JP2013029499A - Inspection method for laminate film and manufacturing method for laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inspection method for a laminate film that enables quick and easy evaluation of a gas barrier property.SOLUTION: An inspection method for a laminate film, which comprises a substrate and a thin layer that is formed at least on one surface of the substrate and contains at least silicon, oxygen and hydrogen, includes the steps of: obtaining an abundance ratio of silicon atoms within the thin layer throughSi solid NMR measurement of the thin layer, with respect to each quantity of neutral oxygen atoms binding to the silicon atoms; and determining a gas barrier property of the thin layer on the basis of a preliminarily-obtained correspondence relationship between the gas barrier property of the thin layer and the abundance ratio of the silicon atoms.

Description

  The present invention relates to a method for inspecting a laminated film having gas barrier properties. Moreover, it is related with the manufacturing method of the laminated film which makes such an inspection method 1 process.

  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 has been proposed in which a plastic film or the like is used as a base material and a thin film is formed on one surface of the base material using a material such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide. Yes.

  As a method for forming such a thin film on the surface of a plastic substrate, a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method, an ion plating method, a low pressure chemical vapor deposition method, a plasma chemistry method, or the like. Chemical vapor deposition (CVD) such as vapor deposition is known. In addition, as a laminated film formed by such a film forming method, for example, a laminated film formed by a film forming apparatus that continuously forms a film on a surface of a base material by a CVD method while conveying a long base material is used. Proposed.

  The gas barrier property of this laminated film is, for example, JIS K 7129: 2008 “Plastics—Films and Sheets—How to Obtain Water Vapor Permeability (Instrument Measurement Method)” Appendix C “How to Obtain Water Vapor Permeability by Gas Chromatography” , Sometimes referred to as JIS gas chromatography method) (see Non-Patent Document 1). The lower the water vapor transmission rate (also referred to as water vapor transmission rate), the better the gas barrier property. The predetermined temperature and humidity for gas barrier property evaluation are, for example, a temperature of 40 ° C. and a humidity of 90% RH.

  The gas barrier property of the laminated film can be evaluated as, for example, a water vapor transmission rate measured by a calcium method. With the calcium method, a metal calcium film is formed by a method such as vapor deposition and sealed. After sealing, it is stored in an atmosphere of a predetermined temperature and humidity for a certain period of time and reacts with moisture that has permeated the laminated film. This is a measurement method for determining the amount of metallic calcium.

  There are several methods in the calcium method, a method for measuring the change in light transmittance, a method for measuring the area change of calcium hydroxide formed by corrosion by reaction with water, and the electrical resistance of unreacted metallic calcium. Examples of the method for measuring the value can be given. Patent Document 1 describes a method for obtaining water vapor permeability by measuring the area of calcium hydroxide formed by corrosion due to reaction with water. The predetermined temperature and humidity for gas barrier property evaluation are, for example, a temperature of 40 ° C. and a humidity of 90% RH.

  In addition, Patent Document 2 discloses that a functional element provided with a gas barrier film whose refractive index changes with changes in gas barrier properties has a refractive index equivalent to that of a non-defective gas barrier film and the refractive index does not change. A configuration in which a marker is provided in advance is disclosed. According to this configuration, the change in the gas barrier property of the gas barrier film can be detected based on whether or not the marker can be identified.

Japanese Patent No. 4407466 Japanese Patent No. 4401231

JIS K 7129: 2008 "Plastics-Film and sheet-Determination of water vapor transmission rate (instrument measurement method)" Appendix C "Method of determination of water vapor transmission rate by gas chromatography"

  However, when it is assumed that the gas barrier property measuring method as described above is used, for example, for quality inspection of the manufactured laminated film, there are the following problems.

  That is, in the JIS gas chromatographic method, the measurement must be repeated until it can be confirmed that a steady state is obtained, and usually a measurement time of about 3 days to 1 week is required. Therefore, in order to adopt the JIS gas chromatographic measurement results each time as a reference value representing gas barrier properties in the quality inspection for inspecting the performance of the manufactured laminated film and judging whether it can be shipped or used, the test time Is too long.

  In addition, measurement by the calcium method usually requires a measurement time of about 1 to 2 months. Therefore, it is difficult to adopt for quality inspection every time for the same reason as the above-mentioned JIS gas chromatography method.

  Furthermore, in the method of Patent Document 2, an extra step is required to separately create a marker on the gas barrier film, which is complicated (that is, productivity is reduced).

  From these things, the method of obtaining a result quicker than before was calculated | required as an inspection method of a laminated film simply and conventionally.

  This invention is made | formed in view of such a situation, Comprising: It aims at providing the test | inspection method of the laminated | multilayer film which makes it easy and can evaluate gas barrier property in a short time. Another object of the present invention is to provide a method for producing a laminated film that includes a quality evaluation step for the laminated film and enables production of a high-quality laminated film.

  The present invention has the following aspects.

A first aspect of the present invention is a method for inspecting a laminated film comprising a base material and a thin film layer formed on at least one surface of the base material and containing at least silicon, oxygen, and hydrogen, ²⁹ Si solid state NMR measurement of the thin film layer was performed to determine the abundance ratio of silicon atoms in the thin film layer for each number of neutral oxygen atoms bonded to silicon atoms, and the gas barrier properties of the thin film layer and the previously determined This is a method for inspecting a laminated film in which the gas barrier property of the thin film layer is determined based on the correspondence with the abundance ratio of silicon atoms.

In the second aspect of the present invention, the abundance ratio of the silicon atoms is a value obtained by summing the peak areas of Q ¹ , Q ² , and Q ³ with respect to the peak area of Q ⁴ in the ²⁹ Si solid state NMR spectrum of the thin film layer. In the first aspect, the gas barrier property of the thin film layer in which the abundance ratio of the silicon atoms is less than the threshold is determined as a non-defective product based on a threshold value that is predetermined with respect to the abundance ratio of the silicon atoms. It is a test | inspection method of the laminated film of description.

  A third aspect of the present invention is the laminated film inspection method according to the second aspect, wherein the threshold value is 1.0.

A fourth aspect of the present invention, abundance ratio of the silicon atoms, to the peak area of the peak area ratio (Q ^4, the ^{29 Si} solid state NMR spectrum of the thin film layer, to the peak area of Q ^4, Q ^1, The ratio of the peak areas of Q ² and Q ³ , which is a ratio of the sum of the peak areas of Q ² and Q ³ , is 0.8 or less.

  A fifth aspect of the present invention is the laminated film inspection method according to the second aspect, wherein the silicon atom abundance ratio is 0.6 or less in terms of the peak area ratio.

  The sixth aspect of the present invention is the laminated film according to any one of the first to fifth aspects, wherein the base material is at least one resin selected from the group consisting of a polyester resin and a polyolefin resin. This is an inspection method.

  A seventh aspect of the present invention is the laminated film inspection method according to the sixth aspect, in which the base material is at least one resin selected from the group consisting of PET, PEN, and cyclic polyolefin. is there.

  The eighth aspect of the present invention is the laminated film inspection method according to any one of the first to seventh aspects, wherein the thickness of the base material is 5 μm to 500 μm.

  The ninth aspect of the present invention relates to the step of forming a thin film layer containing at least silicon, oxygen, and hydrogen on at least one surface of the substrate, and the test piece including the thin film layer. 8. A non-defective product based on the inspection step of determining the gas barrier property of the thin film layer using the inspection method according to any one of aspects 8 and the correspondence relationship between the gas barrier property of the thin film layer and the abundance ratio of the silicon atoms. A method for producing a non-defective laminated film comprising:

  A tenth aspect of the present invention is the lamination according to the ninth aspect, wherein in the step of forming the thin film layer, the thin film layer is continuously formed while continuously conveying a long base material. It is a manufacturing method of a film.

  According to an eleventh aspect of the present invention, in the step of forming the thin film layer, the first film forming roll on which the first base material is wound and the first film forming roll face the second film base. The material for forming the thin film layer generated in the space between the first film forming roll and the second film forming roll by applying an AC voltage between the second film forming roll on which the material is wound It is a manufacturing method of the laminated | multilayer film as described in the said 10th aspect which uses plasma CVD using the discharge plasma of film-forming gas which is.

  According to a twelfth aspect of the present invention, the discharge plasma forms an alternating electric field between the first film forming roll and the second film forming roll, and the first film forming roll and the second film forming roll. By forming an endless tunnel-like magnetic field that swells in a space facing the roll, a first discharge plasma formed along the tunnel-like magnetic field is formed around the tunnel-like magnetic field. And the step of forming the thin film layer transports the base material so as to overlap the first discharge plasma and the second discharge plasma. It is a manufacturing method of the laminated | multilayer film as described in an aspect.

In a thirteenth aspect of the present invention, the distance from the surface of the thin film layer in the thickness direction and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (silicon atomic ratio), In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the ratio of the amount of oxygen atoms (atomic ratio of oxygen) and the ratio of the amount of carbon atoms (atomic ratio of carbon), respectively, the following conditions (i) to (Iii):
(I) In the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Or in the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the thickness of the layer, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 atomic% (ie, at%) or more;
It is a manufacturing method of the laminated | multilayer film as described in the said 12th aspect which controls the mixing ratio of the organosilicon compound contained in the said film-forming gas, and oxygen so that all may be satisfy | filled.

  A fourteenth aspect of the present invention is the method for producing a laminated film according to the thirteenth aspect, wherein the carbon distribution curve has at least three extreme values.

  In the fifteenth aspect of the present invention, the absolute value of the difference in distance from the surface of the thin film layer in the thickness direction of the thin film layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value is both. It is a manufacturing method of the laminated | multilayer film as described in the said 13th or 14th aspect which is 200 nm or less.

  A sixteenth aspect of the present invention is the method for producing a laminated film according to any one of the thirteenth to fifteenth aspects, wherein the carbon distribution curve is substantially continuous.

According to a seventeenth aspect of the present invention, the carbon distribution curve has a distance X from the surface of the thin film layer in the thickness direction of the thin film layer calculated from an etching rate and an etching time, and a carbon atom ratio C is as follows: Formula F1
| DC / dx | ≦ 1... (F1)
It is a manufacturing method of the laminated | multilayer film as described in any one aspect of the said 13th-16th satisfy | filling the relationship of these.

  An eighteenth aspect of the present invention is the method for producing a laminated film according to any one of the above aspects 9 to 17, wherein the thin film layer has a thickness of 5 nm to 3000 nm.

  According to this invention, the gas barrier property of a laminated film can be evaluated easily in a short time. In a preferred embodiment, the evaluation can be performed with high accuracy. Moreover, it becomes possible to manufacture a high-quality laminated film.

It is a schematic diagram about an example of the laminated | multilayer film which is the test object of the test | inspection method of this embodiment, and the manufacturing object of the manufacturing method of this embodiment. It is a schematic diagram which shows one Embodiment of the manufacturing apparatus used for manufacture of a laminated | multilayer film. Is a chart showing the ²⁹ Si solid state NMR measurement. Is a chart showing the ²⁹ Si solid state NMR measurement. Is a chart showing the ²⁹ Si solid state NMR measurement.

  Hereinafter, a laminated film inspection method and a laminated film manufacturing method according to an embodiment of the present invention will be described with reference to FIGS. In all the drawings below, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawings easy to see.

(Laminated film)
FIG. 1 is a schematic diagram of an example of a laminated film that is an inspection target of the inspection method of the present embodiment and a manufacturing target of the manufacturing method of the present embodiment. The laminated film that is the object of the present embodiment is formed by laminating a thin film layer H that ensures gas barrier properties on the surface of a substrate F. The thin film layer H includes at least one of the thin film layers H containing silicon, oxygen, and hydrogen, and a first layer Ha containing a large amount of SiO ₂ formed by a complete oxidation reaction of a film forming gas, which will be described later. It includes a second layer Hb containing a large amount of SiO _x C _y produced by the oxidation reaction, and has a three-layer structure in which the first layer Ha and the second layer Hb are alternately stacked.

  However, the figure schematically shows that there is a distribution in the film composition. In fact, there is no clear interface between the first layer Ha and the second layer Hb, and the composition is It is changing continuously. A plurality of thin film layers H may be stacked.

  The thin film layer H which is a target of the present embodiment is a layer formed on at least one surface of the base material F in the laminated film. Further, at least one of the thin film layers H may further contain nitrogen, aluminum, and titanium. The configuration of the thin film layer H will be described in detail later.

(Base material)
Examples of the base material F used for the laminated film that is the subject of the present embodiment include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE), polypropylene (PP), cyclic polyolefin, and the like. Polyolefin resin; Polyamide resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Polyether sulfide (PES) These two or more types can also be used in combination. The polyester resin and the polyolefin resin are preferably selected in accordance with necessary properties such as transparency, heat resistance, and linear expansion property, and PET, PEN, and cyclic polyolefin are more preferable. In addition, examples of the composite material including a resin include silicone resins such as polydimethylsiloxane and polysilsesquioxane, a glass composite substrate, and a glass epoxy substrate. Among these resins, polyester resins, polyolefin resins, glass composite substrates, and glass epoxy substrates are preferable from the viewpoint of high heat resistance and low linear expansion coefficient. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

When a material containing silicone resin or glass is used as the base material F, the thin film layer H is separated from the base material F in order to avoid the influence of silicon in the base material F in ²⁹ Si solid state NMR measurement. ²⁹ Si solid state NMR of only silicon contained in the layer H is measured.
As a method for separating the thin film layer H and the base material F, for example, a method of scraping the thin film layer H with a metal spatula or the like and collecting it in a sample tube in ²⁹ Si solid state NMR measurement can be mentioned. Alternatively, the base material F may be removed using a solvent that dissolves only the base material F, and the thin film layer H remaining as a residue may be collected.

  The thickness of the base material F is appropriately set in consideration of stability and the like when manufacturing a laminated film. However, since the transport of the base material F is easy even in a vacuum, the thickness is 5 μm to 500 μm. preferable. Furthermore, in the laminated film which is the object of the present embodiment, in the formation of the thin film layer H, since the discharge is performed through the substrate F as described later, the thickness of the substrate F is more preferably 50 μm to 200 μm. It is especially preferable that it is 50 micrometers-100 micrometers.

  The base material F may be subjected to a surface activation treatment for cleaning the surface from the viewpoint of adhesion with the thin film layer H to be formed. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

(Other configurations)
The laminated film that is the subject of the present embodiment includes the base material and the thin film layer, but may further include a primer coat layer, a heat-sealable resin layer, an adhesive layer, and the like as necessary. Good. 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 laminated films may be bonded to each other by such an adhesive layer.
The method for producing the laminated film shown in FIG. 1 will be described in detail later.

(Inspection method for laminated film)
In the inspection method of the present embodiment, the thin film layer H included in the laminated film is used for measurement of gas barrier properties by focusing on the bonding state of silicon atoms constituting the thin film layer H. As a value representing the bonding state of silicon atoms, the peak area determined in ²⁹ Si solid state NMR measurement is used.

That is, at least one thin film layer H contains silicon, oxygen, and hydrogen, and corresponds to the following silicon atoms of Q ¹ , Q ² , Q ³ , and Q ⁴ in the ²⁹ Si solid state NMR measurement of the thin film layer H. A peak is required.

Here, Q ¹ , Q ² , Q ³ , and Q ⁴ indicate the silicon atoms constituting the thin film layer H by distinguishing them according to the nature of oxygen bonded to the silicon atoms. That is, each symbol of Q ¹ , Q ² , Q ³ , and Q ⁴ is bonded to a silicon atom when an oxygen atom that forms a Si—O—Si bond is a “neutral” oxygen atom with respect to a hydroxyl group. The oxygen atom is as follows.
Q ¹ : silicon atom bonded to one neutral oxygen atom and three hydroxyl groups Q ² : silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups Q ³ : three neutral oxygen atoms and 1 Silicon atom bonded to two hydroxyl groups Q ⁴ : Silicon atom bonded to four neutral oxygen atoms

Here, in the case of measuring “ ²⁹ Si solid state NMR of the thin film layer H”, the base material F may be included in the test piece used for the measurement.

The area ratio of each peak obtained in ²⁹ Si solid state NMR measurement indicates the abundance ratio of silicon atoms in each bonded state.

The silicon atom of Q ⁴ is considered to be surrounded by four neutral oxygen atoms around the silicon atom, and the four neutral oxygen atoms are bonded to the silicon atom to form a network structure. On the other hand, since the silicon atoms of Q ¹ , Q ² , and Q ³ are bonded to one or more hydroxyl groups, there are fine voids in which no covalent bond is formed between adjacent silicon atoms. Conceivable.

Therefore, as the number of silicon atoms of Q ⁴ increases, the thin film layer H becomes a dense layer, and a laminated film realizing high gas barrier properties can be obtained. In the inspection method of the present embodiment, the correspondence between the silicon atom area ratio in each bonded state and the gas barrier property of the laminated film is obtained in advance, and thereafter (that is, the second and subsequent measurements) for laminated film to be measured, by performing a ^{29 Si} solid state NMR measurement of a sample comprising a thin film layer may measure gas barrier laminated film.

Specifically, first, to the peak area of ^{Q 4, Q 1, Q 2} , the ratio of the total value of the peak area of ^{Q 3 ((Q 1, Q} 2, total value of the peak area of ^{Q 3)} / (Q peak area of ⁴⁾⁾ (hereinafter, this value may be referred to as "peak area ratio"), determined the gas barrier laminated film, respectively, corresponding with the gas barrier laminate film and the peak area ratio Seeking a relationship.

Next, ²⁹ Si solid state NMR measurement of the sample including the thin film layer is performed on the laminated film to be measured, and the peak area ratio of the sample is obtained.

  Next, a threshold value of the peak area ratio corresponding to the allowable gas barrier property is set, and the gas barrier property of the laminated film to be measured is evaluated by comparing the threshold value with the obtained peak area ratio of the sample. To do. For example, the threshold value of a laminated film showing good gas barrier properties is 1.0, and those having a peak area ratio of less than 1.0 can be determined as non-defective products. The peak area ratio is preferably 0.8 or less, and more preferably 0.6 or less.

  In addition, when obtaining the “corresponding relationship between the peak area ratio and the gas barrier property of the laminated film” as a reference (that is, the first measurement), the gas barrier property is measured using the JIS gas chromatographic method or the calcium method. be able to.

The peak area of ²⁹ Si solid state NMR is calculated as follows, for example.
First, the spectrum obtained by ²⁹ Si solid state NMR measurement is smoothed.

In the following description, the spectrum after smoothing is referred to as “measured spectrum”. ^Since the spectrum obtained by ²⁹ Si solid state NMR measurement often contains noise having a frequency higher than that of the peak signal, the noise is removed by smoothing. A spectrum obtained by ²⁹ Si solid state NMR measurement is first subjected to Fourier transform to remove a high frequency of 100 Hz or more. When high frequency noise of 100 Hz or more is removed, inverse Fourier transform is performed, and this is defined as a “measurement spectrum”.

Next, the measured spectrum ^is separated into peaks of ^{Q 1, Q 2, Q 3} , Q 4. That is, it is assumed that the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ each show a Gaussian (normal distribution) curve centered on a specific chemical shift, and Q ¹ , Q ² , Q ³ , Q Parameters such as the height and the half-value width of each peak are optimized so that the model spectrum obtained by adding ⁴ matches the smoothed spectrum of the measured spectrum.

  The parameter optimization is performed by using, for example, an iterative method. In other words, using an iterative method, a parameter for which the sum of the squares of the deviation between the model spectrum and the measured spectrum converges to a minimum value is calculated.

Next, each peak area is calculated by integrating the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ thus obtained. Using the peak area thus obtained, the above-described peak area ratio is obtained and used as an evaluation index for gas barrier properties.

The value of the peak area ratio is preferably smaller than 1, more preferably 0.8 or less, and further preferably 0.6 or less.
That is, the value of (total value of peak areas of Q ¹ , Q ² , Q ³ ) / (peak area of Q ⁴ ) is preferably 0 or more and 0.8 or less, and more preferably 0 or more and 0.6 or less. It is as follows.

(Laminated film manufacturing method)
Drawing 2 is a mimetic diagram showing one embodiment of a manufacture device used for manufacture of a lamination film. In FIG. 2, the dimensions and ratios of the constituent elements are appropriately changed in order to make the drawing easier to see.

  The manufacturing apparatus 10 shown in the figure includes a delivery roll 11, a take-up roll 12, transport rolls 13 to 16, a film forming roll (first film forming roll) 17, a film forming roll (second film forming roll) 18, and a gas supply pipe. 19, a plasma generation power source 20, electrodes 21 and 22, a magnetic field forming device 23 installed inside the film forming roll 17, and a magnetic field forming device 24 installed inside the film forming roll 18. Among the constituent elements of the manufacturing apparatus 10, at least the film forming rolls 17 and 18, the gas supply pipe 19, and the magnetic field forming apparatuses 23 and 24 are arranged in a vacuum chamber (not shown) when the laminated film is manufactured. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

  When this apparatus is used, discharge plasma of the film forming gas supplied from the gas supply pipe 19 is generated in the space between the film forming roll 17 and the film forming roll 18 by controlling the plasma generating power source 20. In addition, plasma CVD film formation using plasma enhanced chemical vapor deposition can be performed using generated discharge plasma.

  The feed roll 11 is installed in a state where the belt-like base material F before film formation is wound up, and the base material F is sent out while being unwound in the longitudinal direction. Moreover, the winding roll 12 is provided in the edge part side of the base material F, winds up pulling the base material F after film-forming was performed, and accommodates in roll shape.

  The film forming roll 17 and the film forming roll 18 extend in parallel and face each other. Both rolls are formed of a conductive material. The base material F is wound around the film forming roll 17, and the base material F is also wound around the film forming roll 18 disposed downstream of the transport path of the base material F with respect to the film forming roll 17. The base material F is conveyed while rotating each. The film forming roll 17 and the film forming roll 18 are insulated from each other and connected to a common power source 20 for generating plasma. When an AC voltage is applied from the plasma generating power source 20, an electric field is formed in the space SP between the film forming roll 17 and the film forming roll 18.

  Further, the film forming roll 17 and the film forming roll 18 have magnetic field forming devices 23 and 24 stored therein. The magnetic field forming devices 23 and 24 are members that form a magnetic field in the space SP, and are stored so as not to rotate together with the film forming roll 17 and the film forming roll 18.

  The magnetic field forming devices 23 and 24 include the film forming roll 17 and the center magnets 23a and 24a extending in the same direction as the film forming roll 18 and the film forming rolls 17 and 24a while surrounding the center magnets 23a and 24a. And annular outer magnets 23b and 24b arranged extending in the same direction as the film forming roll 18 is extended. In the magnetic field forming device 23, magnetic lines (magnetic field) connecting the central magnet 23a and the external magnet 23b form an endless tunnel. Similarly, in the magnetic field forming device 24, the magnetic field lines connecting the central magnet 24a and the external magnet 24b form an endless tunnel.

  A discharge plasma of the film forming gas is generated by the magnetron discharge in which the magnetic field lines intersect with the AC electric field formed between the film forming roll 17 and the film forming roll 18. That is, as will be described in detail later, the space SP is used as a film formation space for performing plasma CVD film formation, and film formation is performed on the surface (film formation surface) that does not contact the film formation rolls 17 and 18 in the substrate F. A thin film layer using a gas as a forming material is formed.

  In the vicinity of the space SP, a gas supply pipe 19 for supplying a film forming gas such as a plasma CVD source gas into the space SP is provided. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the film forming roll 17 and the film forming roll 18, and the film forming gas is formed in the space SP from openings provided at a plurality of locations. Supply. In the figure, the state in which the deposition gas is supplied from the gas supply pipe 19 toward the space SP is indicated by arrows.

  The source gas can be appropriately selected and used according to the material of the barrier film to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, dimethyldisilazane, trimethyldisilazane, Examples include tetramethyldisilazane, pentamethyldisilazane, and hexamethyldisilazane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling of the compound and gas barrier properties of the resulting barrier film. 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.

  As the film forming gas, a reactive gas may be used in addition to the source 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. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

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

  The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas and the like, but the pressure in the space SP is preferably 0.1 Pa to 50 Pa. When plasma CVD is a low pressure plasma CVD method for the purpose of suppressing gas phase reaction, it is usually 0.1 Pa to 10 Pa. The power of the electrode drum of the plasma generator 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 kW to 10 kW.

  Although the conveyance speed (line speed) of the base material F can be appropriately adjusted according to the type of the raw material gas, the pressure in the vacuum chamber, and the like, it is preferably 0.1 m / min to 100 m / min. More preferably, it is 5 m / min to 20 m / min. When the line speed is less than the lower limit, wrinkles due to heat tend to occur on the base material F. On the other hand, when the line speed exceeds the upper limit, the thickness of the formed barrier film tends to be thin.

  In the manufacturing apparatus (plasma CVD film forming apparatus) 10 as described above, film formation is performed on the base material F as follows.

First, prior to film formation, a pretreatment may be performed so that outgas generated from the substrate F is sufficiently reduced. The amount of outgas generated from the base material F can be determined using the pressure when the base material F is mounted on a manufacturing apparatus and the inside of the apparatus (inside the chamber) is decompressed. For example, if the pressure in the chamber of the manufacturing apparatus is 1 × 10 ⁻³ Pa or less, it can be determined that the amount of outgas generated from the substrate F is sufficiently reduced.

  Examples of the method for reducing the amount of outgas generated from the substrate F include vacuum drying, heat drying, drying by a combination thereof, and drying by natural drying. Regardless of the drying method, in order to accelerate the drying of the inside of the base material F wound up in a roll shape, the rolls are repeatedly rewinded (unwinded and wound) during drying, and the whole base material F is obtained. Is preferably exposed to a dry environment.

  The vacuum drying is performed by putting the base material F in a pressure-resistant vacuum vessel and evacuating the vacuum vessel using a decompressor such as a vacuum pump. The pressure in the vacuum vessel during vacuum drying is preferably 1000 Pa or less, more preferably 100 Pa or less, and even more preferably 10 Pa or less. The exhaust in the vacuum vessel may be continuously performed by continuously operating the decompressor, and intermittently by operating the decompressor intermittently while managing the internal pressure so that it does not exceed a certain level. It is good also to do. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

  Heat drying is performed by exposing the substrate F to an environment of 50 ° C. or higher. The heating temperature is preferably 50 ° C. or higher and 200 ° C. or lower, and more preferably 70 ° C. or higher and 150 ° C. or lower. At a temperature exceeding 200 ° C., the substrate F may be deformed. Moreover, when an oligomer component elutes from the substrate F and precipitates on the surface, defects may occur. The drying time can be appropriately selected depending on the heating temperature and the heating means used.

  The heating means is not particularly limited as long as the substrate F can be heated to 50 ° C. or higher and 200 ° C. or lower under normal pressure. Among the generally known apparatuses, an infrared heating apparatus, a microwave heating apparatus, and a heating drum are preferably used.

  Here, the infrared heating device is a device that heats an object by emitting infrared rays from an infrared ray generating means.

  A microwave heating device is a device that heats an object by irradiating microwaves from microwave generation means.

  A heating drum is a device that heats a drum surface by heat conduction by heating the drum surface and bringing an object into contact with the drum surface.

  The natural drying is performed by placing the base material F in a low humidity atmosphere and maintaining the low humidity atmosphere by passing dry gas (dry air, dry nitrogen). When performing natural drying, it is preferable to arrange a desiccant such as silica gel together in a low-humidity environment where the substrate F is arranged. The drying time is preferably at least 8 hours or more, more preferably 1 week or more, and further preferably 1 month or more.

These dryings may be performed separately before the substrate F is mounted on the manufacturing apparatus, or may be performed in the manufacturing apparatus after the substrate F is mounted on the manufacturing apparatus.
As a method of drying after mounting the base material F on the manufacturing apparatus, the inside of the chamber can be decompressed while the base material F is sent out and conveyed from the feed roll. Moreover, the roll to pass shall be provided with a heater, and it is good also as heating this roll as the above-mentioned heating drum by heating a roll.

  Another method for reducing outgas from the substrate F is to form an inorganic film on the surface of the substrate F in advance. Examples of the film formation method for the inorganic film include physical film formation methods such as vacuum vapor deposition (heat vapor deposition), electron beam (EB) vapor deposition, sputtering, and ion plating. Alternatively, the inorganic film may be formed by a chemical deposition method such as thermal CVD, plasma CVD, or atmospheric pressure CVD. Furthermore, the influence of outgas may be further reduced by subjecting the substrate F having an inorganic film formed on the surface to a drying treatment by the above-described drying method.

  Next, a vacuum chamber (not shown) is set in a reduced pressure environment, and an AC voltage is applied to the film forming roll 17 and the film forming roll 18 to generate an electric field in the space SP.

  At this time, since the magnetic field forming devices 23 and 24 form the above-described endless tunnel-like magnetic field, by introducing the film forming gas, the tunnel is generated by the magnetic field and electrons emitted to the space SP. A discharge plasma of a doughnut-shaped film forming gas is formed. Since this discharge plasma can be generated at a low pressure in the vicinity of several Pa, the temperature in the vacuum chamber can be in the vicinity of room temperature.

  On the other hand, since the temperature of electrons captured at high density in the magnetic field formed by the magnetic field forming devices 23 and 24 is high, discharge plasma is generated due to collision between the electrons and the deposition gas. That is, electrons are confined in the space SP by a magnetic field and an electric field formed in the space SP, so that high-density discharge plasma is formed in the space SP. More specifically, in a space overlapping with an endless tunnel-like magnetic field, a high-density (high-intensity) discharge plasma (first discharge plasma) is formed and does not overlap with an endless tunnel-like magnetic field. In this case, a low density (low intensity) discharge plasma (second discharge plasma) is formed. The intensity of these discharge plasmas changes continuously.

When the discharge plasma is generated, a large amount of radicals and ions are generated and the plasma reaction proceeds, and a reaction between the source gas contained in the film forming gas and the reactive gas occurs. For example, an organosilicon compound that is a raw material gas and oxygen that is a reactive gas react with each other to cause an oxidation reaction of the organosilicon compound.
Here, in a space where high-intensity discharge plasma is formed, there is a lot of energy that can be given to the oxidation reaction, so that the reaction is likely to proceed, and a complete oxidation reaction of the organosilicon compound can be caused mainly. On the other hand, in the space where the low-intensity discharge plasma is formed, the energy that can be imparted to the oxidation reaction is small, so that the reaction does not proceed easily, and an incomplete oxidation reaction of the organosilicon compound can be caused mainly.

In this specification, the “complete oxidation reaction of the organosilicon compound” means that the reaction between the organosilicon compound and oxygen proceeds, and the organosilicon compound is oxidized and decomposed into silicon dioxide (SiO ₂ ), water, and carbon dioxide. Refers to that. The "incomplete oxidation reactions of organic silicon compounds", the organosilicon compound is not a complete oxidation reaction, _SiO x _C y (0 containing carbon in the SiO ₂ without structure <x <2,0 <y <2 ).

Since the discharge plasma is formed in a donut shape on the surfaces of the film forming roll 17 and the film forming roll 18 as described above, the substrate F transported on the surfaces of the film forming roll 17 and the film forming roll 18 has a high strength. The space in which the discharge plasma is formed and the space in which the low-intensity discharge plasma is formed are alternately passed. Therefore, SiO ₂ generated by the complete oxidation reaction and SiO _x C _y generated by the incomplete oxidation reaction are alternately formed on the surface of the base material F passing through the surfaces of the film forming roll 17 and the film forming roll 18. .

  In addition to these, high-temperature secondary electrons are prevented from flowing into the base material F due to the action of the magnetic field, so that high power can be input while the temperature of the base material F is kept low, and high-speed film formation is achieved. Is done. Film deposition mainly occurs only on the film-forming surface of the base material F, and the film-forming roll is covered with the base material F and is not easily soiled.

  The thin film layer H formed in this way is the sum of the distance from the surface of the layer in the thickness direction of the layer and the silicon atoms, oxygen atoms and carbon atoms. Silicon distribution curves showing the relationship between the ratio of the amount of silicon atoms to the amount of silicon (atom ratio of silicon), the ratio of the amount of oxygen atoms (atom ratio of oxygen) and the ratio of the amount of carbon atoms (atom ratio of carbon), In the oxygen distribution curve and the carbon distribution curve, all of the following conditions (i) to (iii) are satisfied.

(I) First, the thin film layer H has a region in which the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more (more preferably 95% or more, particularly preferably 100%) of the thickness of the layer. In the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Or the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more (more preferably 95% or more, particularly preferably 100%) of the thickness of the layer. In the region, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
The condition represented by is satisfied.

  When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon in the thin film layer H satisfy the condition (i), the gas barrier property of the obtained gas barrier laminate film is sufficient.

  (Ii) Next, such a thin film layer H has a carbon distribution curve having at least one extreme value.

  In such a thin film layer H, the carbon distribution curve more preferably has at least two extreme values, and particularly preferably has at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained film of the gas barrier laminate film is bent is insufficient. Further, in the case of having at least three extreme values as described above, the distance from the surface of the thin film layer H in the thickness direction of the thin film layer H at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference is preferably 200 nm or less, and more preferably 100 nm or less.

  In addition, in this embodiment, an extreme value means the maximum value or the minimum value of the atomic ratio of the element with respect to the distance from the surface of the thin film layer H in the thickness direction of the thin film layer H. In this specification, the maximum value is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the thin film layer H is changed, and the atomic ratio of the element at that point. The value of the atomic ratio of the element at the position where the distance from the surface of the thin film layer H in the thickness direction of the thin film layer H from the point is further changed by 20 nm than the value is reduced by 3 atomic% or more. Furthermore, in this embodiment, the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the thin film layer H is changed, and the atomic ratio of the element at that point is changed. The value of the atomic ratio of the element at a position where the distance from the surface in the thickness direction of the thin film layer H from the point to the surface of the thin film layer H is further changed by 20 nm is increased by 3 atomic% or more.

  (Iii) Further, in such a thin film layer H, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 atomic% or more.

  In such a thin film layer H, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 atomic% or more, and particularly preferably 7 atomic% or more. When the absolute value is less than 5 atomic%, the gas barrier property when the obtained gas barrier laminate film is bent is insufficient.

  In the present embodiment, the oxygen distribution curve of the thin film layer H preferably has at least one extreme value, more preferably has at least two extreme values, and particularly preferably has at least three extreme values. When the oxygen distribution curve does not have an extreme value, the gas barrier property tends to decrease when the resulting gas barrier laminate film is bent. In the case of having at least three extreme values as described above, the distance from the surface of the thin film layer H in the thickness direction of the thin film layer H at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present embodiment, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the thin film layer H is preferably 5 atomic% or more, and preferably 6 atomic% or more. More preferably, it is particularly preferably 7 atomic% or more. If the absolute value is less than the lower limit, the gas barrier property tends to decrease when the resulting gas barrier laminate film is bent.

  In the present embodiment, the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve of the thin film layer H is preferably less than 5 atomic%, more preferably less than 4 atomic%. Particularly preferred is less than 3 atomic%. If the absolute value exceeds the upper limit, the gas barrier properties of the resulting gas barrier laminate film tend to be reduced.

  In the present embodiment, the distance from the surface of the thin film layer H in the thickness direction and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (oxygen and carbon In the oxygen carbon distribution curve showing the relationship with the atomic ratio), the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen carbon distribution curve is preferably less than 5 atomic%. It is more preferably less than atomic percent, and particularly preferably less than 3 atomic percent. If the absolute value exceeds the upper limit, the gas barrier properties of the resulting gas barrier laminate film tend to be reduced.

Here, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: atomic%) of each element and the horizontal axis as the etching time (sputtering time). 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 H in the thickness direction of the thin film layer H in the thickness direction. As the “distance from the surface of the thin film layer H in the thickness direction of H”, a distance from the surface of the thin film layer H 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).

  Further, in the present embodiment, the thin film layer H is in the film surface direction (direction parallel to the surface of the thin film layer H) from the viewpoint of forming the thin film layer H having a uniform and excellent gas barrier property over the entire film surface. It is preferably substantially uniform. In this specification, that the thin film layer H is substantially uniform in the film surface direction means that an oxygen distribution curve, a carbon distribution curve, and oxygen at any two measurement points on the film surface of the thin film layer H by XPS depth profile measurement. When a carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum and minimum values of the atomic ratio of carbon in each carbon distribution curve The absolute value of the difference is the same as each other or within 5 atomic%.

Furthermore, in the present embodiment, 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 thin film layer H calculated in the thickness direction and the atomic ratio of carbon (C, unit: atomic%), the following mathematical formula (F1):
| DC / dx | ≦ 1 (F1)
This means that the condition represented by

  The gas barrier laminate film produced by the method of the present embodiment includes at least one thin film layer H that satisfies all of the above conditions (i) to (iii), but includes two or more layers that satisfy such conditions. It may be. Further, when two or more such thin film layers H are provided, the materials of the plurality of thin film layers H may be the same or different. Further, when two or more such thin film layers H are provided, such a thin film layer H may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Further, the plurality of thin film layers H may include a thin film layer H that does not necessarily have a gas barrier property.

  In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are expressed by the formula (1) in a region of 90% or more of the thickness of the layer. When the condition is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer H is preferably 25 atom% or more and 45 atom% or less, and 30 atoms % To 40 atomic% is more preferable. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer H is preferably 33 atom% or more and 67 atom% or less, and 45 atom% or more and 67 atom%. The following is more preferable. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the thin film layer H is preferably 3 atomic percent or more and 33 atomic percent or less, and preferably 3 atomic percent or more and 25 atomic percent. The following is more preferable.

  Further, in the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are expressed by the formula (2) in a region of 90% or more of the thickness of the layer. When the condition is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the thin film layer H is preferably 25 atom% or more and 45 atom% or less, and 30 atoms % To 40 atomic% is more preferable. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the thin film layer H is preferably 1 atom% or more and 33 atom% or less, and preferably 10 atom% or more and 27 atom%. The following is more preferable. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the thin film layer H is preferably 33 atom% or more and 66 atom% or less, and 40 atom% or more and 57 atom%. The following is more preferable.

  The thickness of the thin film layer H is preferably in the range of 5 nm to 3000 nm, more preferably in the range of 10 nm to 2000 nm, and particularly preferably in the range of 100 nm to 1000 nm. If the thickness of the thin film layer H is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the thickness exceeds the upper limit, the gas barrier properties tend to decrease due to bending.

  When the gas barrier laminate film of this embodiment includes a plurality of thin film layers H, the total thickness of the thin film layers H is usually in the range of 10 nm to 10,000 nm, and in the range of 10 nm to 5000 nm. It is preferable that it is in the range of 100 nm or more and 3000 nm or less, and it is particularly preferable that it is in the range of 200 nm or more and 2000 nm or less. If the total thickness of the thin film layer H is less than the lower limit, gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the upper limit is exceeded, gas barrier properties tend to decrease due to bending.

  In order to form such a thin film layer H, the ratio of the raw material gas and the reactive gas contained in the film forming gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio of. When the ratio of the reaction gas is excessively increased, it is difficult to obtain the thin film layer H that satisfies all the above conditions (i) to (iii).

Hereinafter, as a film-forming gas, a gas containing hexamethyldisiloxane (HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a source gas and oxygen (O ₂ ) as a reaction gas is used. Taking a case where a thin film layer is manufactured as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

When forming a silicon-oxygen-based thin film layer by reacting a film-forming gas containing HMDSO as a source gas and oxygen as a reaction gas by plasma CVD, the following reaction formula (1) is established by the film-forming gas. The described reaction takes place and silicon dioxide is produced.
[Chemical 1]
_{(CH 3) 6 Si 2 O} + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2 ... (1)

  In this reaction, the amount of oxygen required to completely oxidize 1 mol of HMDSO is 12 mol. Therefore, when the film forming gas contains 12 mol or more of oxygen with respect to 1 mol of HMDSO and is completely reacted, a uniform silicon dioxide film is formed. Therefore, the above conditions (i) to (iii) ) Cannot be formed. Therefore, when forming the thin film layer H of the present embodiment, the amount of oxygen is less than the stoichiometric ratio of 12 moles with respect to 1 mole of HMDSO so that the reaction of the above formula (1) does not proceed completely. There is a need to reduce it.

  In the reaction in the vacuum chamber of the manufacturing apparatus 10, since the raw material HMDSO and the oxygen of the reaction gas are supplied from the gas supply unit to the film formation region to form a film, the molar amount (flow rate) of oxygen in the reaction gas Even though the molar amount (flow rate) is 12 times the molar amount (flow rate) of HMDSO as a raw material, the reaction cannot actually proceed completely, and the oxygen content is compared with the stoichiometric ratio. Thus, it is considered that the reaction is completed only when a large excess is supplied (for example, in order to obtain a silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is 20 times the molar amount (flow rate) of the raw material HMDSO). Sometimes more than double). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of HMDSO as a raw material is preferably an amount of 12 times or less (more preferably 10 times or less) which is a stoichiometric ratio.

  By including HMDSO and oxygen in such a ratio, the carbon atoms and hydrogen atoms in HMDSO that have not been completely oxidized are taken into thin film layer H, and the thin film satisfies all of the above conditions (i) to (iii) The layer H can be formed, and the obtained gas barrier laminate film can exhibit excellent barrier properties and bending resistance.

  In this case, if the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of HMDSO in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the thin film layer H. Decreases the transparency of the barrier film. Such a gas barrier film cannot be used for a flexible substrate for devices that require transparency, such as organic EL devices and organic thin-film solar cells. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of HMDSO in the film forming gas is preferably set to an amount larger than 0.1 times the molar amount (flow rate) of HMDSO. More preferably, the amount is more than 0.5 times.

  Thus, whether or not the organosilicon compound is completely oxidized depends on the applied voltage applied to the film forming roll 17 and the film forming roll 18 in addition to the mixing ratio of the source gas and the reaction gas in the film forming gas. Can be controlled.

  A thin film layer can be formed on the surface of the base material F wound around the film forming roll 17 and the film forming roll 18 by the plasma CVD method using such discharge plasma.

(Configuration example of thin film layer)
Further, in the laminated film formed as described above, in at least one of the thin film layers, an electron beam indicating the relationship between the distance from the surface of the layer in the thickness direction of the layer and the electron beam transmittance The transmission curve may have at least one extreme value. When the electron beam transmission curve has at least one extreme value, it is possible to achieve a sufficiently high gas barrier property by the thin film layer, and the gas barrier property is sufficiently lowered even when the film is bent. It becomes possible to suppress.

  As such a thin film layer, since a higher effect is obtained, it is more preferable that the electron beam transmission curve has at least two extreme values, and it is particularly preferable that the electron beam transmission curve has at least three extreme values. In the case of having at least three extreme values as described above, the surface of the thin film layer in the thickness direction of the thin film layer at one extreme value and the extreme value adjacent to the extreme value of the electron beam transmission curve. The absolute value of the difference in distance from each other is preferably 200 nm or less, and more preferably 100 nm or less. In this embodiment, the extreme value is the maximum value or the minimum value of a curve (electron beam transmittance curve) in which the magnitude of electron beam transmittance is plotted against the distance from the surface of the thin film layer in the thickness direction of the thin film layer. The value. In the present embodiment, the presence or absence of an extreme value (maximum value or minimum value) of the electron beam transmittance curve can be determined based on a method for determining the presence or absence of an extreme value described later.

Further, in the present embodiment, the electron beam transmittance represents the degree of transmission of the electron beam through the material forming the thin film layer at a predetermined position in the thin film layer. Various known methods can be adopted as the method for measuring the electron beam transmittance. For example, (i) a method for measuring electron beam transmittance using a transmission electron microscope, and (ii) a scanning electron microscope. It is possible to employ a method of measuring electron beam transmittance by measuring secondary electrons and backscattered electrons.
Hereinafter, the case of using a transmission electron microscope will be described as an example, and the method for measuring the electron beam transmittance and the method for measuring the electron beam transmittance curve will be described.

  In the method of measuring the electron beam transmittance when such a transmission electron microscope is used, first, a flaky sample is prepared by cutting a base material having a thin film layer in a direction perpendicular to the surface of the thin film layer. Next, a transmission electron microscope image of the surface of the sample (a surface perpendicular to the surface of the thin film layer) is obtained using a transmission electron microscope. Then, by measuring the image of the transmission electron microscope in this way, the electron beam transmittance at each position of the thin film can be obtained based on the contrast at each position on the image.

  Here, in the case of observing with a transmission electron microscope a flaky sample obtained by cutting a substrate having a thin film layer in a direction perpendicular to the surface of the thin film layer, the contrast at each position of the image of the transmission electron microscope Represents a change in electron beam transmittance of the material at each position. In order to make such contrast correspond to the electron beam transmittance, it is preferable to ensure an appropriate contrast in the image of the transmission electron microscope, and the thickness of the sample (the thickness in the direction parallel to the surface of the thin film layer) It is preferable to appropriately select observation conditions such as the acceleration voltage and the diameter of the objective aperture.

  The thickness of the sample is preferably 10 nm or more and 300 nm or less, more preferably 20 nm or more and 200 nm or less, further preferably 50 nm or more and 200 nm or less, and particularly preferably 100 nm.

  The acceleration voltage is preferably 50 kV or more and 500 kV or less, more preferably 100 kV or more and 300 kV or less, further preferably 150 kV or more and 250 kV or less, and particularly preferably 200 kV.

  The diameter of the objective aperture is preferably 5 μm or more and 800 μm or less, more preferably 10 μm or more and 200 μm or less, and particularly preferably 160 μm.

  Moreover, as such a transmission electron microscope, it is preferable to use what has sufficient resolution about the image of a transmission electron microscope. Such resolution is preferably at least 10 nm or less, more preferably 5 nm or less, and particularly preferably 3 nm or less.

  In addition, in such an electron beam transmittance measurement method, an image (transparency image) of a transmission electron microscope is used to obtain the electron beam transmittance at each position of the thin film based on the contrast at each position on the image. The unit area is divided into repetitions, and a cross-sectional density variable (C) corresponding to the degree of density of the unit area is assigned to each unit area. Such image processing can be easily performed by electronic image processing using a normal computer.

  In such image processing, it is preferable to first cut out an arbitrary region suitable for analysis from the obtained grayscale image.

  The gray image cut out in this way must include at least a portion from one surface of the thin film layer to the other surface facing the thin film layer. Moreover, the layer adjacent to a thin film layer may be included. Thus, as a layer adjacent to a thin film layer, a protective layer required in order to implement the observation which obtains a base material and a light and shade image, for example is mentioned.

  Further, the end face (reference plane) of the grayscale image cut out in this way must be a plane parallel to the surface of the thin film layer. Further, the grayscale image cut out in this way is at least a trapezoid or parallelogram surrounded by two sides facing each other perpendicular to the direction (thickness direction) perpendicular to the surface of the thin film layer. It is more preferable that the shape is a quadrangle having two sides and two sides perpendicular to them (parallel to the thickness direction).

  The gray-scale image cut out in this way is divided into repetitions of a certain unit area. As the division method, for example, a method of dividing by a grid-like section can be adopted. In such a case, each unit area divided by the grid-like sections constitutes one pixel. Such a gray-scale image pixel is preferably as fine as possible in order to reduce the error, but as the pixel becomes finer, the time required for analysis tends to increase. Therefore, the length of one side of such a gray image pixel is preferably 10 nm or less, more preferably 5 nm or less, and particularly preferably 3 nm or less, in terms of the actual size of the sample.

  The cross-sectional density variable (C) given in this way is a value obtained by converting the degree of density in each area into numerical information. The method of conversion into such a cross-sectional density variable (C) is not particularly limited. For example, the darkest unit area is set to 0, the thinnest unit area is set to 255, and 0 to 0 depending on the level of density of each unit area. It is possible to set (256 gradation settings) by giving an integer between 255. However, it is preferable that such a numerical value is determined so that the numerical value of the portion with high electron beam transmittance is large.

  Then, from such a cross-sectional density variable (C), a thickness direction density variable (CZ) at a distance (z) from the reference plane in the thickness direction of the thin film layer can be calculated by the following method. That is, the average value of the cross-sectional density variable (C) of the unit region where the distance (z) from the reference plane in the thickness direction of the thin film layer has a predetermined value is calculated to obtain the thickness direction density variable (CZ).

  Note that the average value of the cross-sectional density variable (C) here is the cross-sectional density variable (C) of any unit region of 100 points or more where the distance (z) from the reference plane is a predetermined value (the same value). An average value is preferred. Further, when the thickness direction gradation variable (CZ) is obtained in this way, it is preferable to appropriately perform noise removal processing for noise removal.

  As the noise removal process, a moving average method, an interpolation method, or the like can be employed. Examples of the moving average method include a simple moving average method, a weighted moving average method, and an exponential smoothing moving average method, but it is more preferable to employ the simple moving average method. In addition, when using the simple moving average method, the range to be averaged is appropriately selected so that it is sufficiently smaller than the typical size of the structure in the thickness direction of the thin film layer and the obtained data is sufficiently smooth. It is preferable to do. Examples of the interpolation method include a spline interpolation method, a Lagrangian interpolation method, and a linear interpolation method, but it is more preferable to employ a spline interpolation method and a Lagrange interpolation method.

  As a result of the noise removal operation, an area where the change in the thickness direction density variable (CZ) with respect to the position in the thickness direction is moderate occurs near both interfaces of the thin film layer (this is called a transition area). It is desirable to remove this transition region from the extreme value determination region of the electron beam transmittance curve of the thin film layer from the viewpoint of clarifying the criterion for determining the presence or absence of the extreme value of the electron beam transmittance curve described later. In addition, as a factor which such a transition region generate | occur | produces, the non-planarity of a thin film interface, the above-mentioned noise removal work, etc. are considered. Therefore, the transition region can be removed from the determination region of the electron beam transmittance curve by adopting the following method.

  That is, first, the position of the distance (z) from the reference plane in the thickness direction of the thin film layer where the absolute value | dCZ / dz | Set as interface position.

Next, the absolute value of the inclination (dCZ / dz) is sequentially checked from the outside of the temporary interface position toward the inside (thin film layer side), and the absolute value is 0.1 nm ⁻¹ (256 gradation setting). A distance (z) from the reference plane in the thickness direction of the thin film layer at the position of (case) (considering a graph in which the vertical axis is the absolute value of dCZ / dz and the horizontal axis is the distance (z) from the machine gun surface) In the case where the absolute value of dCZ / dz falls below 0.1 nm ⁻¹ for the first time, the graph is traced from the distance (z) outside the temporary interface position toward the inside (thin film layer side). The position of (z)) is set as the thin film interface.

  Then, the transition region can be removed from the determination region by removing the region outside the interface from the determination region of the electron beam transmittance curve of the thin film layer. In addition, when obtaining the thickness direction density variable (CZ) in this way, it is preferable to normalize so that the average value of the thickness direction density variable (CZ) in the range corresponding to the thin film layer is 1.

  The thickness direction density variable (CZ) calculated in this way is proportional to the electron beam transmittance (T). Therefore, an electron beam transmittance curve can be created by indicating a thickness direction gradation variable (CZ) with respect to a distance (z) from the reference plane in the thickness direction of the thin film layer. That is, the electron beam transmittance curve can be obtained by plotting the thickness direction light and dark variable (CZ) with respect to the distance (z) from the reference plane in the thickness direction of the thin film layer. Further, by calculating a gradient (dCZ / dz) obtained by differentiating the thickness direction density variable (CZ) by the distance (z) from the reference plane in the thickness direction of the thin film layer, the gradient (dT) of the electron beam transmittance (T) is calculated. / Dz) can also be known.

  In addition, in the electron beam transmittance curve thus obtained, the presence or absence of an extreme value can be determined as follows. That is, when the electron beam transmission curve has an extreme value (maximum value or minimum value), the maximum value of the gradient (dCZ / dz) of the density coefficient in the thickness direction is a positive value and the minimum value is a negative value. When there is no extreme value, the maximum value and minimum value of the slope (dCZ / dz) are both positive or negative values, and the difference between the two values becomes larger. The absolute value of becomes smaller. Therefore, when determining whether or not there is an extreme value, by determining whether the maximum value and minimum value of the slope (dCZ / dz) are both positive values or both negative values. Based on the magnitude of the absolute value of the difference between the maximum value (dCZ / dz) MAX and the minimum value (dCZ / dz) MIN of the slope (dCZ / dz) It can also be determined whether the electron beam transmission curve has an extreme value.

  It should be noted that the thickness direction gradation variable (CZ) should always indicate 1 which is a standardized average value when there is no extreme value, but the signal actually contains slight noise and is normalized. A value close to the average value 1 causes fluctuations in the electron beam transmittance curve due to noise. Therefore, when determining whether or not there is an extreme value in the electron beam transmission curve, whether the maximum value and the minimum value of the slope of the electron beam transmission curve are not positive or negative values and the electron beam When the extreme value is determined based only on the absolute value of the difference between the maximum value and the minimum value of the slope of the transmission curve, it is determined that the electron beam transmission curve has an extreme value due to noise There is.

  Therefore, when determining the presence or absence of the extreme value, the fluctuation due to noise and the extreme value are distinguished according to the following criteria. That is, when a point at which the slope (dCZ / dz) of the thickness direction gray variable (CZ) is reversed with the sign reversed is set to a temporary extreme point, the thickness direction gray variable (CZ) at the temporary extreme point is The absolute value of the difference from the thickness direction gradation variable (CZ) at the adjacent temporary extreme value point (if there are two adjacent temporary extreme value points, the one with the larger absolute value of the difference is selected) is 0.03. In the above case, it can be determined that the temporary extreme point is a point having an extreme value. In other words, the absolute value of the difference between the thickness direction grayscale variable (CZ) at the temporary extreme point and the thickness direction grayscale variable (CZ) at the adjacent temporary extreme point (when there are two adjacent temporary extreme points) Select the larger absolute value of the difference) is less than 0.03, it can be determined that the temporary extreme point is noise.

  When there is only one temporary extreme point, the thickness direction gray variable (CZ) is not noise when the absolute value of the difference from the normalized average value 1 is greater than 0.03. A method for determining that the value is an extreme value can be employed. In addition, such a numerical value of “0.03” is a standard value of the numerical value of the thickness direction shading variable (CZ), where the average value of the thickness direction shading variable (CZ) obtained by the 256 gradation setting described above is 1. (The numerical value “0” of the thickness direction gradation variable obtained by the 256 gradation setting at the time of normalization is assumed to be “0” as it is).

  In the laminated film that is the subject of the present embodiment, at least one thin film layer may have at least one extreme value in the electron beam transmittance curve. It can be said that such a thin film layer having at least one extreme value in the electron beam transmission curve is a layer whose composition varies in the thickness direction. A laminated film including such a thin film layer can achieve a sufficiently high gas barrier property, and even when the film is bent, a decrease in gas barrier property can be sufficiently suppressed.

Moreover, it is preferable that the electron beam transmittance curve is substantially continuous. In this specification, that the electron beam transmission curve is substantially continuous means that the electron beam transmission curve in the electron beam transmission curve does not include a portion in which the electron beam transmission changes discontinuously. It means that the absolute value of the gradient (dCZ / dz) of the direction density variable (CZ) is not more than a predetermined value, preferably not more than 5.0 × 10 ⁻² / nm.

  Further, in the present embodiment, 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. Are preferably uniform. In this specification, the fact that the thin film layer is substantially uniform in the film surface direction is obtained even when the electron beam transmittance curve is created by measuring the electron beam transmittance at any location on the film surface of the thin film layer. It means that the number of extreme values of the electron beam transmission curve is the same. In addition, when the sample for measurement at two arbitrary points was cut out from the film surface of the thin film layer and the electron beam transmission curve of each sample was created, the extreme values of the electron beam transmission curve in all the samples If the numbers are the same, the thin film layer can be assumed to be substantially uniform.

  The manufacturing method of the laminated film of this embodiment includes the above-described inspection method as one step. That is, for the gas barrier laminate film thus obtained, the gas barrier property of the thin film layer can be inspected in a short time by inspecting the gas barrier property of the thin film layer using the above-described inspection method, and the gas barrier property with high productivity. Production of a laminated film can be realized.

In the inspection process, for example, for a laminated film in which a thin film layer H is formed on a long substrate F, a test piece is created as a representative sample at regular intervals in the longitudinal direction, and ²⁹ Si solid state NMR of the test piece is measured. Thus, the gas barrier property of the thin film layer may be inspected.

  Furthermore, the manufacturing method of the laminated film of the present embodiment is based on the inspection result in the inspection process, that is, based on the correspondence relationship between the gas barrier property of the thin film layer and the abundance ratio of the silicon atoms in each bonded state described above. Includes a process of selecting good products. Thereby, the gas barrier property of the obtained laminated | multilayer film can be evaluated simply in a short time, and a good laminated film can be selected efficiently.

  According to the method for inspecting a laminated film having the above configuration, it can have high gas barrier properties.

As one of the indicators for evaluating the gas barrier property of the laminated film of the present invention, as described above, there is water vapor permeability. The water vapor permeability of the laminated film of the present invention is determined by, for example, the measurement method described in the examples. Can be measured. The water vapor permeability of the laminated film of the present invention is preferably 10 ⁻⁵ g / (m ²⁾ , for example, under conditions of a temperature of 40 ° C., a low humidity side humidity of 0% RH, and a high humidity side humidity of 90% RH. · Day) or less, more preferably 10 ^-6 g / (m ² · day) or less.

  Moreover, in the manufacturing method of the above laminated films, it becomes possible to manufacture a high quality laminated film stably by having the test | inspection process which employ | adopts the above-mentioned inspection method.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example. The water vapor permeability of the laminated film and the ²⁹ Si solid state NMR spectrum of the barrier film of the laminated film were measured by the following methods.

(I) Measurement of water vapor permeability of laminated film Water vapor permeability measuring machine (GTR Tech Co., model name “GTR” under the conditions of temperature 40 ° C., humidity 0% RH on the low humidity side and humidity 90% RH on the high humidity side. -3000 "), JIS K 7129: 2008" Plastics-Films and Sheets-Determination of water vapor transmission rate (instrument measurement method) "Appendix C" How to determine water vapor transmission rate by gas chromatography "(JIS According to the gas chromatography method, the water vapor permeability of the laminated film was measured.

(Ii) Measurement of ²⁹ Si solid state NMR spectrum
²⁹ Si solid state NMR (BRUKER manufactured AVANCE300) was measured ²⁹ Si solid state NMR spectrum using. Detailed measurement conditions are as follows (accumulation number: 49152 times, relaxation time: 5 seconds, resonance frequency: 59.58815676 MHz, MAS rotation: 3 kHz, CP method).

The peak area of ²⁹ Si solid state NMR was calculated as follows. The thin film layer to be measured in this embodiment, any of the silicon atoms of Q ³ or Q ⁴ is included, it does not include silicon atoms for Q ¹ or Q ² is known in advance.

First, the spectrum obtained by ²⁹ Si solid state NMR measurement was smoothed.

  In the following description, the spectrum after smoothing is referred to as “measured spectrum”.

The measured spectrum was then separated into Q ³ and Q ⁴ peaks. That is, it is assumed that the peak of Q ^{3 and} the peak of Q ⁴ each show a Gaussian distribution (normal distribution) curve centered on a specific chemical shift (Q ³ : −102 ppm, Q ⁴ : −112 ppm). Parameters such as the height and half-value width of each peak were optimized so that the model spectrum obtained by adding ³ and Q ⁴ coincided with the measured spectrum after smoothing.

  An iterative method was used for parameter optimization, and the calculation was performed so that the sum of the squares of the deviation between the model spectrum and the measured spectrum converged to a minimum value.

Next, the areas of the portions surrounded by the Q ³ and Q ⁴ peaks thus obtained and the baseline were integrated to obtain the peak areas of Q ³ and Q ⁴ . Furthermore, using the calculated peak area, (Q ³ peak area) / (Q ⁴ peak area) was determined, and the value of (Q ³ peak area) / (Q ⁴ peak area) The relationship was confirmed.

Example 1
A laminated film was produced using the production apparatus shown in FIG.
That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 700 mm, manufactured by Teijin DuPont Films Ltd., trade name “Teonex Q65FA”) is used as a base material (base material F), and this is sent out. Mounted on the roll 11. Then, an endless tunnel-like magnetic field is formed in the space between the film forming roll 17 and the film forming roll 18, and power is supplied to the film forming roll 17 and the film forming roll 18, respectively. Plasma is generated by discharging between the film forming roll 18 and a film forming gas (hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas as a reactive gas (also functions as a discharge gas) is generated in such a discharge region. The thin film was formed by the plasma CVD method under the following conditions. By performing this process three times, the laminated film of Example 1 was obtained.

<Film formation conditions>
Deposition gas mixing ratio (hexamethyldisiloxane / oxygen): 100/1000 [unit: sccm (Standard Cubic Centimeter per Minute)]
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 1.6 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

In order to reduce the outgas from the base film sufficiently, after mounting the base film on the delivery roll of the manufacturing device on the day before the film formation date, leave it in a vacuum state overnight, Dried. The degree of vacuum before film formation was 5 × 10 ⁻⁴ Pa or less. The thickness of the barrier film of the laminated film obtained by film formation is 1.02 μm, and the water vapor transmission rate is 2 × under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. 10 ⁻⁵ g / (m ² · day).

Moreover, in order to calculate the ratio of Q ³ / Q ⁴ in the barrier film, the spectrum was measured using ²⁹ Si solid-state NMR. The sample was obtained by finely cutting a substrate with a barrier film with a scissors. The obtained spectrum is shown in FIG. Further, a peak area normalized by the peak area of Q ⁴ in Table 1.

As shown in Table 1, in the obtained spectrum, and calculating the area ratio of ^{Q 3} and ^{Q 4,} was determined the ratio of Q 3 / ^{Q 4,} it was Q ³ / Q 4 = 0.51.

(Example 2)
On the day of the film formation date, the base film was mounted on the delivery roll of the manufacturing apparatus, and then the film was formed after 1 hour in a vacuum state. The degree of vacuum before film formation was about 3 × 10 ⁻³ Pa, and the outgas was continuously emitted from the substrate. A laminated film of Example 2 was produced in the same manner as in Example 1 except that the degree of vacuum in the production apparatus before film formation was different.

The thickness of the barrier film of the obtained laminated film is 1.09 μm, and the water vapor permeability is 2 × 10 ⁻³ under conditions of a temperature of 40 ° C., a low humidity side humidity of 0% RH, and a high humidity side humidity of 90% RH. g / (m ² · day).

In order to investigate the ratio of Q ³ / Q ⁴ in the barrier film, the spectrum was measured using ²⁹ Si solid-state NMR. The sample was obtained by finely cutting a substrate with a barrier film with a scissors. The obtained spectrum is shown in FIG. Further, a peak area normalized by the peak area of Q ⁴ in Table 2.

As shown in Table 2, when the area ratio of Q ³ and Q ⁴ was calculated in the obtained spectrum and the ratio of Q ³ / Q ⁴ was determined, Q ³ / Q ⁴ = 1.10.

(Example 3)
A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) is used as a base material (base material F), and plasma is used under the following conditions. A laminated film of Example 3 was obtained in the same manner as Example 1 except that a thin film was formed by the CVD method.

<Film formation conditions>
Deposition gas mixing ratio (hexamethyldisiloxane / oxygen): 50/500 [unit: sccm (Standard Cubic Centimeter per Minute)]
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.5 m / min

After the base film was mounted on the delivery roll of the manufacturing apparatus, a laminated film was manufactured without taking sufficient time to vacuum and dry in the same manner as in Example 2. The thickness of the barrier film of the obtained laminated film is 1.23 μm, and the water vapor transmission rate is 1.4 × 10 4 at a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. ^-3 g / (m ² · day).

In order to investigate the ratio of Q ³ / Q ⁴ in the barrier film, the spectrum was measured using ²⁹ Si solid-state NMR. The sample was obtained by finely cutting a substrate with a barrier film with a scissors. The obtained spectrum is shown in FIG. Further, a peak area normalized by the peak area of Q ⁴ in Table 3.

As shown in Table 3, when the area ratio of Q ³ and Q ⁴ was calculated and the ratio of Q ³ / Q ⁴ was determined in the obtained spectrum, Q ³ / Q ⁴ = 5.0.

As a result of the above measurement, the sample of Example 1 in which Q ³ / Q ⁴ is less than 1 can be evaluated as having a high gas barrier property due to low water vapor permeability, and Q ³ / Q ⁴ is 1 or more. Since the samples (Examples 2 and 3) have high water vapor permeability, it can be evaluated that they exhibit low gas barrier properties. Thus, according to the inspection method of the present invention, the gas barrier property can be determined easily and in a short time.
From these results, the usefulness of the present invention was confirmed.

  The method for inspecting a laminated film of the present invention can be suitably used for, for example, a method for producing a high-quality laminated film because the gas barrier property can be easily evaluated in a short time.

DESCRIPTION OF SYMBOLS 10 ... Manufacturing apparatus, 13-16 ... Conveyance roll, 17 ... 1st film-forming roll, 18 ... 2nd film-forming roll, F ... Film (base material), SP ... Space (film-forming space)

Claims (13)

A method for inspecting a laminated film comprising: a base material; and a thin film layer formed on at least one surface of the base material and containing at least silicon, oxygen, and hydrogen,
²⁹ Si solid state NMR measurement of the thin film layer was performed to determine the abundance ratio of silicon atoms in the thin film layer for each number of neutral oxygen atoms bonded to silicon atoms,
A method for inspecting a laminated film, wherein the gas barrier property of the thin film layer is determined based on the correspondence relationship between the gas barrier property of the thin film layer and the abundance ratio of the silicon atoms obtained in advance. The abundance ratio of the silicon atoms is a ratio of the sum of the peak areas of Q ¹ , Q ² , and Q ^{3 to} the peak area of Q ⁴ in the ²⁹ Si solid state NMR spectrum of the thin film layer,
The method for inspecting a laminated film according to claim 1, wherein the gas barrier property of the thin film layer in which the abundance ratio of the silicon atoms is less than the threshold is determined as a non-defective product based on a threshold value determined in advance for the abundance ratio of the silicon atoms.   The method for inspecting a laminated film according to claim 2, wherein the threshold value is 1.0.   The said base material is at least 1 sort (s) of resin selected from the group which consists of a polyester resin and polyolefin resin, The inspection method of the laminated | multilayer film as described in any one of Claims 1-3.   The thickness of the said base material is 5 micrometers-500 micrometers, The inspection method of the laminated | multilayer film as described in any one of Claims 1-4. Forming a thin film layer containing at least silicon, oxygen and hydrogen on at least one surface of the substrate;
For a test piece including the thin film layer, an inspection process for determining a gas barrier property of the thin film layer using the inspection method according to any one of claims 1 to 5,
A step of selecting non-defective products based on the correspondence between the gas barrier properties of the thin film layer and the abundance ratio of the silicon atoms;
The manufacturing method of the non-defective laminated film which has NO.   The method for producing a laminated film according to claim 6, wherein in the step of forming the thin film layer, the thin film layer is continuously formed while continuously conveying a long base material.   The step of forming the thin film layer includes a first film forming roll on which the first base material is wound, and a second film forming surface on which the second base material is wound, facing the first film forming roll. By applying an alternating voltage between the first film forming roll and the second film forming roll, a discharge plasma of a film forming gas, which is a material for forming the thin film layer, is generated in a space between the first film forming roll and the second film forming roll. The method for producing a laminated film according to claim 7, wherein the plasma CVD used is used. The discharge plasma forms an AC electric field between the first film-forming roll and the second film-forming roll, and swells in a space where the first film-forming roll and the second film-forming roll face each other. A first discharge plasma formed along the tunnel-like magnetic field and a second discharge plasma formed around the tunnel-like magnetic field by forming an endless tunnel-like magnetic field Have
The method for producing a laminated film according to claim 8, wherein in the step of forming the thin film layer, the base material is conveyed so as to overlap the first discharge plasma and the second discharge plasma. The distance from the surface of the thin film layer in the thickness direction, the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon), the ratio of the amount of oxygen atoms (the ratio of oxygen In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the atomic ratio) and the ratio of the amount of carbon atoms (carbon atomic ratio), the following conditions (i) to (iii):
(I) In the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Or in the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the thickness of the layer, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 atomic% or more,
The manufacturing method of the laminated | multilayer film of Claim 9 which controls the mixing ratio of the organosilicon compound and oxygen contained in the said film-forming gas so that all may be satisfy | filled.   The absolute value of the difference between the distance from the surface of the thin film layer in the thickness direction of the thin film layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value is 200 nm or less. The manufacturing method of laminated film of description.   The method for producing a laminated film according to claim 10 or 11, wherein the carbon distribution curve is substantially continuous.   The manufacturing method of the laminated | multilayer film as described in any one of Claims 6-12 whose thickness of the said thin film layer is 5 nm or more and 3000 nm or less.

Images