laminated to a specific thickness, it was surprisingly found that a vapor-deposited film in which an inorganic thin film was vapor-deposited on this surface could solve the above problems at once.

The polyester film of the present invention is a film composed of a polymer comprising a dicarboxylic acid component and a glycol component.

The dicarboxylic acid component includes, for example, isophthalic acid, terephthalic acid, diphenyl-4,
4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-
1,5-dicarboxylic acid, diphenoxyethane-4,4 '
-Dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, malonic acid, 1,1-dimethylmalonic acid, succinic acid,
Glutaric acid, adipic acid, sebacic acid, decamethylene dicarboxylic acid and the like can be used. Among these dicarboxylic acid components, terephthalic acid and / or 2,2
It is preferable that the film is composed of an acid component containing 6-naphthalenedicarboxylic acid as a main component. That is, when a component other than terephthalic acid and 2,6-naphthalenedicarboxylic acid is the main component, the adhesive strength of the deposited film tends to be poor, and it may be difficult to obtain excellent gas barrier properties.

On the other hand, as glycol components, for example, ethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 1,3
-Glycol components such as aliphatic glycols such as propanediol, alicyclic glycols such as cyclohexanedimethanol, aromatic glycols such as bisphenol-A and bisphenol S, and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyethylene glycol-propylene; Glycol copolymers and the like can be used,
Among these, those composed of a glycol component containing ethylene glycol as a main component are preferable. That is, when a substance other than ethylene glycol is the main component, the adhesive strength of the deposited film is likely to be inferior, and it may be difficult to obtain excellent gas barrier properties. In addition, these dicarboxylic acid components,
Two or more glycol components may be used in combination.

[0014] Other polyesters can be added to the polyester film as long as the effects of the present invention are not impaired. Examples of other polyesters here include polyethylene terephthalate (PET),
Polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexane terephthalate (PHT), polyethylene naphthalate (PE
N), polycyclohexane dimethylene terephthalate (PCT), polyhydroxybenzoate (PHB), and copolymer resins thereof can be used.

The film for vapor deposition of the present invention is characterized in that the hydroxyapatite particles are coated on at least one surface of the base film (layer A) composed of the above-mentioned polyester film with 0.005 to 0.005.
0.01 to 5% by weight of a polyester B layer containing 1.0% by weight.
It is necessary to form a μm layer.

Such hydroxyapatite particles are a double salt of calcium hydroxide and calcium phosphate, and are clearly distinguished from calcium phosphate, just like alum and aluminum sulfate are different compounds. The hydroxyapatite employed in the present invention is represented by the following chemical formula.

Ca (PO4) l (OH) m (CO3) nY
x (where Y is any anion other than a phosphate group, a hydroxyl group, and a carbonate group, l = 0.4 to 0.6, m = 0.1 to
0.4, n = 0-0.2, x = 0-0.2, 3 × l + m
+ 2 × n + z × x (z is the Y valence of the anion). Such hydroxyapatite particles include calcium phosphate and hydrates thereof (eg, Ca (H2PO4) 2.H2O, C
aHPO4 ・ 2H2O) and the like, which have an effect on affinity with polyester, adhesion with a vapor-deposited film and formation of surface roughness, which cannot be achieved by particles such as particles such as aHPO4.2H2O). It is not preferable because it cannot be obtained.

In addition, the hydroxyapatite particles hardly agglomerate individually, tend to be monodisperse particles, and since each particle has a spherical shape, the center line surface roughness (Ra) described later is optimized. This is preferable because it also has the effect of being easily converted.

Among these hydroxyapatite particles, monodisperse particles and spherical hydroxyapatite particles are particularly preferred in that they optimize the center line surface roughness (Ra) and do not cause deposition defects such as pinholes and scratches. .

On the other hand, for example, when agglomerated particles and non-spherical particles are used, the scratch resistance is deteriorated, and when the vapor deposition is performed, the particles are lost, and the vapor deposition defects such as pinholes and the like are lost. Particles are liable to cause deposition defects such as scratches on other deposition portions, and the deposition barrier property is liable to deteriorate, which is not preferable.

In the film for vapor deposition of the present invention, the content of the hydroxyapatite particles must be 0.005 to 1.0% by weight in the polyester B layer.
More preferably, the content is 0.01 to 0.5% by weight. The average particle size of such hydroxyapatite particles is preferably 0.001 to 10 μm, and more preferably 0.01 to 2 μm. If the particle content and the average particle size are less than the lower limits, the handleability of the film is liable to deteriorate, which is not preferable. On the other hand, if the upper limit is exceeded, the scratch resistance is deteriorated, and a pinhole is apt to be generated at the time of vapor deposition.

The layer thickness of the polyester B layer needs to be 0.01 to 5 μm, preferably 0.05 to 5 μm, and more preferably 0.1 to 5 μm. If it is less than 0.01 μm, it is difficult to obtain an excellent vapor deposition barrier property. Conversely, if the lamination thickness exceeds 5 μm, it depends on the thickness of the base film, but it is preferable from the viewpoint of the balance between the cost and the vapor deposition barrier. Absent.

[0023] In addition to the hydroxyapatite particles, other particles can be added to the film for vapor deposition of the present invention as long as the effects of the present invention are not impaired. As such additive particles, inorganic particles, organic particles, crosslinked polymer particles, internal particles generated in a polymerization system, and the like can be employed. Two or more of these particles may be added.

The inorganic particles are not particularly limited, but include calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, and oxide. Titanium,
Zirconium oxide, lithium fluoride, or the like can be used.

As the organic particles, there can be used calcium oxalate and terephthalates such as calcium, barium, zinc, manganese and magnesium.

As the crosslinked polymer particles, homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid and methacrylic acid can be used. In addition, organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.

As the internal particles produced in the polymerization system, those produced by a known method in which an alkali metal compound, an alkaline earth metal compound or the like is added to the reaction system and further a phosphorus compound is added are used. can do.

The film for vapor deposition of the present invention contains a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a pigment, a dye, a fatty acid ester, as long as the effects of the present invention are not impaired. A compound containing an organic lubricant such as wax or an antifoaming agent such as polysiloxane can be used.

In the film for vapor deposition, the center line average roughness (Ra) of at least one surface of the polyester B layer is preferably 0.005 to 0.03 μm, more preferably 0.008 to 0.03 μm, and particularly preferably. Is 0.01 ~
It is preferably 0.02. The center line average roughness (R
If a) is less than 0.005 μm, the handleability of the film tends to deteriorate, which is not preferable. Conversely, 0.
If the thickness exceeds 03 μm, the scratch resistance is deteriorated, and pinholes are liable to occur during the deposition, which is not preferable. A method of setting the center line average roughness (Ra) in the above range is as follows.
Although not particularly limited, a method in which particles are contained in the base film is preferably employed, but a method of transferring irregularities on the surface of the drum to the film by a metal drum having a plain pattern may be used.

In the film for vapor deposition of the present invention, in order to achieve both a barrier property, a workability and a handling property, 2
A composite film composed of layers or more is preferably used. More preferably, the center line average roughness (R
Preferably, the difference (ΔRa) from (a) is 0.003 to 0.045 μm. More preferably, ΔRa is 0.00
The thickness is preferably 5 to 0.045 μm. Ra of the deposition surface is 0.005 to 0.03 μm, more preferably 0.005 to 0.03 μm.
8 to 0.03 μm, particularly preferably 0.01 to 0.02
μm, Ra of the non-deposited surface is preferably 0.008 to 0.0
By setting [Delta] Ra in the range of 0.003 to 0.045 [mu] m by setting the range to 5 [mu] m, more preferably in the range of 0.01 to 0.03 [mu] m, excellent film handling properties (slipperiness) and further excellent. Workability can be obtained. If the Ra of the non-deposited surface is less than 0.008 μm, the slipperiness tends to deteriorate, which is not preferable. Conversely 0.05μ
If it exceeds m, the slipperiness is too high, and the vapor deposition characteristics and workability, such as lowering of handleability, are undesirably deteriorated.

The film for vapor deposition of the present invention preferably has a base film having a plane orientation coefficient (fn) in the range of 0.155 to 0.180, more preferably 0.1625 to 0.1625.
Those in the range of 0.175 are preferred. The plane orientation coefficient (f
When n) is less than 0.155, the orientation of the film is reduced, so that the film is easily stretched with respect to a decrease in strength or external force,
It is not preferable because processability is likely to be reduced. Conversely 0.1
When it exceeds 80, it is not preferable because unevenness in physical properties in the width direction of the film, whitening, and the like are apt to occur.

The film for vapor deposition of the present invention has a temperature of 150.degree.
0% heat shrinkage is 0.5-2% in the longitudinal direction of the film,
It is preferably in the range of -1.2 to 0.5% in the width direction, more preferably 1 to 2% in the longitudinal direction of the film,
Those having a value of -1 to 0% in the width direction are preferable. When such a heat shrinkage exceeds 2% in the longitudinal direction of the film and exceeds 0.5% in the width direction or is less than -1.2% in the width direction, an external force is applied at the time of vapor deposition, lamination, printing process, or the like. This is not preferable because the dimensional change tends to increase during the working. Therefore, it is preferable that the heat shrinkage in the longitudinal direction at 150 ° C. for 30 minutes is as small as possible, but since it has about 0.5%, the lower limit of the heat shrinkage in the longitudinal direction is substantially 0.5%. Is good. Here, the minus (-) value of the heat shrinkage is
It shows elongation.

Further, the thickness of the film for vapor deposition of the present invention is as follows:
Although not particularly limited, it is preferably 1 to 300 μm, more preferably 5 to 100 μm.

The structure of the film for vapor deposition is B
Two layers of / A, three layers of B / A / B and B / A / C, or a multilayer structure of more than three layers may be used, and the thickness ratio of the layers may be arbitrarily set. Further, layers other than these may be laminated, for example, an antistatic layer, a mat layer, a hard coat layer, a lubricious coat layer, an adhesive layer, an adhesive layer, and the like can be laminated.

In the film for vapor deposition of the present invention, the corona discharge treatment is performed on the surface of the polyester B layer on which vapor deposition is performed, and the wetting tension of the surface is increased to 35 mN / m or more. Therefore, it can be preferably adopted. Atmosphere gas at the time of the corona discharge treatment at this time may be any of air, carbon dioxide gas, or a mixed system of nitrogen / carbon dioxide gas, particularly a mixed gas of carbon dioxide gas or nitrogen / carbon dioxide gas (volume ratio = 95/5 to 5/5). 50/50), the film surface has a wetting tension of 35 mN /
m or more.

The film for vapor deposition of the present invention can be formed into a vapor-deposited film by vapor-depositing an inorganic thin film on the surface of the polyester B layer subjected to corona discharge treatment. As the inorganic thin film here, an aluminum thin film and / or a metal oxide such as aluminum, silicon, zinc, and magnesium can be preferably used.

Among such metal oxides, an aluminum oxide thin film can be more preferably used in terms of gas barrier performance and cost. These metal oxides may be used singly, or a mixture of a plurality of these may be used, or a metal oxide partially remaining.

As a method of forming these inorganic thin films by vapor deposition, ordinary vacuum vapor deposition can be used, but ion plating, sputtering, a method of activating vapors by plasma, or the like can also be used. As a method of forming such a metal oxide, a method of depositing a metal oxide by direct evaporation or a method of reactive deposition in an oxidizing atmosphere can be more preferably adopted from the viewpoint of productivity. Chemical vapor deposition (so-called CVD)
Can also be used as a vapor deposition method in a broad sense.

The oxidizing atmosphere referred to here means an oxygen gas alone or a gas obtained by diluting oxygen gas with an inert gas and introducing it into a vacuum evaporation machine in a required amount. The inert gas refers to a rare gas such as argon or helium, a nitrogen gas, and a mixed gas thereof. In addition, the reactive deposition is a method in which a metal or a metal oxide is evaporated from an evaporation source in such an oxidizing atmosphere to cause an oxidation reaction in the vicinity of the base film to form the base on the base film. As an evaporation source for these, a board type of a resistance heating system, a crucible type by radiation or high-frequency heating, a system by electron beam heating, and the like can be adopted, but are not particularly limited.

When the inorganic thin film is a metal oxide, it is most preferable that the inorganic thin film be a complete oxide. However, in general, when a complete oxide is to be formed, there is a high probability that an excessively oxidized portion will be formed. However, the gas barrier performance of this part is inferior, and it is difficult to obtain high gas barrier performance as a whole. Therefore, an incomplete oxide film in which some metal components remain may be used.

The light transmittance of the vapor-deposited film thus obtained is preferably 70% or more, more preferably 8% or more.
When it is used as a packaging bag, it is preferably 0% or more, particularly preferably 85% or more, in order to confirm the quality of the contents. The upper limit of the light transmittance is limited by the light transmittance of the base polyester film, and the upper limit of the light transmittance is 92%. Therefore, the upper limit of the substantial light transmittance of the deposited film is 92%. It is.

As the thickness of such an inorganic thin film, a thickness of 20 to 50 nm is used in the case of an aluminum thin film, and an optical density (logarithm of a reciprocal of light transmittance) of about 1.5 to 3 is preferable. In the case of a metal oxide, it is preferably 5 to 100 n in terms of gas barrier performance and flexibility.
m, more preferably in the range of 8 to 50 nm. If the thickness is less than 5 nm, the gas barrier performance is not sufficient, and if the thickness exceeds 100 nm, the latent surface of the film is melted and whitened due to the latent heat of aggregation of the metal oxide at the time of vapor deposition. Worse,
Further, it is not preferable because, for example, the film is easily bent or peeled off due to bending of the film.

In the vapor deposition film of the present invention, another resin can be laminated on the vapor deposition surface of the inorganic thin film. As such another resin, a film such as a polyolefin resin, a nylon resin, or a polyethylene terephthalate resin is preferable, and a biaxially stretched film or a non-stretched film may be used. When laminating as a heat seal layer, a non-stretched film of a polyolefin resin is preferred, and these films are preferably laminated by an extrusion laminating method or an adhesive. Such a vapor-deposited film is used as a packaging bag, with the heat seal layers being overlapped and sealed.

The film for vapor deposition of the present invention can be produced by using any conventionally known method. For example, in the case of a biaxially stretched film, the polymers constituting the polyester A and the polyester B are dried using a normal hopper dryer, a paddle dryer, a vacuum dryer or the like, and then supplied to separate extruders, respectively, to obtain 200 to 320 The mixture was melt-extruded at a temperature of ℃ C, led to a slit-shaped two-layer die, and rapidly cooled to obtain a polyester A / polyester B laminated unstretched film. When the T-die method is used, a film having a uniform thickness can be obtained by using a so-called electrostatic application contact method during rapid cooling, which is preferable. Next, a method of simultaneously or sequentially biaxially stretching the unstretched film may be mentioned. Also,
In the case of sequential biaxial stretching, the stretching order may be the order of the film in the longitudinal direction and the width direction, or vice versa.
Further, in the sequential biaxial stretching, stretching in the longitudinal direction or the width direction can be performed twice or more. The stretching method is not particularly limited, and methods such as roll stretching and tenter stretching are applied, and the shape may be any shape such as a flat shape and a tube shape. The stretching ratio in the longitudinal direction and the width direction of the film is the target evaporation suitability,
Although it can be arbitrarily set according to the orientation and the like, it is preferably 1.5 to 6.0 times. The stretching temperature can be any temperature as long as it is in the range of the glass transition temperature of the polyester or more and the crystallization temperature or less.
50 ° C. is preferred. Furthermore, the film can be subjected to a heat treatment after the biaxial stretching. The heat treatment temperature can be any temperature lower than the melting point of polyester A, but is preferably from 200 to 240 ° C. The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction.

Next, the film of the present invention is prepared by subjecting a surface (polyester B layer) to be subjected to vapor deposition to a known adhesion promoting treatment before vapor deposition.
For example, corona discharge treatment in air or other atmosphere,
A flame treatment, an ultraviolet treatment, or the like may be performed. In the case of the corona discharge treatment, the atmospheric gas may be any of air, carbon dioxide, and a mixed system of nitrogen / carbon dioxide, and particularly, a gas mixture of carbon dioxide or nitrogen / carbon dioxide (volume ratio = 95).
/ 5/50/50) is preferable because the wet tension on the film surface increases to 35 mN / m or more.

Next, the film for vapor deposition is set in a vacuum vapor deposition device provided with a film traveling device, and travels through a cooling metal drum. At this time, vapor deposition is performed while heating and evaporating the aluminum metal. Alternatively, oxygen gas is supplied to the evaporating vapor, and aluminum is oxidized to be agglomerated and deposited on the running film surface to form an aluminum oxide vapor-deposited layer, and the obtained vapor-deposited film of the present invention is wound. By changing the ratio between the amount of aluminum evaporated and the amount of supplied oxygen gas at this time, the light transmittance of the aluminum oxide deposited film can be changed. After the vapor deposition, the inside of the vacuum vapor deposition apparatus is returned to normal pressure, the wound film is slit, and it is preferable that the film is aged at a temperature of 30 ° C. or more for one day or more because the gas barrier property is stabilized.

[0047]

EXAMPLES Next, the effects of the present invention will be described with reference to examples, but the present invention is not limited to these examples. First, a method for measuring and evaluating a characteristic value will be described below.

[Method of Measuring and Evaluating Characteristic Values] The characteristic values of the present invention are measured by the following measuring methods.

(1) Melting Point (Tm) Using a thermal analyzer DSCII type manufactured by Seiko Instrument Inc., a 5 mg sample was heated from room temperature at a heating rate of 20 ° C./min. The peak temperature was taken as the melting point (Tm).

(2) Intrinsic Viscosity Polyester is dissolved in orthochlorophenol,
Measured in ° C.

(3) Relative viscosity (ηr) Measured according to the polyamide test method (formic acid dissolution method) of JIS K-6810.

(4) Plane Orientation Coefficient fn Using an Abbe refractometer manufactured by Atago Co., Ltd., the refractive index of the film was measured using a sodium lamp as a light source. The refractive index nγ in the longitudinal direction in the film plane, the refractive index nβ in the horizontal direction perpendicular to the film, and the refractive index nα in the thickness direction were determined, and the plane orientation coefficient fn was determined by the following equation: fn = (nγ + nβ) / nα.

(5) Average Particle Size Resin is removed from the film by a plasma low-temperature incineration method,
Expose the particles. The processing conditions cause the resin to ash,
Select the conditions under which the particles will not be damaged. This was observed for 5,000 to 10,000 particles with a scanning microscope, and the average particle diameter was determined from the equivalent circle diameter of the particle image using an image processing apparatus.

When the particles are internal particles, an ultra-thin section having a thickness of about 0.1 to 1 μm is prepared by cutting a cross section of the polymer and photographed at a magnification of about 5,000 to 20,000 using a transmission electron microscope. Photographing was performed (10 sheets: 25 cm × 25 cm), and the average dispersion diameter of the internal particles was calculated from the equivalent circle diameter.

(6) Center Line Average Roughness (Ra) The surface roughness was measured using a high-precision thin film step measuring device ET-10 manufactured by Kosaka Laboratory. The conditions were as follows, and the average value of the 20 measurements was taken as the center line average roughness (Ra).・ Stylus of stylus tip: 0.5 μm ・ Load of stylus: 5 mg ・ Measuring length: 1 mm ・ Cutoff: 0.08 mm The definition of Ra and Rt is, for example, the method of measuring and evaluating surface roughness by Jiro Nara (Sogo Center, 1983).

(7) Heat Shrinkage The film sample was cut at a distance of 200 mm from the marked line, the film was cut into 10 mm, the film sample was suspended in the length direction, and a load of 1 g was applied in the length direction. After heating with hot air for 30 minutes, the length between the marked lines was measured, and the shrinkage of the film was calculated as a percentage (%) of the original size. In addition, the thing which the film extended was shown by minus (-).

(8) Optical Density (OD) According to JIS-K-7605, a filter was applied to the vapor-deposited film using a transmission densitometer TR927 manufactured by Macbeth Co., Ltd.
The transmission density when measured as al was measured and defined as the optical density.

(9) Light transmittance The transmittance of the vapor-deposited film was measured at a wavelength of 550 nm using a spectrophotometer 324 manufactured by Hitachi, Ltd.

(10) Gas Barrier Property Water vapor permeability (moisture proof) Water vapor permeability meter “PERMA” manufactured by Modern Control
The value measured using TRAN "W3 / 31 under the conditions of a temperature of 37.8 ° C and a relative humidity of 100% is shown in units of g / m 2 · day.

B. Oxygen permeability Oxygen permeability meter “OXTRA” manufactured by Modern Control
Using N ″ -100, the value measured under the conditions of a temperature of 23 ° C. and a relative humidity of 80% is shown in the unit of ml / m 2 · day · MPa.

(11) Thickness Configuration of Film and Thickness of Inorganic Thin Film Layer A cross section of the film was photographed with a transmission electron microscope (TEM) under the following conditions, and the thickness configuration of the film and the thickness of the inorganic thin film layer were measured. . Apparatus: JEM-1200EX manufactured by JEOL Ltd. Observation magnification: Film thickness configuration = 1000 times Thickness of inorganic thin film layer = 400,000 times Acceleration electron: 100 kV.

(12) Adhesion of vapor-deposited film Unstretched propylene film (CPP) (3529T, 25 μm, manufactured by Toray Synthetic Film Co., Ltd.) was bonded to the vapor-deposited surface of the vapor-deposited film using a polyurethane adhesive.
After aging at 48 ° C. for 48 hours, the resultant was cut into 15 mm widths, and CPP and the vapor-deposited inorganic thin film were peeled at a peeling rate of 100 mm / min using Tensilon at 180 °. Peel dry (25
C., 50% RH atmosphere) and water resistance (peeling by dropping water on the peeling interface) were measured. A sample having a thickness of 2 N / cm or more was evaluated as ○, a sample less than 1 N / cm was evaluated as x, and an intermediate sample was evaluated as Δ, and the adhesion of the deposited film was evaluated.

(13) Handling Property Regarding the handling properties (slipperiness, etc.) of the film at the time of vapor deposition and processing, those with excellent handling properties were evaluated as ○, and those with poor handling properties were evaluated as x.

Next, the method for producing a film of the present invention will be described with reference to an example in which the film is laminated in the order of film / surface treatment / inorganic thin film. However, the present invention is not limited to this example. is there.

Next, the effects of the present invention will be described with reference to examples.

Example 1 Polyethylene terephthalate (melting point: 256 ° C., intrinsic viscosity: 0.1 mm) was used as a raw material for the base film A of the film of the present invention.
Polyethylene terephthalate (melting point: 256 ° C., extreme limit) was used as polyester B using 100% by weight (pellets melt-mixed to contain 0.05% by weight of wet-process silica particles having an average particle diameter of 1.2 μm). 100% by weight (viscosity 0.64 dl / g) (average particle size 0.8 μm)
(A pellet melt-mixed to contain 0.05% by weight of hydroxyapatite particles). After each pellet is sufficiently dried in vacuum, it is supplied to a separate extruder and melted at 280 ° C., and after obtaining each filtration filter, it is led to a slit-shaped two-layer die, and a base film A layer / polyester The layers are laminated in the order of layer B, and this is
It was wound around a cooling drum at 5 ° C. and solidified by cooling. In order to improve the adhesion between the sheet and the surface of the cooling drum during this time, a wire electrode was arranged on the sheet side and a DC voltage of 6 kV was applied. The unstretched film thus obtained was heated to 105 ° C. and stretched 3.1 times in the longitudinal direction to obtain a uniaxially stretched film. Hold the film with a clip and
Guide into a tenter heated to 00 ° C and continuously
The film was stretched 4.0 times in the width direction in the region heated to 0 ° C., and further subjected to a heat treatment for 5 seconds in an atmosphere at 238 ° C. to form a 12 μm-thick film for vapor deposition (lamination thickness of base film A / polyester B = 11/1 μm).

Next, the obtained film for vapor deposition was heated with a rubber roll heated to 50 ° C. to coat the polyester B laminated surface with a mixed gas of nitrogen / carbon dioxide (nitrogen / carbon dioxide = 85 /
In the atmosphere of 15), a corona discharge treatment is performed under a treatment condition of 40 W · min / m 2, and the wetting tension of the film is 45 m.
N / m or more and wound up in a roll. The temperature of the film at that time was 30 ° C., and the film was allowed to stand for 10 hours and slit into a small width. Next, the film slit in a small width was set in a vacuum deposition apparatus equipped with a film traveling device, and after a high vacuum of 1.00 × 10 −2 Pa was applied, the film was removed by −20.
C. was run through a cooled metal drum. At this time, while heating and evaporating the aluminum metal, the aluminum film was agglomerated and deposited on the corona discharge treated surface of the running film to form a deposited aluminum thin film layer and wound it. After the evaporation, the inside of the vacuum evaporation apparatus was returned to normal pressure, the wound film was rewound, and aged at a temperature of 40 ° C. for 2 days to obtain an evaporation film. The thickness of the inorganic thin film of this vapor deposition film was 45 nm.

Example 2 As a raw material of the base film A of the film of the present invention, polyethylene naphthalate (melting point: 270 ° C., intrinsic viscosity: 0.6
9 dl / g) of 100% by weight (pellet melt-mixed to contain 0.05% by weight of calcium carbonate particles having an average particle size of 0.8 μm), and as a polyester B, hydroxyapatite having an average particle size of 0.8 μm 0.0
5% by weight of polyethylene terephthalate (melting point 2
56 ° C., intrinsic viscosity 0.64 dl / g). After sufficiently vacuum-drying each pellet, it is supplied to a separate extruder and melted at 290 ° C., and after obtaining each filtration filter, it is led to a slit-shaped two-layer die, and the base film A / polyester B And wound around a cooling drum having a surface temperature of 25 ° C. to be cooled and solidified. In order to improve the adhesion between the sheet and the surface of the cooling drum during this time, a wire electrode was arranged on the sheet side and a DC voltage of 6 kV was applied. The unstretched film thus obtained was heated to 135 ° C. and stretched 3.1 times in the longitudinal direction to obtain a uniaxially stretched film. Hold the film with a clip and
Guided into a tenter heated to 00 ° C and continuously 140
The film was stretched 4.0 times in the width direction in the region heated to 0 ° C., and further subjected to a heat treatment for 5 seconds in an atmosphere at 238 ° C. to form a 12 μm-thick film for vapor deposition (lamination thickness of base film A / polyester B = 11/1 μm). The deposited film was deposited in the same manner as in Example 1 to obtain an inorganic thin film having a thickness of 45.
nm was obtained.

Example 3, Comparative Examples 1-2 The film forming conditions of Example 1 were determined based on the composition of the base film A, the composition of the polyester B, the addition of particles, and the lamination ratio of the base film A / polyester B shown in Table 1. Each was changed to obtain a film for vapor deposition and a vapor-deposited film having an average thickness of 12 μm.

Example 4 The polyamide C laminated surface was treated with a mixed gas of nitrogen / carbon dioxide (nitrogen / carbon dioxide = 85/15) through a rubber roll heated to 50 ° C. on the film for vapor deposition obtained in Example 1. The film was subjected to corona discharge treatment under a treatment condition of 40 W · min / m 2 in an atmosphere, and the film was wound into a roll with a wet tension of 45 mN / m or more. The temperature of the film at that time was 30 ° C., and the film was allowed to stand for 10 hours and slit into a small width. Next, the film slit to a small width was set in a vacuum evaporation apparatus equipped with a film traveling device, and 1.00 ×
After a high vacuum of 10 −2 Pa, the sample was run through a cooling metal drum at −20 ° C. At this time, while heating and evaporating the aluminum metal, oxygen gas is supplied to the evaporating vapor point, and while oxidizing the aluminum metal, the aluminum metal is coagulated and deposited on the corona discharge treated surface of the running film to form a vapor-deposited thin film layer of aluminum oxide. I took it. After the evaporation, the inside of the vacuum evaporation apparatus was returned to normal pressure, and the wound film was rewound.
Aging was performed at a temperature of 2 ° C. for 2 days to obtain a transparent vapor-deposited film. This transparent vapor-deposited film has an inorganic thin film thickness of 45n.
m, the light transmittance was 78%.

Table 1 summarizes the quality evaluation results of the above films for vapor deposition and vapor deposition films.

[0072]

[Table 1]

As can be seen from the results in Table 1, Examples 1 to
The film for vapor deposition obtained in 4 was excellent in handling properties and vapor deposition adhesion, and the vapor deposited film was a film excellent in gas barrier properties.

Further, linear polyethylene (LLD-PE) was extrusion-laminated on the vapor-deposited surface of the transparent vapor-deposited film obtained in Example 4, cut into 15 cm × 30 cm, and cut into
When the LD-PE surfaces were overlapped with each other and sealed three-sided with a heat sealer to produce a package, the package was not only transparent, but also excellent in gas barrier properties against oxygen and water vapor.

On the other hand, the vapor-deposited films obtained in Comparative Examples 1 and 2 had poor vapor-depositing workability and gas barrier properties. None of the films was preferred as a film for vapor deposition.

[0076]

According to the present invention, it is possible to stably provide a vapor deposition film having excellent vapor deposition processability and gas barrier properties.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 3/32 C08K 3/32 4K029 C08L 67/02 C08L 67/02 C23C 14/06 C23C 14/06 Q F term (reference ) 3E086 BA04 BA13 BA15 BA35 BA40 BB02 BB05 BB22 BB67 BB68 CA01 CA28 4F006 AA35 AB73 BA05 CA07 DA01 4F071 AA45 AA46 AB18 AB25 AF06Y AF61Y AH04 BA01 BB07 BC01 4F100 AA17C AA20 AA33B AABABAB23A37BAAB EH66C EJ38 EJ55 GB15 GB23 GB66 JD02 JM02C YY00B 4J002 CF061 CF081 DE086 DH046 FD016 4K029 AA11 AA21 AA25 BA03 BA31 BA43 BA44 BC00 CA01 CA02 DB03 FA05

Claims (7)

[Claims] A polyester B containing 0.005 to 1.0% by weight of hydroxyapatite particles on at least one surface of a base film (layer A) made of a polyester film.
A film for vapor deposition characterized by laminating layers in a thickness of 0.01 to 5 μm. 2. The polyester constituting the polyester film, wherein the dicarboxylic acid component is mainly composed of terephthalic acid and / or 2,6-naphthalenedicarboxylic acid, and the glycol component is mainly composed of ethylene glycol. 2. The film for vapor deposition according to 1. 3. The polyester B layer has a thickness of 0.005 to 0.5.
The film for vapor deposition according to claim 1 or 2, having a center line average roughness (Ra) in a range of 03 µm. 4. The film for vapor deposition according to claim 1, wherein said substrate film has a plane orientation coefficient (fn) in the range of 0.155 to 0.180. 5. The heat shrinkage of the base film at 150 ° C. for 30 minutes is in the range of 0.5 to 2% in the longitudinal direction of the film and -1.2 to 0.5% in the width direction. Claim 1
5. The film for vapor deposition according to any one of items 4 to 4. 6. A vapor-deposited film, wherein an inorganic thin film is vapor-deposited on the surface of the polyester B layer of the film for vapor-deposition according to claim 1. 7. The method according to claim 7, wherein the inorganic thin film is an aluminum thin film and / or an aluminum thin film.
7. The vapor-deposited film according to claim 6, which is a metal oxide thin film.