WO2012081555A1 - Gas barrier laminate and method for producing gas barrier laminate - Google Patents

Abstract

A gas barrier laminate of the present invention is obtained by laminating, on at least one surface of a substrate: a stress-alleviating layer that is formed by atmospheric pressure plasma CVD and contains a metal oxide and/or metal nitride; and a barrier layer that is formed by the wet process and comprises a silicon oxynitride. As a result, no cracks are produced and good bending resistance is obtained.

Description

Gas barrier laminate and method for producing gas barrier laminate

The present invention relates to a gas barrier laminate and a method for producing the gas barrier laminate.

A gas barrier film technique is disclosed in which a barrier layer formed by a vacuum dry film formation process such as vacuum deposition or sputtering and a resin (stress relaxation) layer formed by a wet coating process are laminated (for example, Patent Document 1). ) In order to obtain a dense barrier layer by vacuum dry film formation, it is necessary to lower the film formation rate (speed) and the productivity is low, and the combination of the vacuum dry film formation process and the wet coating process is continuous. There was a problem of inferior productivity.

From such a problem, a technique for forming a barrier layer by applying a polysilazane solution, drying, and then modifying with a vacuum ultraviolet light to form a barrier layer is disclosed (Patent Document 2). Repeated lamination to obtain cracks due to stress generated by film shrinkage at the time of polysilazane modification, stress relaxation is insufficient, there is a problem in flex resistance, and gas barrier performance is also insufficient It was.

As a technique for improving the gas barrier performance, a technique in which the above-described polysilazane layer and a layer formed by a plasma CVD method are used in combination as a barrier layer is disclosed (see Patent Document 3). The point of this technology is to use a barrier layer formed by a vacuum plasma CVD method and a barrier layer formed by applying a liquid containing polysilazane and then heat-treating it to complement each other, but the gas barrier performance is mutually complemented. In order to obtain a gas barrier property from a liquid containing polysilazane, it is necessary to perform heat treatment for a long time at a relatively high temperature. For example, a substrate having high heat resistance such as PES is required and has high versatility. It is difficult to apply to PET, etc., and the gas barrier performance is not improved so much, and above all, the barrier layer formed by the vacuum plasma method has a problem in the stress relaxation ability. Cracks are generated by the stress generated in the case, stress relaxation at the time of bending is not sufficient, and the problem of bending resistance has not been improved

JP-A-8-164595 JP 2009-255040 A Japanese Patent Laid-Open No. 8-281186

Therefore, an object of the present invention is to provide a gas barrier laminate and a method for producing the gas barrier laminate that do not generate cracks and have good bending resistance.

The above object of the present invention is achieved by the following means.

1. A stress relaxation layer containing at least one of a metal oxide and a metal oxynitride formed by atmospheric pressure plasma CVD and a barrier layer made of silicon oxynitride formed by a wet process were laminated on at least one surface of the substrate. A gas barrier laminate characterized by that.

2. 2. The gas barrier laminate according to 1 above, wherein the metal oxide and the metal oxynitride contain carbon.

3. 3. The gas barrier laminate according to 1 or 2, wherein the carbon contained in the metal oxide and the metal oxynitride is 0.1% or more and less than 30% in terms of element ratio.

4. The gas barrier laminate according to any one of 1 to 3, wherein the barrier layer is subjected to a modification treatment.

5. When the stress relaxation layer according to any one of 1 to 3 and the barrier layer formed by a wet process are used as a gas barrier layer unit, at least two of the gas barrier layer units are repeatedly stacked on at least one surface of the substrate. The gas barrier laminate according to any one of the above 1 to 4, wherein the gas barrier laminate is characterized in that:

6. A stress relaxation layer including at least one of a metal oxide and a metal oxynitride is formed on at least one surface of the substrate by an atmospheric pressure plasma CVD method, and a barrier layer made of silicon oxynitride is formed on the stress relaxation layer by a wet process. A method for producing a gas barrier laminate, characterized by comprising:

7. 7. The method for producing a gas barrier laminate according to 6, wherein the metal oxide and the metal oxynitride contain carbon.

8. 8. The method for producing a gas barrier laminate according to 6 or 7, wherein carbon contained in the metal oxide and metal oxynitride is 0.1% or more and less than 30% in terms of element ratio.

9. The method for producing a gas barrier laminate according to any one of 6 to 8, wherein the barrier layer is subjected to a modification treatment.

10. Any one of the above 6 to 9, wherein when the stress relaxation layer and the barrier layer are gas barrier layer units, at least two of the gas barrier layer units are repeatedly laminated on at least one surface of the substrate. The manufacturing method of the gas barrier laminated body of description.

Therefore, according to the present invention, it is possible to obtain a gas barrier laminate that does not generate cracks and has good bending resistance.

It is a section lineblock diagram showing an example of a gas barrier layered product concerning the present invention.

The present invention provides a gas barrier having a layer comprising at least one of a metal oxide and a metal oxynitride formed by atmospheric pressure plasma CVD on at least one surface of a substrate, and a layer made of silicon oxynitride formed by a wet process It relates to a laminate.

In the present invention, a layer containing at least one of metal oxide and metal oxynitride formed by atmospheric pressure plasma CVD is used as a stress relaxation layer, and a layer made of silicon oxynitride formed by a wet process is used as a barrier. A gas barrier that has improved flex resistance by suppressing the occurrence of film shrinkage during the barrier layer formation and cracks and peeling due to stress generated by bending by forming a laminate as a layer on a substrate such as a resin film It constitutes a laminate.

FIG. 1 is a cross-sectional configuration diagram showing an example of a gas barrier laminate according to the present invention.

In the gas barrier laminate of the present invention, a layer containing at least one of a metal oxide and a metal oxynitride formed as a stress relaxation layer 2 on the substrate 1 by an atmospheric pressure plasma CVD method is further provided on the stress relaxation layer 2. As the layer 3, for example, a layer made of silicon oxynitride formed by a wet process by modification of polysilazane is laminated and formed.

It is also a preferred aspect of the present invention that the unit in which the stress relaxation layer and the barrier layer are laminated is used as one gas barrier layer unit, and the gas barrier layer unit is repeatedly laminated at least two times.

In the present invention, a layer including at least one of a metal oxide and a metal oxynitride serving as a lower layer is formed as a stress relaxation layer by an atmospheric pressure plasma CVD method which is a dry process. The stress relaxation layer has some gas barrier properties. In the present invention, the barrier layer is formed of a layer made of a silicon oxynitride layer formed by a wet process such as a polysilazane coating layer, for example, and the laminate is configured together with the stress relaxation layer. Yes.

The stress relaxation layer is a flexible layer having a small internal stress. For example, the stress relaxation layer is a layer that can relieve the stress caused by the film shrinkage during film formation of the barrier layer. Even if it raises, the flexible film | membrane (layer) with a small internal stress containing the metal oxide or metal oxynitride which has favorable adhesiveness with a barrier layer can be formed. Note that the vacuum plasma method has a problem of productivity because the film formation rate is low, and it becomes difficult to form a flexible film, resulting in a layer having low stress relaxation ability.
In the configuration of the present invention, when the barrier layer is laminated by a wet process, if the stress relaxation layer is formed as the lower layer by an atmospheric pressure plasma CVD method, the barrier layer is adsorbed to the substrate or the lower layer film. Since it is difficult to receive water, the laminated barrier layer is more susceptible to the influence of water from the lower layer by the stress relaxation layer formed by the atmospheric pressure plasma CVD method. Conceivable.

In addition, the stress relaxation layer formed by atmospheric pressure plasma CVD is flexible, has low internal stress, and does not shrink itself. Therefore, the stress generated when forming a dense barrier layer by modifying polysilazane is sufficiently relaxed. it can.

Also, by using a film made of the same material (material) as the barrier layer for the stress relaxation layer, a laminated film having good adhesion to the barrier layer made of silicon oxynitride formed by a wet process can be obtained.

In addition, according to the atmospheric pressure plasma CVD method, for example, it can be carried out under atmospheric pressure as in the case of a wet process such as polysilazane coating, so a layer containing at least one of a metal oxide and a metal oxynitride (stress relaxation layer) When forming a layered structure of silicon oxynitride (barrier layer) formed by a wet process, continuous processing under atmospheric pressure is possible, which is preferable in production.

真空 Vacuum plasma CVD cannot be performed continuously with the barrier layer deposition process using a wet process. Further, the number of man-hours for the process such as evacuation is increased, so that productivity is deteriorated.

The present invention provides a gas barrier having a layer comprising at least one of a metal oxide and a metal oxynitride formed by atmospheric pressure plasma CVD on at least one surface of a substrate, and a layer made of silicon oxynitride formed by a wet process Although it is a laminated body, it is also preferable that at least two such gas barrier layer units are repeatedly laminated on at least one surface of the substrate. The number of laminated layers is determined by the required gas barrier performance, but even when the film thickness is increased in the present invention, the flexibility of the gas barrier layer unit is good, so that the flexibility is not deteriorated.

Hereinafter, each layer of the present invention will be described in detail.

(Stress relaxation layer)
One feature of the present invention is that the stress relaxation layer is formed by an atmospheric pressure plasma CVD method.

(Atmospheric pressure plasma CVD)
In general, vacuum deposition, sputtering, vacuum plasma CVD, and the like are known as a method for forming a layer containing at least one of a metal oxide and a metal oxynitride. The layer containing at least one of the metal oxynitrides cannot obtain sufficiently excellent stress relaxation performance as described above.
In particular, the compressive stress of the layer containing at least one of the metal oxide and metal oxynitride formed by the multi-pressure plasma CVD method is at least one of the metal oxide and metal oxynitride formed by the vacuum plasma CVD method. It is about 1/100 of the compressive stress of the containing layer. As a method for measuring the compressive stress, each layer was formed to a thickness of 1 μm on a quartz glass having a thickness of 100 μm, a width of 10 mm, and a length of 50 mm, and the compressive stress (residual stress, MPa) can be measured.

The thickness of the layer (thin film) containing at least one of these metal oxides and metal nitrides in the present invention varies depending on the type and configuration of the materials used and is appropriately selected, but is within the range of 5 to 2000 nm. It is preferable that

For example, when the thickness is smaller than the above range, there are many film defects, a uniform film cannot be obtained, and sufficient stress relaxation ability is difficult to obtain. In addition, if the thickness of the layer having a metal oxide or metal nitride is larger than the above range, the internal stress also increases, and the barrier layer is formed during film formation or after the film is bent or pulled. There is a risk that cracks may occur due to mechanical factors, and preferable stress relaxation properties may not be obtained.

In the present invention, it is preferable that a silicon oxynitride thin film laminated on a layer containing at least one of the metal oxide and the metal nitride by a wet process is transparent. This is because the gas barrier laminate can be made transparent by being transparent, and can also be used for applications such as transparent substrates such as EL elements and photoelectric conversion elements. As the light transmittance of the gas barrier laminate, for example, when the wavelength of the test light is 550 nm, the transmittance is preferably 80% or more, and more preferably 90% or more.

The plasma CVD method, or the plasma CVD method under atmospheric pressure or near atmospheric pressure, is performed by selecting conditions such as organometallic compounds, decomposition gas, decomposition temperature, and input power as raw materials (also referred to as raw materials). It is preferable because a ceramic layer of a metal, a metal nitride, a metal carbide, etc., and a mixture with these metal oxynitrides, metal nitride carbides, etc. can be formed separately.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. In addition, because highly active charged particles and radicals exist in the plasma space at a high density, multistage chemical reactions are promoted very rapidly in the plasma space, and the elements present in the plasma space are This is because it is converted into a thermodynamically stable compound in a very short time.

As such an inorganic material, as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. The solvent may be diluted with a solvent, and an organic solvent such as methanol, ethanol, n-hexane or a mixed solvent thereof can be used as the solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

Various metal oxides, metal nitrides, and metal carbides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

In the present invention, as a source gas containing a metal element, for example, as a silicon compound, tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxy Silane, diethyldiethoxysilane, diethylsilanedi (2,4-pentanedionate), methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and other silicon hydride compounds include tetrahydrogenated silane, hexahydrogenated Examples of the silicon halide compound such as disilane include tetrachlorosilane, methyltrichlorosilane, and diethyldichlorosilane, and any of these can be preferably used in the present invention. Two or more of these may be mixed and used at the same time. From the viewpoint of handling, the above silicon compounds are preferably silicon alkoxides, alkyl silanes, and silicon hydrogen compounds, and are not corrosive, do not generate harmful gases, and have little contamination in the process. preferable.

Examples of titanium compounds include organic titanium compounds, titanium hydrogen compounds, and titanium halides. Examples of organic titanium compounds include triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, and tetraethoxy titanium. , Tetraisopropoxy titanium, methyl dimethoxy titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, triethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, tetradimethylamino titanium, dimethyl titanium di (2,4-pentanedionate), ethyltitanium tri (2,4-pentanedionate), titanium tris (2,4-pentanedionate), titanium tris (acetomethyl) SETATE), triacetoxytitanium, dipropoxypropionyloxytitanium, etc., dibutyryloxytitanium, titanium hydrogen compound as monotitanium hydrogen compound, dititanium hydrogen compound, etc., and halogenated titanium as trichlorotitanium, tetrachlorotitanium, etc. Any of these can be preferably used in the present invention. Two or more of these can be mixed and used at the same time.

Examples of the tin compound include organic tin compounds, tin hydrogen compounds, tin halides, and the like. Examples of the organic tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, and tetraoctyl. Tin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, Tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, etc., tin hydride compounds, etc. Examples of tin halides include tin dichloride and tin tetrachloride. Any of these can be preferably used in the present invention. Two or more of these may be mixed and used at the same time.

Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s-butoxide, and the like. Can be mentioned.

Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane , Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptane dione , Ferrocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetra Examples include methyl heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, diethylzinc, and the like.

Among these, in the present invention, it is preferable to use a silicon compound, and silicon oxide, silicon oxynitride or silicon nitride formed from a silicon compound is preferable.

These discharge gases are mixed with a discharge gas that tends to be in a plasma state, and the gas is sent to a plasma discharge generator.

As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

The film is formed by mixing the discharge gas and the reactive gas and supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. Further, if silazane or the like is used as a raw material compound, silicon oxynitride is generated.

This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

In the present invention, the layer containing at least one of metal oxide and metal nitride is preferably a silicon oxide film, and is preferably a silicon oxide film having a carbon content of 1 to 30 at%. In the present invention, the carbon content (at%) represents the atomic concentration (atomic concentration).

The metal oxide and the metal oxynitride have a carbon content within the above range, so that the metal oxide and the metal oxynitride become a film that is more flexible and has low internal stress, and the film formation rate by the atmospheric pressure plasma method can be increased.

When forming a thin film using the atmospheric pressure plasma CVD method, depending on the manufacturing conditions and the thin film forming gas used (type, ratio, etc. of source gas and additive gas), the degree of filling of silicon oxide particles and the amount of contamination Since there is a difference in impurity particles, etc., the carbon content is adjusted by adjusting these. Thereby, physical properties, density, and the like are different, and flexibility is also different.

(X-ray reflectivity method)
The outline of the X-ray reflectivity method is described in page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000, International Literature Printing Co., Ltd.) 22 can be performed.

Specific examples of measurement methods useful in the present invention are shown below.

This is a method in which row lines are incident on a material having a flat surface at a very shallow angle, and measurement is performed using MXP21 manufactured by Mac Science. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1, and each parameter is obtained so that the residual sum of squares of the actual measurement value and the fitting curve is minimized. The refractive index, thickness and density of the laminated film can be obtained from each parameter. The film thickness evaluation of the laminated film in the present invention can also be obtained from the X-ray reflectivity measurement.

The density of the silicon oxide film is closely correlated with the carbon content, which is a trace component. For example, a film having a low carbon atom concentration (less than 0.1 at%) is a film having a high density. A film of 1 at% or more and less than 30 at%, which is higher than the above, is a softer composition having a lower film density and suitable as a stress relaxation layer.

The atomic concentration% (at%) indicating the carbon content can be determined using a known analysis means, but in the present invention, it is calculated by the following XPS method and is defined below.

Atomic concentration% = number of carbon atoms / number of all atoms × 100
As the XPS surface analyzer, ESCALAB-200R manufactured by VG Scientific, Inc. was used in the present invention. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

As a measurement, first, the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as atomic concentration (at%).

Before performing the quantitative process, the calibration of the Count Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

(Method for forming stress relaxation layer)
In the method for producing a gas barrier laminate of the present invention, an atmospheric pressure plasma CVD method that can be suitably used for forming a layer containing at least one of the metal oxide and the metal oxynitride according to the present invention will be described in more detail. .

In CVD (chemical vapor deposition), volatilized and sublimated organometallic compounds adhere to the surface of a high-temperature support, causing a thermal decomposition reaction to produce a thermally stable inorganic thin film. In such a normal CVD method (also referred to as a thermal CVD method), since a substrate temperature of 500 ° C. or higher is usually required, it is difficult to use for forming a film on a plastic support. In the CVD method, an electric field is applied to the space in the vicinity of the support to generate a space (plasma space) in which a gas is present (plasma space). Volatilized and sublimated organometallic compounds are introduced into the plasma space and decomposed. After the occurrence of this, it is sprayed onto the support to form an inorganic thin film. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support on which the inorganic material is formed and can sufficiently form the film on the resin film support.

In the plasma discharge treatment apparatus, the source gas containing metal and the decomposition gas are appropriately selected from the gas supply means, and a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases. The above layer can be obtained by feeding a gas into the plasma discharge generator.

In the atmospheric pressure plasma CVD method, the plasma discharge treatment is performed under atmospheric pressure or a pressure in the vicinity thereof, but the atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and the good effects described in the present invention are obtained. In order to obtain it, 93 kPa to 104 kPa is preferable.

The discharge condition is such that the first high-frequency electric field and the second high-frequency electric field are superimposed on the discharge space, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, and The relationship between the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the strength IV of the discharge start electric field is:
V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied,
The output density of the second high frequency electric field is 1 W / cm ² or more.

«High frequency means that has a frequency of at least 40 kHz.

When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

The strength of the electric field at which discharge starts is the lowest electric field strength that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method. The discharge start electric field strength varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but is controlled by the discharge start electric field strength of the discharge gas in the same discharge space.

Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves, one of them may be continuous, and the other may be pulse waves. Further, it may have a third electric field.

As a specific method for applying a high-frequency electric field to the same discharge space, a first power source for applying a first high-frequency electric field having a frequency ω1 and an electric field strength V1 is connected to the first electrode constituting the counter electrode. The use of an atmospheric pressure plasma discharge treatment apparatus in which a second power source for applying a second high-frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode.

The above atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a reactive gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high-frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge treatment apparatus has a capability of applying a high-frequency electric field strength higher than that of the second power source.

Here, the high-frequency electric field strength (applied electric field strength) and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of high-frequency electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode section, and the output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as a discharge starting electric field strength IV. The measuring instrument is the same as the high frequency electric field strength measurement.

By adopting predetermined discharge conditions, even a discharge gas with a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and perform high-performance thin film formation. I can do it.

When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first high frequency electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 40 kHz.

On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. It is an important point of the present invention that the plasma density can be increased by the high power density.

Also, by increasing the output density of the first high-frequency electric field, it is possible to improve the output density of the second high-frequency electric field while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated.

In the atmospheric pressure plasma discharge processing apparatus used in the present invention, the first filter facilitates passage of the current of the first high-frequency electric field from the first power source to the first electrode, and grounds the current of the second high-frequency electric field. Thus, it is difficult to pass the current of the second high-frequency electric field from the second power source to the first power source. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. The current of the first high-frequency electric field to the power supply is made difficult to pass. In the present invention, any filter having such properties can be used without limitation.

For example, as the first filter, a capacitor of several tens of pF to tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

Supply power higher well, the first power source is preferably 1W / cm ² or more, 2W / cm ² or more is more preferable, 5W / cm ² or more is more preferable. The second power source is preferably 1 W / cm ² or more, more preferably 5 W / cm ² or more, and even more preferably 11 W / cm ² or more.

Further, as the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost. The reactive gas is not limited as long as the silicon compound can be changed to silicon oxide, but oxygen and water are preferable.

As an atmospheric pressure plasma discharge treatment apparatus applicable to the present invention, for example, atmospheric pressure plasma discharge treatment described in JP-A-2004-68143, 2003-49272, International Patent No. 02/48428, etc. A device can be mentioned.

As for the power source installed in the atmospheric pressure plasma discharge treatment apparatus, Shinko Electric SPG50-4500 (frequency 50 kHz), Hayden Laboratory PHF-6k (100 kHz), Pearl Industry CF-2000-200k (200 kHz), CF-2000- 400k (400kHz), CF-2000-800k (800kHz), CF-2000-2M (2MHz), CF-2000-13M (13.56MHz), CF-2000-27M (27MHz), CF-2000-150M (150MHz) ) And the like, and any of them can be preferably used.

[Barrier layer]
The barrier layer in the present invention is a film that contains silicon atoms and oxygen atoms and prevents the permeation of oxygen and water vapor. Specifically, the constituent material is preferably an inorganic oxide containing silicon, and a silicon oxynitride layer Can be mentioned.

With such a barrier layer, the water vapor transmission rate measured according to the JISK7129B method is 10 ⁻⁴ g / (m ² · 24 h) or less, preferably 10 ⁻⁵ g / (m ² · 24 h) or less, rate is ^{0.01cm 3 / (m 2 · 24h} · atm) or less, preferably ^{0.001cm 3 / (m 2 · 24h} · atm) or less is barrier excellent in gas barrier layered product is obtained.

As the water vapor permeability of the gas barrier laminate (barrier film) of the present invention, when used for applications requiring high water vapor barrier properties such as organic EL displays and high-definition color liquid crystal displays, particularly for organic EL display applications, Even if it is extremely small, a growing dark spot may be generated and the display life of the display may be extremely shortened. Therefore, the water vapor permeability measured according to the JISK7129B method is preferably not more than the above value.

In order to achieve such a barrier property, the surface roughness of the barrier layer surface is 10 nm or more and 30 nm or less in terms of the maximum cross-sectional height Rt (p) of the roughness curve obtained according to JIS B0601: 2001. Preferably there is.

(Method for forming barrier layer)
In the production of the gas barrier laminate of the present invention, a layer containing at least one of a metal oxide and a metal nitride was formed on at least one surface of a substrate as a stress relaxation layer by atmospheric pressure plasma CVD as described above. On top of this, a liquid containing at least one silicon compound is applied at 20 ° C. to 120 ° C. (wet process) and dried to form a silicon compound thin film, and the silicon compound thin film is subjected to a modification treatment, and silicon A thin film of oxynitride is laminated.

As the liquid containing a silicon compound formed by a wet process, for example, application, a polysilazane-containing application liquid is preferable.

(Formation of barrier layer with polysilazane-containing coating solution)
The barrier layer according to the present invention is formed by laminating and applying a coating liquid containing a polysilazane compound on a stress relaxation layer formed by an atmospheric pressure plasma CVD method.

Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc. SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _y. Such as a ceramic precursor inorganic polymer.

In order not to damage the film substrate, a compound which is converted to silica by being ceramicized at a relatively low temperature is preferable. For example, it is represented by the following general formula (1) described in JP-A-8-112879. A compound having a main skeleton composed of units is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. .

In the present invention, perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a gas barrier layer to be obtained.

On the other hand, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an improved adhesion to the base substrate by having an alkyl group such as a methyl group, and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the above general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208) A metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (see, for example, JP-A-6-299118), and an acetylacetonate complex obtained by reacting a metal-containing acetylacetonate complex Additional polysilazanes (eg, Unexamined see JP 6-306329), fine metal particles added polysilazane obtained by adding metal particles (e.g., Japanese Unexamined see JP 7-196986), and the like.

Furthermore, in addition to the above polysilazane, silsesquioxane can also be used. The silsesquioxanes such, Mayaterials Co. Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3- ethyl-3-oxyethyl) methoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octalyloxetanes silsquioxane, Octa [(3-Propylglycidylethyl) ) Dimethylsiloxy] silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane; Octakis (dimethylvinylsilyloxy) octasisilsesquioxane, Octakis [(3-hydroxypropyloyl) dimethylsiloxy] octasilsesquixane, methacryloylpropyl) dimethylsilyloxy] silsesquioxane Octakis [(3-methacryloxypropyl) dimethylsiloxy] octasilsesquioxane, the compounds of the like.

As the organic solvent for preparing a coating liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

The polysilazane concentration in the polysilazane-containing coating solution is preferably about 0.2 to 35% by mass, although it varies depending on the film thickness of the target barrier layer and the pot life of the coating solution.

In the polysilazane-containing coating solution, an amine or metal catalyst may be added to promote conversion to a silicon silicate nitrogen compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

(Operation for removing organic solvent and moisture from barrier layer)
The barrier layer formed by the polysilazane-containing coating solution according to the present invention preferably has moisture removed before or during the modification treatment. Therefore, it is preferable to divide into the 1st process aiming at the removal of the organic solvent in a barrier layer, and the subsequent 2nd process aiming at the removal of the water | moisture content in a barrier layer.

In the present invention in which the stress relaxation layer is formed by a dry process by the atmospheric pressure plasma CVD method, it is considered preferable in this respect because the stress relaxation layer itself and the substrate or the lower layer film adsorbed water are hardly received.

In the first step, in order to mainly remove the organic solvent, the drying conditions can be appropriately determined by a method such as heat treatment, and at this time, the moisture may be removed. The heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but it is preferable to appropriately determine the temperature and treatment time in consideration of thermal damage to the resin film substrate. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the heat treatment temperature can be set to 200 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate is reduced. If the heat treatment temperature is 200 ° C. or less, the treatment time can be set within 30 minutes.

The second step is a step for removing moisture in the barrier layer, and the method for removing moisture is preferably in the form of dehumidification while maintaining a low humidity environment. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or lower, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). (Humidity 1%) or less, and the maintained time is preferably set appropriately depending on the thickness of the barrier layer. Under the condition that the thickness of the barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −8 ° C. or less and the maintaining time is 5 minutes or more. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.

As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a treatment time of 1 to 30 minutes in the first step, the dew point of the second step is 4 ° C. or less. The treatment time can be selected from 5 minutes to 120 minutes to remove moisture. The first process and the second process can be distinguished by a change in dew point, and the difference can be made by changing the dew point of the process environment by 10 ° C. or more.

The barrier layer according to the present invention is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

(Water content of the barrier layer)
The moisture content of the barrier layer according to the present invention can be measured according to the analysis method shown below.

Headspace-gas chromatograph / mass spectrometry instrument: HP6890GC / HP5973MSD
Oven: 40 ° C. (2 min), then heated to 150 ° C. at a rate of 10 ° C./min Column: DB-624 (0.25 mm × 30 m)
Inlet: 230 ° C
Detector: SIM m / z = 18
HS condition: 190 ° C, 30min
The moisture content in the barrier layer in the present invention is defined as a value obtained by dividing the moisture content obtained by the above analysis method by the volume of the barrier layer, and is preferably 0 in a state where moisture is removed by the second step. 0.1% or less, and a more preferable water content is 0.01% or less (below the detection limit).

In the present invention, it is preferable to remove water before or during the reforming treatment from the viewpoint of promoting the dehydration reaction of the barrier layer converted to silanol.

[Modification of barrier layer]
The modification treatment in the present invention refers to a conversion reaction of a polysilazane compound to silicon oxynitride.

For the modification treatment in the present invention, a known method based on the conversion reaction of the barrier layer can be selected. The formation of the silicon oxynitride film by the substitution reaction of the polysilazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate such as plastic.

Therefore, in producing the gas barrier laminate of the present invention, from the viewpoint of adapting to a plastic substrate, a conversion reaction using plasma, ozone, or ultraviolet rays that can be converted at a lower temperature is preferable.

(Plasma treatment)
As the plasma treatment that can be used as the modification treatment, a known method can be used, but the aforementioned atmospheric pressure plasma treatment is preferable.

(UV irradiation treatment)
In the present invention, treatment by ultraviolet irradiation is also preferable as one of the modification treatment methods. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.

The substrate is heated by this ultraviolet irradiation, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated, so that polysilazane is excited and polysilazane ceramics. Is promoted, and the resulting ceramic film becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

In the method according to the present invention, any commonly used ultraviolet ray generator can be used.

The ultraviolet ray referred to in the present invention generally means an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 350 nm. Use ultraviolet light.

For the irradiation of ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the barrier layer to be irradiated is not damaged.

Taking the case of using a plastic film as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ² . The distance between the substrate and the ultraviolet irradiation lamp can be set so that the irradiation can be performed for 0.1 seconds to 10 minutes.

Generally, when the substrate temperature at the time of ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the substrate are impaired in the case of a plastic film or the like, for example, the substrate is deformed or its strength is deteriorated. However, in the case of a film having high heat resistance such as polyimide or a substrate such as metal, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

Examples of such ultraviolet ray generating means include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. )), UV light laser, and the like. Moreover, when irradiating the generated ultraviolet rays to the barrier layer, it is desirable to apply the ultraviolet rays from the generation source to the barrier layer after reflecting the ultraviolet rays from the generation source with a reflecting plate from the viewpoint of achieving efficiency improvement and uniform irradiation.

UV irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a substrate having a barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known, and for example, an ultraviolet baking furnace manufactured by Eye Graphics Co., Ltd. can be used. Further, when the substrate having the barrier layer on the surface is a long film, the substrate is ceramicized by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while being conveyed. be able to. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, depending on the composition and concentration of the substrate and barrier layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and only bonds photons called photon processes. By this action, a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.

As a vacuum ultraviolet light source necessary for this, a rare gas excimer lamp is preferably used.

Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

¡Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric), the electric discharge accumulates on the surface of the dielectric, and the micro discharge disappears. This micro discharge spreads over the entire tube wall, and is a discharge that repeatedly generates and disappears. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

As a method for efficiently obtaining excimer light emission, electrodeless field discharge is possible in addition to dielectric barrier discharge.

Electrode-free electric field discharge due to capacitive coupling, also called RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

In the case of dielectric barrier discharge, since micro discharge occurs only between the electrodes, the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to cause discharge in the entire discharge space. Must be a thing. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

To prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation device, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

Since the outer diameter of the double-cylindrical lamp is about 25 mm, the difference in distance to the irradiation surface cannot be ignored directly below the lamp axis and on the side of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

¡When electrodeless field discharge is used, it is not necessary to make the external electrode mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector, usually made of an aluminum block, is used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. Therefore, a very inexpensive light source can be provided.

二 重 Double-cylindrical lamps are easily damaged by handling and transportation compared to thin-tube lamps because they are processed by connecting both ends of the inner and outer tubes. The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm. If it is too thick, a high voltage is required for starting.

The discharge mode can be either dielectric barrier discharge or electrodeless field discharge. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

¡Excimer lamps have high light generation efficiency and can be lit with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as polyethylene terephthalate which are considered to be easily affected by heat.

It is preferable in the present invention that the barrier layer is sufficiently homogeneously modified and has high gas barrier performance.

As in the present invention, a barrier layer obtained by forming a film by a wet process and subjecting it to a modification treatment is used together with at least one of a metal oxide and a metal nitride formed by an atmospheric pressure plasma CVD method as a stress relaxation layer. By forming, it is possible to prevent cracking due to stress concentration, to achieve both high barrier properties and a stress relaxation function, and to obtain a gas barrier laminate excellent in flex resistance. In addition, by adopting vacuum ultraviolet treatment as the barrier layer modification treatment method, it is preferable that treatment at a high temperature is not necessary and it is easy to produce continuously with the stress relaxation layer.

In the present invention, a layer (stress relaxation layer) containing at least one of a metal oxide and a metal nitride formed by an atmospheric pressure plasma CVD method, and a layer (barrier) made of silicon oxynitride formed by a wet process Layer) to form a gas barrier layer unit, at least two gas barrier layer units may be repeatedly laminated on at least one surface of the substrate.

In the case of laminating each layer unit, layers containing metal oxides (or nitrides) having an approximate composition are also good, and adhesion is good, and in the present invention, it is continuously produced at atmospheric pressure. This is preferable in terms of productivity.

When stacking gas barrier layer units, the number of stacks is determined by the required gas barrier performance, but in the present invention, the range of 2 to 3 is preferable as the gas barrier layer unit, and when the number of stacks is increased and the film thickness is increased. However, since the gas barrier layer unit has good bending resistance, there is no deterioration in flexibility.

Next, a resin film support used as a substrate in the gas barrier laminate according to the present invention will be described.

The resin film support as a substrate is not particularly limited as long as it is formed of an organic material capable of holding the stress relaxation layer and the barrier layer.

For example, acrylic ester, methacrylate ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP) Polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and other resin films, silsesquioxane having an organic-inorganic hybrid structure And a heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin film formed by laminating two or more layers of the resin. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

The resin film support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.

In addition, the resin film support using the above-described resins or the like may be an unstretched film or a stretched film.

The resin film support used in the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

In the present invention, the resin film support may be subjected to corona discharge treatment before the barrier layer is formed.

Furthermore, an anchor coat agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion with the metal oxide film or the metal nitride film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(Smooth layer)
In this invention, it is preferable that the smooth layer is provided on the resin film support body which is a board | substrate.

The smooth layer of the present invention flattens the rough surface of the transparent resin film support on which protrusions and the like are present, or fills irregularities and pinholes generated in the stress relaxation layer or barrier layer with the protrusions on the transparent resin film support. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive resin.

As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, grease Zyl acrylate, 2-hydroxyethyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propane Diol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, and the like, and The above acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pi Lolidon etc. are mentioned. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

The composition of the photosensitive resin contains a photopolymerization initiator. Examples of photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, dibenzyl ketone, fluorenone, and 2,2-diethoxyacetophenone. 2,2-dimethoxy-2-phenylacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, Benzanthrone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2 (O-methoxycarbonyl) oxime, Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl)- Photoreductive dyes such as butanone-1, naphthalenesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, carbon tetrabromide, tribromophenylsulfone, methylene blue and the like, ascorbic acid, tri The combination of reducing agents, such as ethanolamine, is mentioned, These photoinitiators can be used by 1 type, or 2 or more types of combination.

The method for forming the smooth layer is not particularly limited, but is preferably formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, α- or β- Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aromatic hydrocarbons such as toluene, xylene, tilcellosolve, Glycol ethers such as ethyl cellosolve, carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cell Examples include acetates such as losolve acetate and propylene glycol monomethyl ether acetate, diethylene glycol dialkyl ether, ethyl 3-ethoxypropionate, methyl benzoate, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If the value is smaller than this range, adhesion may be impaired when a stress relaxation layer is formed by atmospheric pressure plasma CVD, or when a barrier layer is further formed. On the other hand, if it is larger than this range, it may be difficult to smooth the unevenness after the stress relaxation layer or barrier layer is formed.

The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

(Additive to smooth layer)
One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the above-described photosensitive resin. Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, by using it in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm, which will be described later, optical characteristics satisfying a good balance between anti-glare properties and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties. From the viewpoint of making it easier to obtain such effects, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. Addition of 20% or more improves adhesion with the stress relaxation layer and the barrier layer. On the other hand, if it exceeds 60%, the film may be bent or cracked when heat-treated, or optical properties such as transparency and refractive index of the gas barrier film may be affected.

In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.

Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

The thickness of the smooth layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer has a high transparency. When the film is provided on only one surface of the molecular film, curling of the smooth film can be easily suppressed.

(Bleed-out prevention layer)
The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers are transferred from the film support to the surface and contaminate the contact surface. Provided on the opposite side of the substrate having a layer.

The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

Examples of the polyunsaturated organic compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate , Etc.

Examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate Doors and the like.

) Matting agents may be added as other additives. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

The bleed-out preventing layer of the present invention may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, etc. as other components of the hard coat agent and the matting agent.

Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

Also, examples of the thermosetting resin include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like.

Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane, α-acyloxime ester, thioxanthone and the like.

The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and hardening. As a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

The gas barrier laminate of the present invention can be used as various sealing materials and substrate films.

For example, it can be used for organic EL elements and organic photoelectric conversion elements. When used as a support for such an element, the gas barrier laminate of the present invention is transparent, so that it can receive sunlight from the support side or extract light from the gas barrier resin film side. That is, on this gas barrier resin film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute an organic EL element or an organic photoelectric conversion element. In addition, an organic EL element or an organic photoelectric conversion element is formed, and another sealing material is stacked on the organic EL element or the organic photoelectric conversion element (which may be the same), and the gas barrier film support and the periphery are bonded together. Thus, it is possible to seal the influence of the moisture of the outside air and gas such as oxygen on the device. The gas barrier laminate according to the present invention can also be used as such a sealing material.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
(Support)
As a thermoplastic resin support, a substrate of a 125 μm thick polyester film (Tetoron O3, manufactured by Teijin DuPont Films Ltd.) that was easily bonded on both sides was annealed at 170 ° C. for 30 minutes and used.

The barrier film was produced by adhering an adhesive protective film after forming a bleed-out prevention layer on one side and a smooth layer on the opposite side by the following forming method while transporting the support at a speed of 20 m / min. A roll-shaped barrier film was obtained.

<Production of film having smooth layer and bleed-out preventing layer>
(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the support, and the film was coated with a wire bar so that the film thickness after drying was 4 μm, followed by curing conditions: 500 mJ / cm Under high pressure using a high-pressure mercury lamp in ² air, curing was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the support, and the film was dried with a wire bar so that the film thickness after drying was 4 μm, and then drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 500 mJ / cm ² curing was performed to form a smooth layer.

The maximum cross-sectional height Rt (p) at this time was 21 nm.

The maximum cross-sectional height Rt (p) is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius. This is the average roughness of the amplitude of fine irregularities measured many times in a section with a measurement direction of 30 μm.

<Production of gas barrier laminate (gas barrier film)>
(Formation of stress relaxation layer)
Next, a silicon oxide layer was formed on the smooth layer of the support provided with the smooth layer and the bleed-out prevention layer by atmospheric pressure plasma CVD under the following conditions.

(Formation of silicon oxide thin film by atmospheric pressure plasma CVD method)
A thin film was formed on the support provided with the smooth layer and the bleed-out preventing layer by atmospheric pressure plasma CVD using an organic silicon compound and oxygen as raw materials under the following conditions. The film thickness is 50 nm. Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes opposed to the roll electrode were installed in parallel to the film transport direction, and raw materials and electric power were supplied to each electrode part to form a thin film as follows.

Here, the dielectric was coated with 1 mm of single-sided ceramic sprayed material, with both electrodes facing each other. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. As the power source used here, a high frequency power source (100 kHz) manufactured by Applied Electric and a high frequency power source (13.56 MHz) manufactured by Pearl Industry were used. Samples were prepared under the following conditions.

<Plasma CVD layer>
<Stress relaxation layer mixed gas composition 1>
Discharge gas: Nitrogen gas 94.85% by volume
Thin film forming gas: hexamethyldisiloxane 0.15% by volume
Additive gas: Oxygen gas 5.0% by volume
<Buffer film formation conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Formation of barrier layer)
Next, a barrier layer was formed on the sample stress relaxation layer by a wet process using a silicon compound layer coating solution.

(Silicon compound layer coating solution)
Perhydropolysilazane (PHPS) 20% by weight dibutyl ether solution (Aquamica NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.), wireless bar count and perhydropolysilazane solution so that the film thickness after drying is 200 nm. Was diluted with dehydrated dibutyl ether and adjusted to obtain a sample coated on the silicon oxide film layer at 23 ° C. and 50% RH and then dried at 80 ° C. for 1 minute.

The dried sample was further dehumidified by being held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.).

[Modification treatment]
The sample subjected to the dehumidification treatment was subjected to a modification treatment under the following conditions. The dew point temperature during the reforming process was -8 ° C.

(Modification equipment)
Equipment: Ex D irradiation system MODEL manufactured by M.D. Com: MECL-M-1-200
Wavelength: 172nm
Lamp filled gas: Xe
(Reforming treatment conditions)
The sample fixed on the operation stage was subjected to a modification treatment under the following conditions to form a barrier layer.

Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer irradiation time: 5 seconds As described above, gas barrier laminate sample 1 as a gas barrier film was produced.

Samples 2 to 6 were produced in the same manner.

Samples 2 and 3 were prepared by changing the plasma CVD layer formation conditions as follows.

Sample 2
<Plasma CVD layer>
<Stress relaxation layer mixed gas composition 2>
Discharge gas: Nitrogen gas 99.0% by volume
Thin film forming gas: Hexamethyldisiloxane 0.5% by volume
Additive gas: 0.5% by volume of oxygen gas
<Buffer film formation conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 12 W / cm ² (the voltage Vp at this time was 6 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
Sample 3
<Plasma CVD layer>
<Stress relaxation layer mixed gas composition 3>
Discharge gas: Nitrogen gas 94.99 volume%
Thin film forming gas: tetraethoxysilane 0.01% by volume
Additive gas: Oxygen gas 5.0% by volume
<Silicon dioxide film formation conditions>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
Sample 4
The stress relaxation layer of Sample 1 was prepared using a coating method. Instead of using the atmospheric pressure plasma method, the silicon oxide layer was replaced by a modification treatment of perhydropolysilazane (PHPS) used in the barrier layer of Sample 1.

Sample 5
In sample 4, the stress relaxation layer was formed by applying organic polysilazane (methylhydropolysilazane) instead of perhydropolysilazane (PHPS), coating, drying, and modifying treatment under the same conditions to prepare sample 5.

Sample 6
Sample 6 was obtained by changing the stress relaxation layer to the following resin composition in Sample 1.

(Stress relaxation layer formation)
On the smooth layer of the support provided with the smooth layer and the bleed-out prevention layer, the following composition was applied so that the dry film thickness was 400 nm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured.

<Composition>
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer or higher component 20 parts by mass Diethoxybenzophenone (UV photoinitiator) 2 parts by mass methyl ethyl ketone 50 50 parts by weight ethyl acetate 50 parts by weight Isopropyl alcohol 50 parts by weight The above composition was dissolved while stirring.

Sample 7
On the smooth layer of the support provided with the smooth layer and the bleed-out prevention layer, tetramethyldisiloxane (TMDSO) vaporized at 40 ° using a vacuum plasma apparatus is used, and TMDSO / oxygen = 0.5. Introduced into the vacuum vessel at a flow rate ratio, while maintaining a vacuum of 13.3 Pa, a high frequency of 13.56 MHz was introduced into the parallel plate electrodes to cause plasma discharge, and silicon oxide with a film thickness of 50 nm was formed by vacuum plasma CVD. A physical layer was formed. The power density was 5 W / cm ² .

Next, similarly to Sample 1, a barrier layer similar to Sample 1 was formed by wet process using a silicon compound layer coating solution, and Sample 7 was obtained.

Sample 8
As a vacuum plasma CVD layer formation condition, Sample 8 was prepared in the same manner as Sample 7 except that the degree of vacuum was 26.6 Pa and the output density was changed to 2 W / cm ² .

For the samples 1 to 8, the carbon% (atomic number concentration) was measured for each of the stress relaxation layers.

[Evaluation of carbon content]
The carbon contents of the produced first, second, and third silicon oxide layers were measured by XPS (atomic concentration%). The carbon content is an atomic number concentration% calculated by the following XPS method and is defined below.

Atomic concentration (at%) = number of carbon atoms / number of all atoms × 100
As the XPS surface analyzer, ESCALAB-200R manufactured by VG Scientific, Inc. was used in the present invention. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

As a measurement, first, the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

The obtained spectrum is COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as atomic concentration (at%).

Before performing the quantitative process, the calibration of the Count Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used.

The produced gas barrier laminate (gas barrier film) was subjected to the following evaluations on crack resistance, flex resistance, and barrier performance.

<< Evaluation of gas barrier laminate >>
[Evaluation 1: Evaluation of crack resistance]
The occurrence of cracks in the barrier layer due to the stress generated by the film shrinkage during the polysilazane modification was evaluated by visually observing the prepared sample surface using a 100-fold magnifier.

Evaluation rank of crack resistance 5: No crack generation 4: Some cracks are generated, but there are no problems in use 3: Cracks are generated, but there are concerns in use 2: Cracks are generated, there are problems in use 1: Cracks are generated, usable None [Evaluation 2: Evaluation of gas barrier properties]
About each produced gas barrier laminated body, the water-vapor-permeation rate was measured in accordance with the following method, and this was made into the scale of gas barrier property.

<Evaluation of water vapor transmission rate (WVTR)>
The following measurement methods were used for evaluation.

Device vapor deposition device: JEE-400 vacuum vapor deposition device manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments.

Metal that corrodes by reacting with raw material moisture: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Each sample No. Using a vacuum vapor deposition apparatus (JEOL-made vacuum vapor deposition apparatus JEE-400) on the 1 to 8 barrier layer surfaces, a portion other than the measurement area of the sample (12 mm × 12 mm 9 positions) was masked to deposit metallic calcium. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample with both surfaces sealed is stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. Was calculated.

In addition, in order to confirm that there is no permeation of water vapor other than from the barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm, The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

The following evaluation rank was followed.

Less than 5: 1 × 10 ⁻⁴ g / (m ² · 24 h) 4: 1 × 10 ⁻⁴ g / (m ² · 24 h) or more and less than 1 × 10 ⁻³ g / (m ² · 24 h) 3: 1 × 10 ⁻³ g / (m ² · 24 h) or more, less than 1 × 10 ⁻² g / (m ² · 24 h) 2: 1 × 10 ⁻² g / (m ² · 24 h) or more, 1 × 10 ⁻¹ Less than g / (m ² · 24 h) 1: 1 × 10 ⁻¹ g / (m ² · 24 h) or more.

[Evaluation 3: Evaluation of bending resistance]
Each gas barrier laminate was repeatedly bent 100 times at an angle of 180 degrees so that the radius of curvature was 10 mm, and then the gas barrier layer surface of each gas barrier laminate was observed under a microscope, and the water vapor transmission rate was deteriorated according to the following equation: The ratio was measured and bending resistance was evaluated according to the following criteria.

Deterioration ratio of water vapor transmission rate = water vapor transmission rate after bending operation / water vapor transmission rate before bending operation 5: No crack is generated in the ceramic layer, and the deterioration rate of water vapor transmission rate before and after the winding operation is 1.2. 4: There is no occurrence of cracks in the ceramic layer, and the deterioration rate of the water vapor transmission rate before and after the winding operation is 1.2 or more and less than 1.5. 3: Generation of extremely small cracks in the ceramic layer. In addition, the deterioration ratio of the water vapor transmission rate before and after the winding operation is 1.5 or more and less than 2.0 2: the occurrence of obvious cracks in the ceramic layer is recognized, and the water vapor transmission rate before and after the winding operation Deterioration ratio is 2.0 or more and less than 5.0 1: Clear cracks are observed in the ceramic layer, and the deterioration ratio of water vapor permeability before and after the winding operation is 5.0 or more.

Sample 7 (the stress relaxation layer is formed using a vacuum plasma CVD method) has an operating rate of 80% compared to samples 1 to 3 (the stress relaxation layer is formed using an atmospheric pressure plasma CVD method). (Samples 1 to 3 were taken as 100%). That is, it was found that the atmospheric pressure plasma CVD method has a higher operation rate and better productivity.

Example 2
Example of Lamination A gas barrier laminate (samples 9 and 10) in which two or three gas barrier units of sample 1 are repeatedly laminated (stress relaxation layers and barrier layers are alternately laminated) is formed, and cracks are formed in the same manner as in Example 1. Evaluation of resistance, bending resistance, and barrier performance showed that barrier performance was greatly improved, sufficient stress relaxation performance was maintained, and a good level of bending resistance was maintained despite an increase in film thickness. I understood.

The present invention can be used for gas barrier film technology in which metal oxynitride layers are laminated.

1 substrate 2 stress relaxation layer 3 barrier layer

Claims (10)

1. A stress relaxation layer containing at least one of a metal oxide and a metal oxynitride formed by atmospheric pressure plasma CVD and a barrier layer made of silicon oxynitride formed by a wet process were laminated on at least one surface of the substrate. A gas barrier laminate characterized by that.
2. The gas barrier laminate according to claim 1, wherein the metal oxide and the metal oxynitride contain carbon.
3. The gas barrier laminate according to claim 1 or 2, wherein carbon contained in the metal oxide and the metal oxynitride is 0.1% or more and less than 30% in terms of element ratio.
4. The gas barrier laminate according to any one of claims 1 to 3, wherein the barrier layer is subjected to a modification treatment.
5. When the stress relaxation layer according to any one of claims 1 to 3 and the barrier layer formed by a wet process are used as a gas barrier layer unit, at least two of the gas barrier layer unit are repeated on at least one side of the substrate. The gas barrier laminate according to any one of claims 1 to 4, wherein the laminate is laminated.
6. A stress relaxation layer including at least one of a metal oxide and a metal oxynitride is formed on at least one surface of the substrate by an atmospheric pressure plasma CVD method, and a barrier layer made of silicon oxynitride is formed on the stress relaxation layer by a wet process. A method for producing a gas barrier laminate, characterized by comprising:
7. The method for producing a gas barrier laminate according to claim 6, wherein the metal oxide and the metal oxynitride contain carbon.
8. The method for producing a gas barrier laminate according to claim 6 or 7, wherein carbon contained in the metal oxide and the metal oxynitride is 0.1% or more and less than 30% in terms of element ratio.
9. The method for producing a gas barrier laminate according to any one of claims 6 to 8, wherein the barrier layer is subjected to a modification treatment.
10. 10. The gas barrier layer unit according to claim 6, wherein when the stress relaxation layer and the barrier layer are gas barrier layer units, at least two of the gas barrier layer units are repeatedly stacked on at least one surface of the substrate. The manufacturing method of the gas barrier laminated body as described in any one of.

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