JP2012081630A - Gas barrier laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminated film which has sufficient gas barrier properties and sufficiently suppresses deterioration in the gas barrier properties even when the film is bent.SOLUTION: The gas barrier laminated film includes a base and at least one thin film layer formed on at least one surface of the base, wherein, at least one layer of the thin film layer(s) comprises silicon, oxygen and carbon, and also, the following conditions(i) are satisfied: (i), in a carbon distribution curve showing the relation between the distance from the surface of the thin film layer in the film thickness direction of the layer and the ratio of the quantity of carbon atoms (the atomic ratio of carbon) to the total of silicon atoms, oxygen atoms and the carbon atoms, a difference between the maximum value of the ratio of the carbon atoms and the minimum value of the ratio of the carbon atoms in the thin film layer is ≤5% ((the maximum value of the ratio of the carbon atoms)-(the minimum value of the ratio of the carbon atoms)≤5%).

Description

  The present invention relates to a gas barrier laminate film that can be suitably used for flexible lighting using organic electroluminescence elements (organic EL elements), organic thin-film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

  The gas barrier film can be suitably used as a packaging container suitable for filling and packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, a gas barrier film in which a thin film of an inorganic oxide such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide is formed on one surface of a base film such as a plastic film has been proposed.

As a method for forming an inorganic oxide thin film on the surface of a plastic substrate in this manner, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, thermochemical vapor deposition, etc. A chemical vapor deposition method (CVD) such as a method (thermal CVD method) or a plasma chemical vapor deposition method is known.
Further, as a gas barrier film using such a film forming method, for example, in Japanese Patent Laid-Open No. 4-89236 (Patent Document 1), two silicon oxide vapor-deposited films are formed on the surface of a plastic substrate. A gas barrier film provided with a laminated vapor deposition film layer laminated as described above is disclosed.

JP-A-4-89236

  However, the gas barrier film as described in Patent Document 1 can be used as a gas barrier film for articles that are satisfactory even if the gas barrier property is relatively low, such as foods and drinks, cosmetics, and detergents. As a gas barrier film for an electronic device such as an EL element or an organic thin film solar cell, the gas barrier property is not always sufficient. Further, the gas barrier film as described in Patent Document 1 has a problem that the gas barrier property against oxygen gas or water vapor is lowered when the film is bent, and the film has a bending resistance like a flexible liquid crystal display. The required gas barrier film is not always sufficient in terms of gas barrier properties when the film is bent.

  The present invention has been made in view of the above-described problems of the prior art, has a sufficient gas barrier property, and can sufficiently suppress a decrease in gas barrier property even when the film is bent. An object of the present invention is to provide a gas barrier laminate film.

To solve the above problem,
The present invention is a gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate,
At least one of the thin film layers contains silicon, oxygen and carbon, and the following condition (i):
(I) Carbon indicating the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio). In the distribution curve, the difference between the maximum value of the carbon atom ratio in the thin film layer and the minimum value of the carbon atom ratio is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
A gas barrier laminate film characterized by satisfying the above is provided.
In the gas barrier laminate film of the present invention, the following condition (ii):
(Ii) In the thin film layer, a ratio of a total amount of oxygen atoms and carbon atoms to silicon atoms is greater than 1.98 and not more than 2.03.
1.98 <((amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2.03
It is preferable to satisfy.
In the gas barrier laminate film of the present invention, the following condition (iii):
(Iii) silicon showing the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon) In the distribution curve, the silicon atom ratio is 30.0% or more and 37.0% or less in a region of 90% or more in the thin film layer.
(30% ≦ ((amount of silicon atoms) / ((amount of oxygen atoms) + (amount of carbon atoms) + (amount of silicon atoms)) ≦ 37%)
It is preferable to satisfy.
In the gas barrier laminate film of the present invention, the following condition (iv):
(Iv) The thin film layer is formed by a plasma CVD method, a film formation gas of the plasma CVD method is an organic silicon compound gas and an oxygen gas, and the organic silicon compound is hexamethyldisiloxane (HMDSO). .
It is preferable to satisfy.
In the gas barrier laminate film of the present invention, in the thin film layer, the ratio of the total amount of oxygen atoms and carbon atoms to the amount of silicon atoms is preferably 2 or less.
((Amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2
The gas barrier laminate film of the present invention has a barrier layer in which two or more thin film layers are laminated, and the film thickness of each thin film layer is larger than 50 nm, and the film of the barrier film in which the thin film layers are laminated. The thickness is preferably greater than 100 nm and not greater than 3000 nm.
In the gas barrier laminate film of the present invention, in the thin film layer, the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) is 1% or more and 67% or less. Is preferred.
In the gas barrier laminate film of the present invention, the density of the thin film layer is preferably 0.9 g / cm ³ or more and 2.2 g / cm ³ or less.
In the gas barrier laminate film of the present invention, a pair of electrodes are separated from the base material by a predetermined distance so as to face the base material, and are arranged on the same side with respect to the surface of the base material. The thin film layer is preferably formed by a plasma chemical vapor deposition method in which a plasma is generated by discharging at a pair of electrodes.
In the gas barrier laminate film of the present invention, it is preferable that the polarities of the pair of electrodes are alternately reversed when discharging is performed on the pair of electrodes.
In the gas barrier laminate film of the present invention, the content of the oxygen gas in the film forming gas completely oxidizes the entire amount of hexamethyldisiloxane (HMDSO), which is the organosilicon compound, in the film forming gas. It is preferable that the amount of oxygen be less than or equal to the theoretical oxygen amount required.
In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a continuous film forming process.
In the gas barrier laminate film of the present invention, it is preferable that the base material is made of at least one resin selected from the group consisting of polyester resins and polyolefin resins.
In the gas barrier laminate film of the present invention, it is preferable that the substrate is made of at least one resin selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate.
Moreover, this invention provides the organic electroluminescent element characterized by including the gas-barrier laminated film of the said invention.
The present invention also provides an organic thin film solar cell comprising the gas barrier laminate film of the present invention.
The present invention also provides a liquid crystal display comprising the gas barrier laminate film of the present invention.
Further, the present invention is a method for producing a gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate,
A pair of electrodes are spaced apart from the base material by a predetermined distance so as to face the base material, arranged on the same side of the surface of the base material, and discharge is generated at the pair of electrodes to generate plasma. The plasma chemical vapor deposition method includes silicon, oxygen, and carbon, and the following condition (i):
(I) Carbon indicating the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio). In the distribution curve, the difference between the maximum value of the carbon atom ratio in the thin film layer and the minimum value of the carbon atom ratio is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
Provided is a method for producing a gas barrier laminate film, wherein at least one thin film layer satisfying the above condition is formed on a substrate.

  According to the present invention, it is possible to provide a gas barrier laminated film that has a sufficient gas barrier property and can sufficiently suppress a decrease in gas barrier property even when the film is bent. .

It is a schematic diagram which shows an example of a batch type manufacturing apparatus suitable for manufacturing the gas-barrier laminated | multilayer film of this invention. It is a schematic diagram which shows an example of the continuous manufacturing apparatus suitable for manufacturing the gas-barrier laminated | multilayer film of this invention. 2 is a graph showing a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve in the gas barrier laminate film obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The gas barrier laminate film of the present invention is a gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate,
At least one of the thin film layers contains silicon, oxygen and carbon, and the following condition (i):
(I) Carbon indicating the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio). In the distribution curve, the difference between the maximum value of the carbon atom ratio in the thin film layer and the minimum value of the carbon atom ratio is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
It is characterized by satisfying.
That is, the gas barrier laminate film of the present invention has a small variation in the ratio of carbon atoms in the film thickness direction of the thin film layer and a high uniformity.

  As a base material used for this invention, the film or sheet | seat which consists of colorless and transparent resin is mentioned. Examples of the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin. Among these resins, polyester resins and polyolefin resins are preferred, and PET and PEN are particularly preferred from the viewpoints of high heat resistance and linear expansion coefficient and low production cost. If it is PEN, for example, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) may be mentioned as a preferred commercial product. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the base material can be appropriately set in consideration of the stability when producing the gas barrier laminate film of the present invention. The thickness of the substrate is preferably in the range of 5 to 500 μm from the viewpoint that the film can be conveyed even in a vacuum.

  Moreover, it is preferable to perform the surface activation process for cleaning the surface of a base material to the said base material from an adhesive viewpoint with the thin film layer mentioned later. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

  The thin film layer concerning this invention is a layer formed in the at least single side | surface of the said base material. In the gas barrier laminate film of the present invention, it is necessary that at least one of the thin film layers is a layer containing silicon, oxygen and carbon. Further, at least one of the thin film layers may further contain nitrogen, aluminum, or titanium.

In the present invention, at least one of the silicon, oxygen, and carbon-containing thin film layers satisfies the above condition (i). That is, such a thin film layer first includes (i) the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms ( In the carbon distribution curve showing the relationship with the carbon atomic ratio), the difference between the maximum value of the carbon atom ratio and the minimum value of the carbon atom ratio in the thin film layer is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
Thus, the high uniformity of the carbon atom ratio in the film thickness direction of the thin film layer allows the gas barrier laminated film to have a sufficient gas barrier property and to reduce the gas barrier property when the film is bent. A remarkable suppression effect is obtained.

Moreover, such a thin film layer further includes the following conditions (ii) to (iv):
(Ii) In the thin film layer, a ratio of a total amount of oxygen atoms and carbon atoms to silicon atoms is greater than 1.98 and not more than 2.03.
1.98 <((amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2.03
(Iii) silicon showing the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon) In the distribution curve, the silicon atom ratio is 30.0% or more and 37.0% or less in a region of 90% or more in the thin film layer.
(30% ≦ ((amount of silicon atoms) / ((amount of oxygen atoms) + (amount of carbon atoms) + (amount of silicon atoms)) ≦ 37%)
(Iv) The thin film layer is formed by a plasma CVD method, a film formation gas of the plasma CVD method is an organic silicon compound gas and an oxygen gas, and the organic silicon compound is hexamethyldisiloxane (HMDSO). .
It is preferable to satisfy any one or more of the above, and it is more preferable to satisfy all of (ii) to (iv).
By satisfying such a condition, the gas barrier property is further improved, and when the film is bent, a higher effect of suppressing the gas barrier property can be obtained.

The carbon distribution curve is a so-called XPS in which surface composition analysis is sequentially performed while exposing the inside of a sample by using measurement of X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon in combination. It can be created by depth profile measurement. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of elements (unit: at%) and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the thin film layer in the film thickness direction of the thin film layer in the film thickness direction. As the distance from the surface of the thin film layer in the film thickness direction of the thin film layer, the distance from the surface of the thin film layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement may be adopted. it can. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

In the thin film layer, the ratio of the total amount of oxygen atoms and carbon atoms to the amount of silicon atoms is preferably 2 or less.
((Amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2
By satisfying such a condition, the gas barrier property is further improved, and when the film is bent, a higher effect of suppressing the gas barrier property can be obtained.

In the thin film layer, the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio) is preferably 1% to 67%, preferably 6% to 67%. Or less, more preferably 12% or more and 67% or less.
By satisfying such conditions, the gas barrier property is further improved, and even when the film is bent, a higher effect of suppressing the gas barrier property can be obtained.

  In the present invention, the thin film layer is substantially in the film surface direction (direction parallel to the surface of the thin film layer) from the viewpoint of forming a thin film layer having a uniform and excellent gas barrier property over the entire film surface. Preferably it is uniform. In this specification, the thin film layer being substantially uniform in the film surface direction means that when the carbon distribution curve is created at any two measurement points on the film surface of the thin film layer by XPS depth profile measurement, The number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in each carbon distribution curve is the same. The difference is within 5 at%.

Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. In the present specification, the carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion in which the atomic ratio of carbon changes discontinuously. Specifically, the etching rate, the etching time, From the relationship between the distance (x, unit: nm) from the surface of the layer in the film thickness direction of at least one of the thin film layers calculated from the above, and the atomic ratio of carbon (C, unit: at%) The following mathematical formula (F1):
| DC / dx | ≦ 1 (F1)
This means that the condition represented by

In the present invention, the density of the thin film layer is preferably 0.9 g / cm ³ or more and 2.2 g / cm ³ or less. The density of the thin film layer can be adjusted, for example, by changing the ratio of the source gas to the reaction gas at the time of forming the thin film layer, can be increased by increasing the ratio of the source gas, and can be reduced by reducing the ratio of the source gas. Can be small.
By satisfying such a condition, the gas barrier property is further improved, and when the film is bent, a higher effect of suppressing the gas barrier property can be obtained.

  The gas barrier laminate film of the present invention needs to include at least one thin film layer that satisfies the above condition (i), but may include two or more layers that satisfy such a condition. Further, when two or more such thin film layers are provided, the materials of the plurality of thin film layers may be the same or different. When two or more such thin film layers are provided, such a thin film layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Moreover, as such a some thin film layer, the thin film layer which does not necessarily have gas barrier property may be included.

  The thickness of the thin film layer is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. When the thickness of the thin film layer is not less than the lower limit, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are further improved. Further, by being below the upper limit value, it is possible to obtain a higher effect of suppressing a decrease in gas barrier properties when bent.

  Moreover, when the gas barrier laminate film of the present invention has a barrier layer in which two or more thin film layers are laminated, the total thickness of these thin film layers (the film thickness of the barrier film in which the thin film layers are laminated) is , Greater than 100 nm and preferably 3000 nm or less. When the total thickness of the thin film layers is equal to or greater than the lower limit, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are further improved. Further, by being below the upper limit value, it is possible to obtain a higher effect of suppressing a decrease in gas barrier properties when bent. And it is preferable that the film thickness per layer of the said thin film layer is larger than 50 nm.

  The gas barrier laminate film of the present invention includes the base material and the thin film layer, and may further include a primer coat layer, a heat sealable resin layer, an adhesive layer, and the like as necessary. Such a primer coat layer can be formed using a known primer coat agent capable of improving the adhesion between the substrate and the thin film layer. Moreover, such a heat-sealable resin layer can be suitably formed using a well-known heat-sealable resin. Furthermore, such an adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier laminate films may be adhered to each other by such an adhesive layer.

  In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a plasma chemical vapor deposition method. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a gas containing an organosilicon compound and oxygen is preferable, and the content of oxygen in the film forming gas is the above-described amount in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound. In the gas barrier laminate film of the present invention, the thin film layer may be a layer formed by a continuous film forming process. A method for forming a thin film layer using such plasma chemical vapor deposition will be described below.

  The gas barrier laminate film of the present invention can be produced by forming the thin film layer on the surface of the substrate. As a method of forming such a thin film layer according to the present invention on the surface of the substrate, it is preferable to employ plasma chemical vapor deposition (plasma CVD) from the viewpoint of gas barrier properties. The plasma chemical vapor deposition method is preferably a plasma chemical vapor deposition method in which a connection is made to a plasma power source having a function of alternately inverting the polarities of the two electrodes. As the plasma power source, a bipolar pulse unit is preferably used.

FIG. 1 is a schematic view showing an example of a production apparatus suitable for producing the gas barrier laminate film of the present invention.
The manufacturing apparatus 1 shown in FIG. 1 is a batch type manufacturing apparatus, which includes a stage 10, a first electrode 31, a second electrode 32, a gas supply pipe 41, a plasma generating power supply 51, a first magnetic field generating apparatus 61, and The second magnetic field generator 62 is arranged in a vacuum chamber (not shown), and a vacuum pump (not shown) is connected to the vacuum chamber and is schematically configured. The pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  The stage 10 is used to place a film 100 that is a target for forming a thin film layer. Here, the film 100 is obtained by previously forming the thin film layer on the base material or the base material. By using the base material on which the thin film layer is formed in advance as the film 100, the thickness of the thin film layer can be further increased.

A plate-like first electrode 31 and a second electrode 32 are arranged above the stage 10 so as to face the stage 10. The first electrode 31 and the second electrode 32 preferably have the same size of their surfaces (electrode surfaces). The first electrode 31 and the second electrode 32 are preferably arranged so that their electrode surfaces are parallel to each other, and are arranged so that these electrode surfaces are included in the same plane. More preferably.
The electrode surfaces of the first electrode 31 and the second electrode 32 are preferably arranged so as to be parallel to the film formation surface of the film 100 placed on the stage 10.

  The first electrode 31 and the second electrode 32 are electrically connected to the plasma generating power source 51 so that the polarity is alternately inverted between one electrode and the other electrode. A first magnetic field generator 61 for applying a magnetic field to the first electrode 31 is disposed in the vicinity of the surface of the first electrode 31 opposite to the stage 10. A second magnetic field generator 62 for applying a magnetic field to the second electrode 32 is disposed in the vicinity of the surface of the electrode 32 opposite to the stage 10. With this configuration, when power is supplied from the plasma generation power source 51 to the first electrode 31 and the second electrode 32, plasma is generated by discharge in the vicinity of these electrode surfaces. Yes.

The gas supply pipe 41 is capable of supplying or discharging a raw material gas or the like at a predetermined speed. And it arrange | positions in the vicinity of the 1st electrode 31 and the 2nd electrode 32, and the supplied gas is decomposed | disassembled with plasma efficiently.
The plasma generating power source 51 may be used as a power source for a known plasma generating device, supplying power to the first electrode 31 and the second electrode 32 connected thereto, It can be used as an electrode for discharging. As the plasma generating power source 51, since the plasma CVD can be performed more efficiently, the first electrode 31 and the second electrode 32 that can alternately reverse the polarity (AC power source or the like) are used. It is preferable. Further, as the plasma generating power source 51, for the same reason, it is preferable that the applied power can be set to 100 W to 10 kW and the AC frequency can be set to 50 Hz to 500 kHz.
The first magnetic field generator 61 and the second magnetic field generator 62 may be known ones.

The gas barrier laminate film of the present invention can be produced by using the production apparatus 1 shown in FIG. 1 and appropriately adjusting the type of source gas, supply power, pressure in the vacuum chamber, and the like as follows.
That is, while the film forming gas (raw material gas or the like) is supplied into the vacuum chamber, plasma 91 is generated by discharge at the first electrode 31 and the second electrode 32, thereby forming the film forming gas (raw material gas or the like). Is decomposed by the plasma 91, and the thin film layer is formed on the surface of the film 100 on the stage 10 (plasma CVD method). In FIG. 1, reference numeral 92 indicates magnetic field lines generated by supplying power to the first electrode 31 and the second electrode 32.

The source gas in the film forming gas used for forming the thin film layer can be appropriately selected according to the material of the thin film layer, and examples thereof include silicon-containing organosilicon compounds.
Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, Examples include propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoints of properties such as the handleability of the compound and gas barrier properties of the obtained thin film layer, and hexamethyldisiloxane is preferred. Siloxane is more preferred. Since 1,1,3,3-tetramethyldisiloxane has high flammability and vapor has explosive properties, hexamethyldisiloxane which is stable even in air is more preferable. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
Furthermore, it is good also as using as a silicon source of the barrier film | membrane which contains monosilane other than the above-mentioned organosilicon compound as source gas, and forms.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. Examples of the reaction gas for forming the oxide include oxygen and ozone. Examples of the reaction gas for forming nitride include nitrogen and ammonia. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reactive gas.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, a thin film that satisfies any of the above conditions (i) to (iii) cannot be obtained. In this case, excellent barrier properties and bending resistance cannot be obtained depending on the formed thin film layer. In addition, when the film forming gas contains a gas of the organosilicon compound and an oxygen gas (the oxygen gas also functions as a discharge gas), the oxygen gas content in the film forming gas The total amount of the organosilicon compound is preferably less than the theoretical amount necessary for complete oxidation.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reactive gas is reacted by plasma CVD to form a silicon-oxygen-based thin film In this case, the following reaction formula (1):
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
Reaction occurs as described in 1 to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. Will not remain. Therefore, in the present invention, when the thin film layer is formed, the oxygen amount is set to a stoichiometric ratio with respect to 1 mol of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely. Less than 12 moles. Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is the raw material hexamethyldisiloxane. (It may be about 20 times or more of the molar amount (flow rate).) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably 12 times or less the stoichiometric ratio, and preferably 10 times or less. More preferred. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the thin film layer, and the above conditions (i) to (iii) ) Can be formed. As a result, the obtained gas barrier laminate film exhibits more excellent barrier properties and bending resistance. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, carbon atoms and hydrogen atoms that have not been oxidized are excessively taken into the thin film layer. In this case, the transparency of the barrier film decreases, and the barrier film cannot be used for a flexible substrate for a device that requires transparency such as an organic EL device or an organic thin film solar cell. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen in the film forming gas is preferably 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, and is 0.5 times. It is more preferable.

  At the time of film formation, the stage 10 may be kept stationary. For example, the film thickness and the carbon distribution of the thin film layer are rotated by rotating the axis in a direction perpendicular to the mounting surface of the film 100 as a rotation axis. Can be made more uniform.

  What is necessary is just to adjust suitably the pressure (vacuum degree) in the vacuum chamber at the time of film-forming according to the kind etc. of source gas, for example, it is preferable to set it as 0.1 Pa-50Pa. However, when the film formation rate may be low, it is preferable to set the pressure as low as possible within the range in which plasma discharge is possible.

  In such a plasma CVD method, in order to discharge at the first electrode 31 and the second electrode 32, the power applied to the plate electrode connected to the plasma generating power source 51 depends on the type of source gas and the vacuum. Although it can adjust suitably according to the pressure in a chamber, etc. and it cannot generally say, it is preferable to set it as the range of 0.1-10 kW. By setting the applied power to the lower limit value or more, a higher effect of suppressing the generation of particles can be obtained. In addition, by setting the upper limit value or less, excessive heat generation during film formation and excessive temperature rise on the substrate surface associated therewith are suppressed, generation of wrinkles due to heat loss of the substrate, and dissolution of the film 100 A higher effect of suppression can be obtained.

In the manufacturing apparatus 1, plasma is generated in the vicinity of these electrode surfaces by supplying electric power to the first electrode 31 and the second electrode 32 from the plasma generation power source 51. Due to the effect, a plasma intensity distribution is produced at a position closer to these electrodes. However, in the manufacturing apparatus 1, the first electrode 31 and the second electrode 32 are disposed opposite to each other on the same side (upper side) with respect to the surface of the film 100 with a predetermined distance X ₁ from the film 100. ing. Thus, in the position spaced from the electrodes by a predetermined distance X _1, distribution of plasma intensity is reduced to a negligible, it can be regarded as almost constant. Therefore, by forming a thin film layer in a region where the plasma intensity is more stable than in the prior art, the obtained thin film has a carbon atom ratio from the surface of the thin film layer to the deep part in the film thickness direction. The difference between the maximum value of the carbon atom and the minimum value of the carbon atom ratio is suppressed to 5% or less, the carbon ratio becomes more uniform, and the condition (i) is satisfied.

Note that FIG. 1 shows a manufacturing apparatus in which two magnetic field generators are arranged, but the number of magnetic field generators is not limited to this, and may be adjusted as appropriate according to the purpose.
And the distance between the magnetic field generators, the number of magnets (shown as having “N pole” and “S pole” in FIG. 1) constituting each magnetic field generator, the distance between the magnets, etc. May be adjusted as appropriate according to the purpose.

So far, although the manufacturing method of the gas-barrier laminated | multilayer film at the time of using a batch type manufacturing apparatus was demonstrated, using a continuous type manufacturing apparatus and using the long thing as the film 100, moving this By forming a thin film, the thin film layer can be formed even in a continuous film forming process.
For that purpose, instead of placing the film 100 on the stage 10 in FIG. 1, as shown in FIG. 2, as shown in FIG. The apparatus 2 may be used to perform plasma CVD while conveying the long film 101 to form a thin film layer. In the continuous manufacturing apparatus 2, after the long film 101 is fed from the feed roll 20, the take-up roll 23 is passed through a pair of transport rolls (first transport roll 21 and second transport roll 22). It is comprised so that it may be wound up by. Distance X ₂ between the case of long film 101 on the surface and the surface of the first electrode 31 and second electrode 32, the film 100 in FIG surface of the first electrode 31 and second electrode 32 same as the distance X ₁ between the surfaces. 2 that are the same as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed descriptions thereof are omitted.

  In this case, the conveyance speed (line speed) of the film 101 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably 0.1 to 100 m / min. More preferably, it is 5 to 20 m / min. By setting the line speed to be equal to or higher than the lower limit, a higher effect of suppressing generation of wrinkles due to excessive heating of the film 101 can be obtained. Moreover, the more excellent effect which makes the thickness of the thin film layer formed stable and makes a desired value by setting it as the said upper limit or less is acquired.

  The gas barrier laminate film of the present invention has a sufficient gas barrier property, and even when the film is bent, it is possible to remarkably suppress a decrease in gas barrier property, so that an organic EL element, an organic thin film solar cell, a liquid crystal It is particularly suitable as a film for use in elements and devices that require high gas barrier properties such as displays.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

Example 1
A gas barrier laminate film was produced using the batch production apparatus shown in FIG. A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as a substrate (165 mm × 170 mm), and this was set at the bottom of the vacuum chamber. Then, a plasma generating power source 51 was connected to the first electrode 31 and the second electrode 32 arranged at the upper portion so that the polarity was alternately inverted between one electrode and the other electrode. . Then, the first magnetic field generator 61 and the second magnetic field generator 62 are arranged on the back of these electrodes, and electric power is supplied to these electrodes to discharge them, and plasma is generated between the electrodes. A film forming gas (a mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (which also functions as a discharge gas) as a reaction gas) is supplied to form a thin film by a plasma CVD method, A gas barrier laminate film was obtained. At this time, the base material was set at a predetermined distance from the electrode so that the distribution of the plasma intensity generated by the magnetic field effect could be ignored. Further, as described above, in order to prevent the reaction of the formula (1) from proceeding completely, the oxygen amount is less than the stoichiometric ratio of 12 mol with respect to 1 mol of hexamethyldisiloxane. The film formation was performed under the condition that the flow rate of HMDSO was 7 sccm (0 ° C., 1 atm reference) and the flow rate of oxygen was 73 sccm (0 ° C., 1 atm reference) (HMDSO / (HMDSO + O ₂ ) = 8.75%). Since the film formation rate was 0.89 nm / s, film formation was performed for 337 seconds so that the film thickness was 300 nm The film thickness of the formed thin film layer was about 300 nm. The carbon distribution curve, silicon distribution curve and oxygen distribution curve of the thin film layer are shown in Fig. 3. The carbon distribution curve, silicon distribution curve and oxygen distribution curve were prepared by the above XPS depth profile measurement, where the vertical axis represents the vertical axis. Each element The atomic ratio (unit: at%), the horizontal axis indicates the distance (unit: nm) from the surface of the thin film layer in the thickness direction of the thin film layer, and the sputtering method employed for such XPS depth profile measurement As this, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species was employed.
As apparent from FIG. 3, the difference between the maximum value and the minimum value of the carbon distribution curve was 5%, which was the following. In addition, using a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. When the water vapor permeability of the obtained gas barrier laminate film was measured, the barrier property was recognized.
In this embodiment, the film was formed using the batch type manufacturing apparatus shown in FIG. 1, but the film can be continuously formed by the roll-to-roll method using the continuous type manufacturing apparatus shown in FIG. .

  INDUSTRIAL APPLICABILITY The present invention can be used for flexible illumination using organic electroluminescence elements (organic EL elements), organic thin film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

DESCRIPTION OF SYMBOLS 1 ... Batch type manufacturing apparatus, 2 ... Continuous manufacturing apparatus, 10 ... Stage, 20 ... Sending roll, 21 ... 1st conveyance roll, 22 ... 2nd conveyance roll , 23 ... take-up roll, 31 ... first electrode, 32 ... second electrode, 41 ... gas supply pipe, 51 ... power source for generating plasma, 61 ... first the magnetic field generator, 62 ... second magnetic field generator, 91 ... plasma, 92 ... magnetic field lines, 100 ... film, 101 ... elongated _film, the _X 1 ... film 100 Spacing between the surface and the surfaces of the first electrode 31 and the second electrode 32, X ₂ ... Spacing between the surface of the long film 101 and the surfaces of the first electrode 31 and the second electrode 32.

Claims (18)

A gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate,
At least one of the thin film layers contains silicon, oxygen and carbon, and the following condition (i):
(I) Carbon indicating the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio). In the distribution curve, the difference between the maximum value of the carbon atom ratio in the thin film layer and the minimum value of the carbon atom ratio is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
A gas barrier laminate film characterized by satisfying Furthermore, the following condition (ii):
(Ii) In the thin film layer, a ratio of a total amount of oxygen atoms and carbon atoms to silicon atoms is greater than 1.98 and not more than 2.03.
1.98 <((amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2.03
The gas barrier laminate film according to claim 1, wherein: Furthermore, the following condition (iii):
(Iii) silicon showing the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon) In the distribution curve, the silicon atom ratio is 30.0% or more and 37.0% or less in a region of 90% or more in the thin film layer.
(30% ≦ ((amount of silicon atoms) / ((amount of oxygen atoms) + (amount of carbon atoms) + (amount of silicon atoms)) ≦ 37%)
The gas barrier laminate film according to claim 1 or 2, wherein: Furthermore, the following condition (iv):
(Iv) The thin film layer is formed by a plasma CVD method, a film formation gas of the plasma CVD method is an organic silicon compound gas and an oxygen gas, and the organic silicon compound is hexamethyldisiloxane (HMDSO). .
The gas barrier laminate film according to any one of claims 1 to 3, wherein the gas barrier laminate film is satisfied. The gas barrier property according to any one of claims 1 to 4, wherein in the thin film layer, a ratio of a total amount of oxygen atoms and carbon atoms to silicon atoms is 2 or less. Laminated film.
((Amount of oxygen atoms) + (amount of carbon atoms)) / (amount of silicon atoms) ≦ 2   It has a barrier layer in which two or more thin film layers are stacked, the film thickness per layer of the thin film layer is larger than 50 nm, and the film thickness of the barrier film in which the thin film layers are stacked is larger than 100 nm and not larger than 3000 nm The gas barrier laminate film according to any one of claims 1 to 5, wherein:   The ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) in the thin film layer is 1% or more and 67% or less. The gas barrier laminate film according to any one of the above. Gas barrier laminate film according to any one of claims 1 to 7, wherein the density of the thin layer, characterized in that at 0.9 g / cm ³ or more 2.2 g / cm ³ or less.   A pair of electrodes are spaced apart from the base material by a predetermined distance so as to face the base material, arranged on the same side of the surface of the base material, and discharge is generated at the pair of electrodes to generate plasma. The gas barrier laminate film according to any one of claims 1 to 8, wherein the thin film layer is formed by plasma chemical vapor deposition.   The gas barrier laminate film according to claim 9, wherein when discharging is performed in the pair of electrodes, the polarities of the pair of electrodes are alternately reversed.   The content of the oxygen gas in the film forming gas is equal to or less than the theoretical oxygen amount necessary for complete oxidation of the total amount of hexamethyldisiloxane (HMDSO) that is the organosilicon compound in the film forming gas. The gas barrier laminate film according to any one of claims 1 to 10, wherein:   The gas barrier laminate film according to any one of claims 1 to 11, wherein the thin film layer is a layer formed by a continuous film forming process.   The gas barrier laminate film according to any one of claims 1 to 12, wherein the substrate is made of at least one resin selected from the group consisting of polyester resins and polyolefin resins.   The gas barrier laminate film according to any one of claims 1 to 13, wherein the substrate is made of at least one resin selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate.   An organic electroluminescence device comprising the gas barrier laminate film according to claim 1.   An organic thin film solar cell comprising the gas barrier laminate film according to any one of claims 1 to 14.   A liquid crystal display comprising the gas barrier laminate film according to claim 1. A method for producing a gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate,
A pair of electrodes are spaced apart from the base material by a predetermined distance so as to face the base material, arranged on the same side of the surface of the base material, and discharge is generated at the pair of electrodes to generate plasma. The plasma chemical vapor deposition method includes silicon, oxygen, and carbon, and the following condition (i):
(I) Carbon indicating the relationship between the distance from the surface of the thin film layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio). In the distribution curve, the difference between the maximum value of the carbon atom ratio in the thin film layer and the minimum value of the carbon atom ratio is 5% or less.
(Maximum carbon atom ratio)-(Minimum carbon atom ratio) ≤ 5%
A method for producing a gas barrier laminate film, comprising forming at least one thin film layer satisfying the above conditions on a substrate.

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