WO2014061617A1 - Modification method - Google Patents

Abstract

The purpose of the present invention is to provide a high-productivity, fast modification method that makes it possible to modify a laminate all the way to the interior thereof, said laminate being provided with one or more film layers selected from among oxide films, nitride films, oxynitride films, and oxycarbide films, containing at least one element selected from among silicon, aluminum, and titanium. The present invention is a modification method for modifying at least part of a laminate provided with the following: a substrate; and, formed on top of said substrate, one or more film layers selected from among oxide films, nitride films, oxynitride films, and oxycarbide films, containing at least one element selected from among silicon, aluminum, and titanium. Said modification method is characterized by including a modification step in which the aforementioned one or more film layers are exposed to vacuum ultraviolet light so as to modify at least part of the laminate. The modification method is further characterized in that said vacuum ultraviolet light is generated via a plasma formed from a gas containing at least one compound selected from among CO, CO₂, and CH₄.

Description

Modification method

The present invention relates to a method for modifying a laminate. More specifically, the present invention relates to a method for modifying a laminate that can increase the degree of modification by irradiation with vacuum ultraviolet light generated by plasma of a specific introduced gas.

Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is to prevent deterioration due to various gases such as water vapor and oxygen. It is widely used in packaging applications that require the blocking of various gases. In addition to the packaging applications described above, in order to prevent alteration due to various gases, it is used for sealing electronic devices such as solar cells, liquid crystal display elements, organic electroluminescence elements (hereinafter abbreviated as organic EL elements). Has also been used. In these applications, a very high gas barrier property is required. In addition, from the viewpoint of guaranteeing gas barrier performance, moisture and heat resistance is required such that the gas barrier property does not deteriorate even after a wet heat test (for example, 85 ° C., relative humidity 85%, left for 200 hours). The gas barrier film is superior in flexibility to the glass substrate, and is superior in terms of roll-type production suitability, weight reduction of electronic devices, and handleability.

As a method for producing such a gas barrier film, a gas barrier layer is formed on a substrate such as a film mainly by a plasma CVD method (chemical vapor deposition method) as a dry method. As a method or a wet method, there is known a method in which a coating liquid containing polysilazane as a main component is applied onto a substrate, and then a surface treatment (modification treatment) is applied to the coating film to form a gas barrier layer. Unlike the dry method, the wet method does not require large-scale equipment, is not affected by the surface roughness of the base material, and cannot be pinholed. Therefore, it has attracted attention as a method for obtaining a uniform gas barrier film with good reproducibility. Yes.

Conventionally known methods for modifying polysilazane include a method of irradiating with vacuum ultraviolet light using an excimer lamp (peak wavelength near 172 nm) or the like (see Patent Literatures 1 and 2 below), or a method of plasma irradiation (Patent Literature below) 3).

In the method described in Patent Document 1, a film having a gas barrier property can be formed by irradiation with vacuum ultraviolet light, but in order to obtain a sufficient barrier property, it is necessary to increase the irradiation amount of vacuum ultraviolet light, and productivity is increased. Cannot be secured. Although it is conceivable to arrange a plurality of vacuum ultraviolet light sources to supplement the irradiation amount, the running cost becomes enormous.

In the prior art described in Patent Document 2, the processing time can be shortened by irradiating with vacuum ultraviolet light having a peak at 150 nm or less in a plasma generator. However, if the wavelength used for modification is too short, the film is cut to Si—O in the film, leaving a defect in the film, and sufficient barrier properties cannot be obtained. In addition, because the wavelength is too short, only the resurface of the film is modified, and the film is insufficiently modified. The insufficient part deteriorates when the substrate is exposed to high temperatures, resulting in a decrease in barrier performance. I found out.

As described in Patent Document 3, in the case of modification by plasma irradiation, only the very surface is exposed to plasma, and the outermost surface is a film having a high barrier property, but the inner film has insufficient energy. A sufficient barrier property cannot be obtained. Therefore, when it is going to obtain sufficient modification | reformation to the inside of a film | membrane, the long processing time of several minutes or more is required and it is inferior to productivity.

JP 2009-255040 A JP 2012-143996 A JP 2007-237588 A

The present invention has been made to solve the above-described problems of the prior art, and its purpose is to provide at least one of an oxide film, a nitride film, a nitrogen oxide film, and a carbonated film containing at least one of Si, Al, and Ti. An object of the present invention is to provide a reforming method capable of reforming a laminated body having a single layer film to the inside, having high productivity and short processing time. Furthermore, when a laminated body is a gas barrier film, it is providing the modification method which can improve gas barrier property with high productivity, short processing time.

The above-mentioned problem according to the present invention is solved by the following means.

That is, according to the present invention, a base material and at least one layer of an oxide film, a nitride film, a nitrogen oxide film, and a carbonized film containing at least one of Si, Al, and Ti formed on the base material A modification method for modifying at least a part of a laminate comprising: a reforming step of modifying at least a part of the laminate by exposing the at least one layer of film to vacuum ultraviolet light. There is provided a reforming method characterized in that the vacuum ultraviolet light is generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ .

It is a schematic diagram for demonstrating a magnetron combined capacitive coupling plasma generator. It is another schematic diagram for demonstrating a magnetron combined capacitive coupling plasma generator. It is a schematic diagram for demonstrating a microwave line plasma generator. It is a schematic diagram for demonstrating the example using a microwave line plasma generator.

Hereinafter, preferred embodiments for carrying out the present invention will be described. The present invention is a laminate comprising a base material and at least one film of an oxide film, a nitride film, a nitrogen oxide film, and a carbonated film containing at least one of Si, Al, and Ti formed on the base material. A modification method for modifying at least a part of a body. The method of the present invention includes a reforming step of modifying at least a part of the laminate by exposing the at least one layer of film to vacuum ultraviolet light. The vacuum ultraviolet light is converted into CO, CO ₂ and CH. It is characterized in that it is generated by a plasma of a gas containing at least one of ₄ . As a preferred embodiment, the method of the present invention can further include a step of forming a laminate, and hereinafter, (1) a step of forming a laminate, (2) a reforming step, and (3) other steps. Will be described in detail.

(1) Laminate formation step In the laminate formation step, a base material to which the modification method of the present invention is applied, and an oxide film formed on the base material and containing at least one of Si, Al, and Ti. Then, a laminate including at least one layer of a nitride film, a oxynitride film, and a carbonation film is formed. Typically, the laminate forming process can be (1-1) a film forming process by solution coating or (1-2) a film forming process by sputtering. Each will be described below.

(1-1) Film formation process by solution application (Coating solution)
In film formation by solution coating, a coating solution is first prepared. As the coating solution, a polysilazane solution can be preferably used, and film formation by applying the polysilazane solution is particularly suitable for the production of a gas barrier film. This is because polysilazane is preferable from the viewpoints of film formability, the resulting gas barrier layer has few defects such as cracks, and few residual organic substances. In other words, a preferred embodiment of the present invention is a reforming method in which at least one layer of an oxide film, a nitride film, a nitrogen oxide film, and a carbonated film containing at least one of Si, Al, and Ti contains polysilazane.

There are no particular limitations on the preparation of the coating solution, and the following materials such as the polysilazane compound may be added to an organic solvent and stirred until dissolved. The concentration of the polysilazane compound in the coating solution varies depending on the film thickness of the target gas barrier layer and the pot life of the coating solution, and can be appropriately selected. However, it is preferably 0.5 to 20% by mass, more preferably 1 to 8% by mass. %.

“Polysilazane” is a polymer having a silicon-nitrogen bond, and is a ceramic precursor such as SiO ₂ , Si ₃ N _{4 made of} Si—N, Si—H, NH or the like, and an intermediate solid solution SiO _x N _{y of} both. It is an inorganic polymer. Particularly preferred are polysilazanes such as perhydropolysilazane and organopolysilazane. In order not to damage the resin base material, a compound that is ceramicized at a relatively low temperature and modified to silica (low-temperature ceramicized polysilazane) is preferable, for example, the following general formula described in JP-A-8-112879 A compound having a main skeleton composed of the unit represented by (1) is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms). An alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms) ), A silyl group (preferably a silyl group having 3 to 20 carbon atoms), an alkylamino group (preferably an alkylamino group having 1 to 40 carbon atoms, more preferably an alkylamino group having 1 to 20 carbon atoms) or an alkoxy group (preferably Represents an alkoxy group having 1 to 30 carbon atoms. However, it is preferable that at least one of R ¹ , R ² and R ³ is a hydrogen atom.

The alkyl group in R ¹ , R ² and R ³ is a linear or branched alkyl group. Specific examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2 -Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropylene Group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, Examples thereof include an n-pentacosyl group, an n-hexacosyl group, an n-heptacosyl group, an n-octacosyl group, and an n-triacontyl group.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group and 2-pentenyl group. .

Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include non-condensed hydrocarbon groups such as a phenyl group, a biphenyl group, and a terphenyl group; a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, and a heptaenyl group. Group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylenyl group, pyrenyl group, Examples thereof include condensed polycyclic hydrocarbon groups such as a chrycenyl group and a naphthacenyl group.

Examples of the silyl group having 3 to 20 carbon atoms include alkyl / arylsilyl groups, and specifically include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, methyldiphenylsilyl group, t -Butyldiphenylsilyl group and the like.

The alkylamino group having 1 to 40 carbon atoms is not particularly limited, and examples thereof include dimethylamino group, diethylamino group, diisopropylamino group, methyl-tert-butylamino group, dioctylamino group, didecylamino group, dihexadecyl group. An amino group, a di-2-ethylhexylamino group, a di2-hexyldecylamino group and the like can be mentioned.

Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, eicosyloxy group, Henecosyloxy group, docosyloxy group, tricosyloxy group, tetracosyloxy group, pentacosyloxy group, hexacosyloxy group, heptacosyloxy group, octacosyloxy group, triacontyloxy group, etc. Is mentioned.

The compound having a main skeleton composed of the unit represented by the general formula (1) preferably has a number average molecular weight of 100 to 50,000. The number average molecular weight can be measured by gel permeation chromatography (GPC).

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 the gas barrier layer to be obtained. 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. Examples of commercially available products include Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd., TutProm Series manufactured by Clariant Japan Co., Ltd., and the like.

On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The 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.

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 (eg, 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. Alternatively, a commercially available polysilazane may be used.

In the polysilazane-containing coating solution, an amine or a metal catalyst can be added in order to promote the conversion to a silicon oxide compound. Commercially available coating liquids of polysilazane compounds to which such a catalyst is added include AQUAMICA NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

Specific examples of the organic solvent that can be used to prepare the coating solution include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, and fatty acids. Ethers such as aromatic 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 the polysilazane compound material and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed. However, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane.

(Application method)
The coating liquid of the polysilazane compound prepared as described above is applied onto a substrate to form a coating film. In order to form a coating film, a conventionally known thin film forming method using a coating solution can be used as a simple method. Typically, a wet coating method such as a die coating method, a spin coating method, a spray coating method, a plate coating method, a bar coating method, or a dip coating method can be given. Among these, the die coating method is particularly preferable because the production efficiency is high and the coating film can be formed stably.

The coating thickness of the coating film is not particularly limited, but can be applied so that the film thickness after drying becomes a desired thickness. The film thickness of the gas barrier layer containing the polysilazane compound is not particularly limited, but the film thickness after drying is preferably 1 to 600 nm, and more preferably 30 to 300 nm. If it is such a range, it will be excellent in high gas barrier performance, bending resistance, and cutting processability.

(Base material)
The base material used in the laminate according to the present invention is particularly limited as long as it can hold the above-described polysilazane solution coating film or a film formed by sputtering or CVD described later. However, a resin base material is preferable from the viewpoint of excellent flexibility.

Specific examples include polyolefin (PO) resins such as homopolymers or copolymers such as ethylene, polypropylene and butene, non-quality polyolefin resins (APO) such as cyclic polyolefins, polyethylene terephthalate (PET), polyethylene 2,6 naphthalate. Polyester resins such as (PEN), polyamide (PA) resins such as nylon 6, nylon 12 and copolymer nylon, polyvinyl alcohol resins such as polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer (EVOH) , Polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, polyvinyl butyrate ( VB) resin, polyarylate (PAR) resin, ethylene tetrafluoride ethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), fluoride Fluorine resins such as vinylidene (PVDF), vinyl fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA) can be used.

In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as urethane acrylate, polyester acrylate, or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a laminate coating, as a resin base material.

These materials can be used alone or in combination as appropriate. Among them, ZEONEX and ZEONOR (manufactured by ZEON Corporation), ARTON of non-quality cyclopolyolefin resin film (manufactured by JSR Corporation), Pure Ace of polycarbonate film (manufactured by Teijin Limited), Konica Katak KC4UX of cellulose triacetate film Commercially available products such as KC8UX (manufactured by Konica Minolta Opto), polyethylene terephthalate film with a clear hard coat layer (manufactured by Kimoto), polyester film PET Q83 (manufactured by Teijin DuPont Films) can be preferably used.

Also, the resin base material is preferably transparent. Since the resin base material is transparent and the coating film made of the polysilazane compound formed on the resin base material is also transparent, it becomes a transparent gas barrier film, so that it can be used as a transparent substrate such as an organic EL element. It is.

Further, the resin base material listed above may be an unstretched film or a stretched film.

The resin substrate according to the present invention can be manufactured by a conventionally known general method. For example, an unstretched substrate 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. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

Further, the substrate on which the polysilazane compound is applied may be a substrate having gas barrier properties. Specific examples of the method for imparting gas barrier properties include a base material in which an inorganic oxide, an inorganic nitride, or an inorganic oxynitride is formed on the base material. For example, metal oxides such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, indium tin oxide (ITO), metal nitrides such as silicon nitride and silicon oxynitride, metal oxynitrides Etc. Moreover, metals, such as aluminum, platinum, gold | metal | money, silver, nickel, chromium, can also be mentioned. These formation methods include vacuum deposition, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, plasma CVD, vapor deposition, ALD (Atomic Layer Deposition), sputtering, Examples include dry processes such as atmospheric pressure plasma, spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, and die coating. Can be selected as appropriate.

Among these, as the dry process, the atmospheric pressure plasma method is preferable because a roll-to-roll process under atmospheric pressure is possible.

Also, the coating process is more preferable because it is highly safe, can be formed easily and at a lower cost.

It is preferable to use the base material having the gas barrier property because the gas barrier performance is greatly improved together with the film formed from the polysilazane compound. That is, a preferred embodiment of the present invention is a modification method in which the laminate is a gas barrier film.

The gas barrier property referred to in the present invention is a condition of 40 ° C. × 90% RH using a water vapor permeability measuring apparatus manufactured by MOCON in accordance with the measuring method shown in JIS K7129 B method and ASTM F1249-90. It means that the water vapor transmission rate when measured by is less than 0.1 g / m ² · day.

Further, in the resin base material according to the present invention, surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. may be performed before forming the polysilazane compound coating film. Good.

The resin substrate is conveniently a long product wound up in a roll. Since the thickness of the resin base material varies depending on the use of the obtained gas barrier film, it cannot be specified unconditionally, but when the gas barrier film is used for packaging, there is no particular limitation, and from the suitability as a packaging material, It is preferably in the range of 3 to 400 μm, especially 6 to 150 μm.

(1-2) Film Forming Step by Sputtering Method In the present invention, in order to form a laminated body, at least one oxide film, nitride film, oxynitride film or carbonated film of Si, Al and Ti is formed by a sputtering method. May be. When a film is formed by sputtering, a gas barrier film is preferable because it can easily obtain a dense film having high adhesion and high gas barrier properties. Film formation by sputtering of at least one oxide film of Si, Al and Ti, nitride film, oxynitride film or carbonation film is a combination of DC (direct current) sputtering method, RF (high frequency) sputtering method, and magnetron sputtering. Conventional techniques such as the method and dual magnetron (DMS) sputtering using an intermediate frequency region can be used alone or in combination. In addition, a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, an oxide can be deposited at a high deposition rate, which is preferable. When sputtering a Si, Al or Ti oxide film, nitride film, oxynitride film or carbonation film by DC sputtering or DMS sputtering, Si, Al or Ti can be used as the target. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film of oxide, nitride, nitride oxide, or carbonate of Si, Al, or Ti can be formed. When the film is formed by RF (high frequency) sputtering, a ceramic target such as SiO ₂ or Si ₃ N ₄ can also be used. As the process gas, an inert gas such as He, Ne, Ar, Kr, or Xe, or at least one process gas selected from oxygen, nitrogen, carbon dioxide, and carbon monoxide can be used. Examples of film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected according to the sputtering apparatus, the material of the film, the film thickness, and the like.

In addition to the sputtering method, the laminate may be a vapor deposition method, a physical vapor deposition method (PVD) method such as an ion plating method, a plasma CVD (chemical vapor deposition) method, a chemical vapor deposition method such as ALD (Atomic Layer Deposition), or It can be produced by a sol-gel method or the like.

(2) Modification process In the modification process, the oxide film, nitride film, oxynitride film, and carbonation film containing at least one of Si, Al, and Ti of the laminate formed as described above are converted into a plasma containing a carbon-containing gas. The modification treatment is performed by exposing to the vacuum ultraviolet light generated by.

In the present invention, the modification treatment means that a film such as vacuum ultraviolet light irradiation is subjected to some change to obtain a dense film as a whole. For example, in the case of a coating film by applying a polysilazane solution, the conversion reaction of polysilazane to silicon oxide or silicon oxynitride is applicable, and the modification treatment is applied to the physical properties such as film composition change and gas barrier performance derived therefrom. It can be confirmed from the improvement. In the case of a film formed by sputtering, vapor deposition, plasma CVD, or sol-gel method, whether or not the modification treatment has been performed can be confirmed by checking whether the gas barrier performance or the insulation performance has improved from before the treatment. .

According to the reforming method of the present invention, by using vacuum ultraviolet rays generated by plasma of a specific gas, at least one of an oxide film containing at least one of Si, Al, and Ti, a nitride film, a nitrided oxide film, and a carbonated film is used. A laminate including one layer can be modified to the inside, and a denser film can be produced in a short time. As a result, the productivity of the modified laminate can be improved. Moreover, since the obtained film is denser and the degree of modification is high, in the case of a gas barrier film, a film having improved heat and moisture resistance can be obtained.

In the modification step of the present invention, the vacuum ultraviolet light that exposes the laminate is characterized by being generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Hereinafter, a gas type used for generating vacuum ultraviolet light, a power supply frequency for generating vacuum ultraviolet light, and a plasma generation method will be described.

[Gas type]
By using a gas containing at least one of CO, CO ₂ and CH ₄ for plasma generation, emission of vacuum ultraviolet light having a peak wavelength exceeding 150 nm can be obtained. A preferred embodiment of the present invention is a modification method in which the peak wavelength of the vacuum ultraviolet light at a wavelength of 100 nm or more and less than 200 nm exceeds 150 nm. Such vacuum ultraviolet light is generated near the surface of the laminated body, and the laminated body can be exposed to this, compared with the case of using a vacuum ultraviolet light lamp. It can reach more inside. Therefore, the degree of modification of the entire film of the laminate can be increased, and a denser film can be produced in a short time. Furthermore, since the peak wavelength of the light emission is in the region exceeding 150 nm, the vacuum ultraviolet light reaches the inside of the film, and the chemical bonds constituting the film on the surface of the laminate are unnecessarily cut to cause defects in the film. Can be avoided. Of CO, CO ₂ and CH ₄ , CO or a combination of CO and CO ₂ is more preferable in order to achieve the intended effect of the present invention more reliably.

In the modification method of the present invention, the laminate is modified by exposing it to vacuum ultraviolet light from plasma, but it is more preferable to expose the laminate simultaneously to the plasma itself generating vacuum ultraviolet light. That is, a preferred embodiment of the present invention is a method in which at least one layer of the above-described oxide film, nitride film, oxynitride film, and carbonation film containing at least one of Si, Al, and Ti is further formed into plasma simultaneously with vacuum ultraviolet light. It is a modification method that is exposed to water. In this case, since the surface of the laminate is modified by plasma, the time required for the modification can be further shortened. In addition, the amount of oxidation of the film can be controlled by intentionally exposing the film surface to O radicals and ions, so that the film quality can be easily adjusted, and in the case of a gas barrier film, the heat and moisture resistance can be improved. . In order to expose the laminate to the plasma, the distance between the gas generating the plasma and the surface of the laminate may be adjusted.

Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. That is, a preferred embodiment of the present invention is a reforming method in which the gas further contains a rare gas or H ₂ . This is because when the rare gas or H ₂ is used as the main gas, the excitation efficiency of the carbon-containing gas added due to the Penning effect is improved and strong emission intensity is obtained, rather than using the carbon-containing gas alone. In particular, when CO and / or CO ₂ is used as the carbon-containing gas, it is preferable because stronger emission intensity can be obtained than when the carbon-containing gas is used alone.

Concentration of adding a carbon-containing gas to the rare gas or _{H 2} is preferably added 0.1 ~ 20 vol% of a rare gas or _{H 2,} and more preferably from 0.1 ~ 5 vol%. If the concentration of the carbon-containing gas is higher than the above range, the carbon-containing gas to which the emitted vacuum ultraviolet light is added may be self-absorbed, and the vacuum ultraviolet light reaching the film is reduced, preferably Absent. On the other hand, if the amount is too small, the amount of carbon-containing gas that is a light-emitting source is reduced, so that the amount of generated vacuum ultraviolet light exceeding 150 nm is reduced, and strong emission intensity may not be obtained. The rare gas is preferably Ar, Ne, Xe, or Kr in view of availability and ease of handling. A preferred embodiment of the present invention is a reforming method in which the rare gas is at least one of Ar, Ne, Xe and Kr.

The carbon-containing gas preferably further contains a gas that generates ultraviolet light having a wavelength of 200 nm to 300 nm by plasma. That is, a preferred embodiment of the present invention is a reforming method that further includes a gas that generates ultraviolet light having a wavelength of 200 nm to 300 nm by plasma. By including such a gas, the laminate is irradiated with ultraviolet light together with vacuum ultraviolet light. Therefore, vacuum ultraviolet light reaches the surface from the outermost surface of the film, and ultraviolet light reaches the inside of the film more inside. Can be modified. As a result, the time required for the reforming process can be further shortened. As a gas that generates ultraviolet light having a wavelength of 200 nm or more and 300 nm or less by plasma, a nitrogen-containing gas is preferable, and at least one of NO, N ₂ O, NO _2, and NH ₃ is preferable. That is, a preferred embodiment of the present invention is a reforming method in which the gas that generates ultraviolet light having a wavelength of 200 nm or more and 300 nm or less is a nitrogen-containing gas. Furthermore, a preferred embodiment of the present invention is a reforming method in which the nitrogen-containing gas is at least one of NO, N ₂ O, NO ₂ and NH ₃ . Among these, NO is conventionally known to obtain an emission spectrum called a γ spectrum from 150 nm to 230 nm. Therefore, considering that ultraviolet light can be generated strongly, NO is more preferable. When NO is turned into plasma, it generates ultraviolet light having a wavelength of 200 to 250 nm. For example, the SiO ₂ film has a high absorption rate at a wavelength of 200 nm or less, and most of the vacuum ultraviolet light is absorbed in the vicinity of the surface (up to 50 nm depth), so that the light does not reach the inside of the film and reaches the inside of the film. The reform does not progress. Therefore, it can be modified into the film by combining ultraviolet irradiation with a wavelength longer than that of light outside the vacuum. By generating ultraviolet light simultaneously with vacuum ultraviolet light, not only the surface but also the inside of the film can be modified at the same time, which is preferable because the processing time can be shortened.

The nitrogen-containing gas is preferably 0.01 to 50 vol%, more preferably 0.05 to 10 vol% with respect to the carbon-containing gas. Even when a nitrogen-containing gas is used, it is more preferable to expose the laminate to the plasma itself as described above.

Furthermore, it is preferable to add a trace amount of an oxidizing gas such as CO ₂ , O _2, H ₂ O, or H ₂ gas to the carbon-containing gas. CO generates a carbon compound by plasma, and there is a possibility that the carbon compound adheres to the surface of the laminate to be treated. Therefore, in order to remove the carbon compound, it is preferable to add a small amount of oxidizing gas or H ₂ gas. Further, it is preferable to add H ₂ O or H ₂ gas because H atoms and H radicals are also generated by the plasma to promote the dehydration condensation reaction on the film surface. A preferable amount of H ₂ O or H ₂ gas added is 0.01 to 1 vol% with respect to a rare gas when a rare gas is used, and 0.01 to 1% with respect to a carbon-containing gas when a rare gas is not used. It is 50 vol%. Further, H ₂ O or H ₂ gas may be added together with the nitrogen-containing gas. In addition, when a rare gas such as Ar, Xe, Ne, or Kr is used as the main gas, vacuum ultraviolet light of 150 nm or less due to the rare gas may be generated. There is a possibility of modification to a film that impairs the properties. However, since O ₂ and CO ₂ absorb vacuum ultraviolet light of 150 nm or less, they also serve to block vacuum ultraviolet light having a wavelength of 150 nm or less that reaches the laminate. In particular, CO ₂ is preferable as an oxidizing gas because it generates ultraviolet light of 200 nm or more and 250 nm or less in plasma, and also generates vacuum ultraviolet light because it generates CO when decomposed by plasma. A preferable amount of O ₂ is 1 to 100 vol%, more preferably 1 to 30 vol%, with respect to the carbon-containing gas.

In addition, the purity of the gas used is preferably 99.9 or higher, more preferably 99.99% or higher.

Although the pressure of the whole gas introduced for the reforming treatment varies depending on the plasma generation method, it is preferably 1 to 1000 Pa, more preferably 5 to 400 Pa in the case of CCP and ICP. In the case of microwave plasma, it is preferably 1 to 100 kPa, more preferably 100 to 20 kPa. In addition, the time for irradiation with vacuum ultraviolet light and / or plasma depends on the plasma generation method, but the shorter the time from the viewpoint of productivity, the higher the production capacity, and thus the more preferable.

In the present invention, a plasma processing apparatus that forms plasma at or near the atmospheric pressure as described in Japanese Patent No. 4000830 and Japanese Patent No. 4433680 can also be used. The atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa, and 93 kPa to 104 kPa is preferable in order to obtain the good effects described in the present invention.

[Power frequency]
The frequency of the power source required for generating low-pressure plasma that emits vacuum ultraviolet light (hereinafter also referred to as VUV) having peak illuminance in the wavelength range exceeding 150 nm used in the present invention is preferably 10 kHz to 100 GHz. At a frequency of 1 MHz or higher, ions cannot follow the change in the electric field, so that energy can be efficiently given to the electrons, and the electron density, that is, the plasma density increases. Along with this, the intensity of VUV generated by plasma also increases. However, if it exceeds 100 GHz, it becomes difficult for electrons to follow changes in the electric field, and in order to ensure energy transfer efficiency, 100 GHz or less is suitable. Preferably, it is in the range of 50 kHz to 10 GHz.

[Plasma generation method]
As a method for generating plasma that emits VUV having a wavelength exceeding 150 nm used in the present invention, a conventionally known method can be used. Preferably, a method that can deal with the treatment of a film formed on a wide substrate is good, and examples thereof include the following methods (A) to (E).

(A) Capacitively coupled plasma (CCP)
In this method, plasma is generated between the electrode to which high-frequency power is applied and the ground electrode. The opposed plate electrodes are a typical electrode structure. The electrode on the side to which the high-frequency power is applied is not limited to a flat plate shape, and for example, an electrode having a concavo-convex shape as disclosed in JP-A-2-113521 can be used. By providing a concavo-convex shape on the plate electrode, the plasma density can be increased due to the electric field concentration at the protrusion and the effect of the hollow cathode, and the intensity of VUV having a peak illuminance in the range exceeding 150 nm generated by the plasma is also increased. Become stronger.

(B) Capacitively coupled plasma combined with magnetron In the present invention, capacitively coupled plasma using magnetron as described below can also be used. By installing the magnetron, the plasma can be easily converged, the plasma density can be increased, and the intensity of VUV having a peak illuminance at 150 nm or more generated in the plasma is also increased. Further, since the ions generated in the plasma are accelerated by the magnetic field and the bombardment effect becomes stronger than the above (A), further improvement in modification can be expected. Further, it is preferable to use a roll electrode because it can be continuously processed and irradiated twice with one discharge. The magnetron combined capacitively coupled plasma will be described below.

As a configuration example of a capacitively coupled plasma apparatus used in combination with a magnetron, one described in JP-A-11-61416 can be used. A schematic diagram of such a magnetron combined capacitively coupled plasma generator is shown in FIG.

In FIG. 1, the magnetic field forming member 11 is provided inside the reforming roll, on the side of the electrode 7 disposed facing the reforming roll, in a range corresponding to at least the size of the electrode 7. The short-circuit member 3 is attached so as to generate a uniform magnetic flux. Thus, the electrons trapped in the magnetic flux generated from the magnetic field forming member through the non-magnetic reforming roll 4 occur near the surface of the film on which the plasma travels and are reformed. When a high frequency potential is applied from the plasma forming power source 5, it is configured to be applied only to the reforming roll 4. The magnetic field generating member 11 includes a central magnetic field 1, an outer peripheral magnetic field 2 having a polarity different from that of the central magnetic field, and a magnetic field short-circuit member 3 that supports them. The reforming roll 4 is provided with a magnetic field generating member 11 so that the positional relationship is maintained even when the roll rotates. The electrode 7 is disposed along a part of the surface of the reforming roll 4 so as to face the surface, and includes a plurality of gas introduction holes. A discharge gas is introduced from the introduction hole into the surface of the film S by the gas supply pipe 6. Thus, plasma is generated where the plasma forming power source 5 is maintained and the magnetic field forming member 3 has a magnetic flux outside the reforming roll 4.

In the present invention, the capacitively coupled plasma apparatus combined with the magnetron described in Japanese Patent Application Laid-Open No. 2008-196001 can also be used. As a configuration example of such an apparatus, a schematic diagram is shown in FIG. In FIG. 2, a base material S having a strip-like film that is wound in a roll shape passes over a pair of reforming rolls 4 and 4 'that are arranged to face each other so that the roll axes are parallel to each other. It is configured. Further, magnetic field generating members 11 and 11 ′ are provided inside the respective reforming rolls 4 and 4 ′, and a plasma forming power source 5 for supplying plasma power to the reforming rolls 4 and 4 ′ is provided. . The reforming rolls 4 and 4 'are provided with magnetic field generating members 11 and 11' so that the positional relationship is maintained even when the rolls rotate. A plurality of gas ejection nozzles directed to the roll space 8 between the reforming rolls 4 and 4 ′ are provided with a gas supply pipe 6 in the length direction, and the vacuum exhaust port 9 is directly below the roll space 8. Is arranged.

A gas forming plasma is supplied from the gas supply pipe 6 to the roll space 8. In the plasma forming power source 5, one electrode is connected to one reforming roll 4 and the other electrode is connected to the other film forming roll 4 ′. The plasma forming power source 5 outputs a voltage whose polarity is alternately inverted. Thereby, plasma with high plasma density can be formed on the roll surfaces of the modified rolls 4 and 4 ′.

(C) Inductively coupled plasma (ICP)
A high frequency current is passed through the antenna coil, and plasma is generated by an induced electric field generated by a magnetic field generated by the coil. Generally, a higher electron density (plasma density) is obtained than capacitively coupled plasma. Either an external antenna type in which the antenna coil is placed outside the chamber through a dielectric window or an internal antenna type in which the antenna coil is installed in the chamber may be adopted. Moreover, in order to correspond to a wide base material, you may devise, such as arrange | positioning an antenna coil in an array form.

(D) Microwave plasma
A plasma generation method using a microwave can also be used in the present invention. From the viewpoint of treating a wide substrate, a line type microwave plasma generation method can be preferably used. As such a type of microwave plasma generator, one described in Japanese Patent Application Laid-Open No. 2006-269151 or Japanese Patent Application Laid-Open No. 2007-317499 can be used. In addition, since it is a plasma formation method that does not require an electrode on the substrate side, it is possible to perform modification only with vacuum ultraviolet light without exposing to plasma by sufficiently separating the substrate and the microwave plasma source. . By using a frequency in the microwave band, the plasma density is higher than that of the capacitive coupling type, and the intensity of vacuum ultraviolet light having a peak illuminance in the generated wavelength range exceeding 150 nm is increased. As a result, the time required for reforming can be shortened.

An example of a line-type microwave plasma generator is shown in FIG. 3, and an example of a case where a film is reformed using such a generator is shown in FIG. FIG. 3 is a diagram showing a schematic configuration of a microwave line plasma generation apparatus that introduces microwaves from both sides of a rectangular TE mode waveguide 24. Microwaves supplied from the first and second microwave generation sources 21a and 21b from both ends of the waveguide 24 are supplied via the waveguides 22a and 22b and the tapered waveguides 23a and 23b. The waveguides 22a and 22b are configured by combining a straight waveguide, a waveguide bend, and the like.

Also, an opening (not shown) on the slit is provided below the waveguide 24. By supplying gas to the gas processing chamber 26 (vacuum) through the gas supply pipe 25 in the vicinity of the slit portion, the gas is made into plasma by touching the microwave in the waveguide 24.

As shown in FIG. 4, in a preferred embodiment, the base material 32 provided with the film to be modified is unwound from the unwinding portion 34 and modified by the microwave plasma generator 31 as shown in FIG. Quality. After the modification, the base material 32 is wound up by the winding unit 35 through the guide roller 33.

[Pulse drive]
When generating plasma by the plasma generation method as described above, electric power may be applied in pulses. It is known that application by pulses makes it difficult to shift from glow discharge to arc discharge as compared to the case of continuous application, and uniform glow plasma can be formed with higher power or higher pressure. Therefore, vacuum ultraviolet light can be emitted more strongly by the discharge applied with electric power in a pulse. In particular, when the pressure is high, the number of molecules of the carbon-containing gas that is the source of vacuum ultraviolet light can be increased, which is effective in increasing the emission intensity. A preferable pulse frequency is 100 Hz to 500 kHz, more preferably 1 to 200 kHz. A preferred DUTY ratio is 10 to 80, more preferably 20 to 70.

[Other conditions]
In general, when the substrate temperature during vacuum ultraviolet light irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, for example, the substrate is deformed or its strength is deteriorated. It will be. Therefore, it is preferable to perform the reforming treatment around room temperature (25 ° C.). 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.

The reforming treatment of the present invention can be applied 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, the resin base material can be processed in a vacuum chamber equipped with the plasma generator as described above. Moreover, when a resin base material is a elongate film form, it can be ceramicized by exposing to a vacuum ultraviolet light continuously, conveying this.

(3) Other Steps The laminated body manufactured in the present invention includes the above-described oxide film, nitride film, oxynitride film, and carbonated film containing at least one of Si, Al, and Ti. It is preferable to have an intermediate layer between the substrate and these films, and the method of the present invention may further include a step for that purpose. The intermediate layer according to the present invention is not particularly limited as long as it has a layer structure, and includes, for example, an anchor coat layer, a smooth layer, a bleed-out layer, and the like. It is more preferable that the laminated body manufactured by this invention is equipped with these intermediate | middle layers according to a use on practical use. For example, in the case of a gas barrier film, it is more preferable to provide an anchor coat layer on the substrate surface for the purpose of improving the adhesion with the gas barrier layer. It is more preferable to provide a smooth layer between the base material and the gas barrier layer in order to flatten the rough surface of the base material surface and fill unevenness and pinholes. When a smooth layer is provided, the surface of the resin base material having a smooth layer for the purpose of suppressing the phenomenon that unreacted oligomers migrate to the surface from the resin base material and contaminate the contact surface. It is more preferable to provide a bleed-out layer on the opposite side of the surface.

In order to form these intermediate layers, a solution of the following materials can be applied to form a coating film, dried, and completed by ultraviolet light curing or the like as necessary.

Examples of the anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. These may be used alone or in combination of one or more.

Examples of the photopolymerizable monomer forming the smooth layer include a photopolymerizable monomer composition containing an acrylate compound having a radical reactive unsaturated compound, and a photopolymerizable monomer containing an acrylate compound and a mercapto compound having a thiol group. Examples thereof include a photopolymerizable monomer composition in which a polyfunctional acrylate monomer such as a composition, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate is dissolved. The bleed-out prevention layer may basically have the same configuration as the smooth layer.

The modification method of the present invention is particularly suitable for the production of a gas barrier film. However, it is suitable not only for the gas barrier film but also for the surface treatment of the substrate, the production of a passivation film or an insulating film. That is, the present invention also provides a laminate modified by the above-described modification method. In the case of the surface treatment of the substrate, the wettability can be improved in a short time as compared with the corona discharge treatment and the excimer lamp treatment. As the passivation film, a film containing at least one of Si, Al, and Ti is often used in the same manner as the gas barrier film, and plays a role of blocking the movement of the metal in the upper and lower layers of the passivation film. Therefore, the wet heat resistance of the gas barrier film is improved by the method of the present invention, i.e., the film can further block the permeation of oxygen and water vapor. The movement of metal ions larger than oxygen and water vapor can be further blocked. It is also known that the insulating film is manufactured by modifying an oxide film, a nitride film, a nitrogen oxide film, and a carbonated film containing at least one of Si, Al, and Ti, similarly to the gas barrier film. Therefore, according to the modification method of the present invention, it can be modified to the inside of the film, and the degree of modification of the whole film can be increased. Therefore, even when an insulating film is manufactured, the degree of modification is further increased. A dense film having excellent insulating properties can be obtained.

Hereinafter, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to the following examples.

<Preparation of sample>
(Base material)
A 125 μm thick polyester film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET Q83), which is a thermoplastic resin and is easily bonded on both sides, was used as a base material.

[Production of gas barrier film]
(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 substrate, and after applying with a die coater so that the film thickness after drying was 4 μm, drying conditions: 80 ° C., After drying for 3 minutes, curing was performed in air using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² 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 is applied to the opposite surface of the base material, and is applied with a die coater so that the film thickness after drying is 4 μm, followed by drying conditions; After drying at 80 ° C. for 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a smooth layer.

The maximum cross-sectional height Rt (p) at this time was 16 nm.

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

<Example 1>
[Production of Gas Barrier Film 1]
(Formation of polysilazane layer)
A polysilazane layer was applied and dried on the smooth layer surface of the film provided with the smooth layer and the bleed-out prevention layer to form a coating film. The coating solution containing a polysilazane compound contains 5% by mass of a non-catalytic perhydropolysilazane 20% by mass dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst. Perhydropolysilazane 20% by mass dibutyl ether solution (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed and used to adjust the amine catalyst to 1% by mass with respect to perhydropolysilazane. By diluting, it was prepared as a 5% by weight dibutyl ether solution of perhydropolysilazane. This solution was applied using a die coater at a line speed of 1.0 m / min, dried for 1 minute at a drying temperature of 50 ° C. and a drying atmosphere dew point of 10 ° C., and then dried at a drying temperature of 80 ° C. and a drying atmosphere dew point of 5 ° C. After partial drying, a polysilazane layer having a thickness of 150 nm was formed after drying.

<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1. In addition, the surface energy before a process was 55 mN / m.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: CO
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 1.0 second.

<Example 2>
[Preparation of gas barrier film 2]
A gas barrier film 2 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: CO ₂ (CO is 1 vol%)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 3 seconds.

<Example 3>
[Preparation of gas barrier film 3]
A gas barrier film 3 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO (CO is 1 vol%)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.5 seconds.

<Example 4>
[Production of Gas Barrier Film 4]
A gas barrier film 4 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO + CO ₂ (CO is 1 vol% with respect to Ar, CO ₂ is 10 vol% with respect to CO)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.3 seconds.

<Example 5>
[Preparation of gas barrier film 5]
A gas barrier film 5 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ne + CO (CO is 1 vol% with respect to Ne)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.5 seconds.

<Example 6>
[Production of Gas Barrier Film 6]
A gas barrier film 5 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Xe + CO (CO is 1 vol% with respect to Xe)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.3 seconds.

<Example 7>
[Preparation of gas barrier film 7]
A gas barrier film 5 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.

<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO + NO (CO, NO is 1 vol% with respect to Ar)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.2 seconds.

<Example 8>
[Preparation of gas barrier film 8]
A gas barrier film 7 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.

<Reforming treatment>
The gas barrier film 1 was produced by performing plasma irradiation treatment using the apparatus shown in FIG. 4 in which the microwave plasma generator shown in FIG. 3 was introduced to the produced polysilazane film under the following conditions. Note that the distance between the substrate and the plasma source was set to 150 mm so that the gas barrier film was not directly exposed to plasma.

Plasma processing apparatus: microwave plasma apparatus Distance between substrate and microwave plasma source: 150 mm
Gas: Ar + CO (CO is 1 vol%)
Pressure: 300Pa
Substrate heating temperature: room temperature Input power density: 2.5 kW / 500 mm width Frequency: 2.45 GHz
Processing time: 2.4 seconds Film transport speed: 10 m / min
In addition, since the discharge length in the conveyance direction of the base material is about 50 mm, the processing time is calculated as 50 / 166.6 (mm / sec) = processing when passing through the discharge space once. Since the discharge space is passed 10 times at a conveyance speed of 10 m / min, the process is performed for about 2.4 sec.

<Example 9>
[Preparation of gas barrier film 9]
A gas barrier film 7 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. In addition, the surface energy before a process was 55 mN / m.

<Reforming treatment>
The gas barrier film 1 was produced by performing plasma irradiation treatment using the apparatus shown in FIG. 4 in which the microwave plasma generator shown in FIG. 3 was introduced to the produced polysilazane film under the following conditions. Note that the distance between the substrate and the plasma source was set at 30 mm so that the gas barrier film was directly exposed to plasma.

Plasma processing device: microwave plasma device Distance between substrate and microwave plasma source: 30 mm
Gas: Ar + CO (CO is 1 vol%)
Pressure: 300Pa
Substrate heating temperature: room temperature Input power density: 2.5 kW / 500 mm width Frequency: 2.45 GHz
Processing time: 0.24 seconds Film transport speed 10 m / min
In addition, since the discharge length in the conveyance direction of the base material is about 50 mm, the processing time is calculated as 50 / 166.6 (mm / sec) = processing when passing through the discharge space once. Since the discharge space is passed once at a conveyance speed of 10 m / min, the processing is performed for about 0.24 sec.

<Example 10>
[Production of Gas Barrier Film 10]
A plastic film base material formed to the same smooth layer as that used in the gas barrier film 1 is set in a vacuum chamber of a sputtering apparatus, evacuated to 10-4 Pa level, and argon and oxygen are discharged at a partial pressure of 0 to a discharge gas. .5 Pa was introduced. When the atmospheric pressure was stabilized, discharge was started, plasma was generated on the Si target, and a sputtering process was started. When the process was stabilized, the shutter was opened and the formation of a silicon oxide layer on the film was started. When the 60 nm film was deposited, the shutter was closed and the film formation was completed. Then, the modification | reformation process described below was implemented and the gas barrier film 8 was produced. At this time, the gas barrier property of the substrate on which the SiO ₂ film before the modification treatment was formed was 0.01 g / m ² / day. The surface energy before the treatment was 58 mN / m.

<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO (CO is 1 vol%)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.5 seconds.

<Example 11>
[Production of Gas Barrier Film 11]
A plastic film base material formed to the same smooth layer as that used in the gas barrier film 1 is set in a vacuum chamber of a sputtering apparatus, evacuated to 10-4 Pa level, and argon and oxygen are discharged at a partial pressure of 0 to a discharge gas. .5 Pa was introduced. When the atmospheric pressure was stabilized, discharge was started to generate plasma on the Al target, and the sputtering process was started. When the process was stabilized, the shutter was opened and the formation of a silicon oxide layer on the film was started. When the 60 nm film was deposited, the shutter was closed and the film formation was completed. Then, the modification | reformation process described below was implemented and the gas barrier film 8 was produced. At this time, the gas barrier property of the base material on which Al ₂ O ₃ before reforming was formed was 0.1 g / m ² / day. The surface energy before the treatment was 60 mN / m.

<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO (CO is 1 vol%)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.5 seconds.

<Example 12>
[Production of Gas Barrier Film 12]
A plastic film base material formed to the same smooth layer as that used in the gas barrier film 1 is set in a vacuum chamber of a sputtering apparatus, evacuated to 10-4 Pa level, and argon and oxygen are discharged at a partial pressure of 0 to a discharge gas. .5 Pa was introduced. When the atmospheric pressure was stabilized, discharge was started to generate plasma on the Ti target, and the sputtering process was started. When the process was stabilized, the shutter was opened and the formation of a silicon oxide layer on the film was started. When the 60 nm film was deposited, the shutter was closed and the film formation was completed. Then, the modification | reformation process described below was implemented and the gas barrier film 8 was produced. At this time, the gas barrier property of the base material on which the TiO ₂ film before the modification treatment was formed was 0.08 g / m ² / day. The surface energy before the treatment was 62 mN / m.

<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar + CO (CO is 1 vol%)
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 0.5 seconds.

<Comparative Example 1>
[Preparation of gas barrier film 13]
A gas barrier film 10 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows. The surface energy before the treatment was 55 mN / m.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 10.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 30 seconds.

<Comparative Example 2>
[Production of Gas Barrier Film 14]
A gas barrier film 11 was produced in the same manner as the gas barrier film 1 except that the modification treatment was performed as follows.
<Reforming treatment>
(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 second 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: 0.1%
Film transport speed 0.6m / min
Excimer irradiation time: 5 seconds A gas barrier film was prepared as described above.

<Comparative Example 3>
[Production of Gas Barrier Film 15] SiO ₂ Treatment Gas barrier film 10 was produced in the same manner as gas barrier film 9 except that gas barrier film 9 was modified as described below.
<Reforming treatment>
The produced polysilazane film was subjected to low-pressure plasma treatment under the following conditions to produce a gas barrier film 1.
Plasma processing equipment: Low-pressure capacitively coupled plasma processing equipment (manufactured by UTEC Co., Ltd.)
Gas: Ar
Pressure: 10Pa
Substrate heating temperature: Room temperature Input power density: 2.0 W / cm ²
Frequency: 13.56MHz
Processing time: 20 seconds.

<Comparative example 4>
[Production of Gas Barrier Film 16] SiO ₂ Treatment Gas barrier film 10 was produced in the same manner as gas barrier film 9 except that gas barrier film 9 was modified as described below.
<Reforming treatment>
(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 second 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: 0.1%
Film transport speed 0.6m / min
Excimer irradiation time: 4 seconds A gas barrier film was produced in the manner described above.

<Comparative Example 5>
[Preparation of gas barrier film 17]
In the gas barrier film 1, a gas barrier film 14 was produced in the same manner as the gas barrier film 9 except that the modification treatment was performed as follows.
<Reforming treatment>
Reformer: Hot plate 100 ° C
Atmosphere: Oxygen concentration 0.1%
Processing time: 60 seconds.

<Evaluation>
The barrier film No. obtained as described above. 1 to 17 were evaluated as follows. The evaluation results are also shown in Table 1 below, and the evaluation criteria are shown in Table 2-1 and Table 2-2.

<Measurement of water vapor transmission rate>
The measurement was carried out using a water vapor permeability measuring apparatus (“AQUATRAN”, manufactured by MOCON) using an isobaric method-infrared sensor method in an atmosphere of 40 ° C. and 90% RH. The lower limit of detection of this device is 0.0005 g / m ² / day.

<Method for evaluating wet heat resistance>
[Moisture and heat resistance test]
Using a thermo-hygrostat, left for 100 hours to 300 hours under conditions of 85 ° C. and 85% RH, and then measured the water vapor transmission rate by the method described above. It was evaluated whether sex was maintained. In addition, the wet heat resistance was given Rank as follows.
○: Before and after the moist heat resistance test, A is less than 50 in the following formula. Δ: Before and after the moist heat resistance test, A is from 50 to 200. ×: Before and after the moist heat resistance test, A Has a change of 200 or more A = (water vapor transmission rate before wet heat test ÷ water vapor transmission rate after wet heat resistance × 100)
-100 (%).

<Surface roughness>
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.

<Γ measurement of surface free energy>
As an index of modification, surface free energy (hereinafter also referred to as surface energy) was evaluated. In this embodiment, the surface energy does not indicate the degree of modification of the entire film, but is used as an index for indicating how much processing time is required to modify the film on the outermost surface. As a method for quantitatively obtaining the surface energy of the treated surface before and after the modification treatment, the method described in “Nasakiaki Kitasaki et al., Journal of Japan Adhesion Society, Vol. 8, No. 3, 1972, pp. 131-141” is used. Using.

It is assumed that the surface energy is composed of a dispersion component γd, a polar component γp, and a hydrogen bonding component γh. The surface energy γ is
γ = γd + γp + γh
It is expressed.

The relationship between the liquid surface energy γl, the solid surface energy γs, and the contact angle θ is

Given in. The contact angle was measured using water, diiodomethane, and nitromethane with known γL, and the surface energy was determined. As the surface energy increases, the surface modification progresses.
The contact angle was measured using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.) to measure the static contact angle with a 2 mg mass droplet, and the surface energy was calculated using the equation (1).

<Method of measuring the wavelength and illuminance of the generated vacuum ultraviolet light>
The wavelength and intensity of the vacuum ultraviolet light were measured using a vacuum ultraviolet spectrometer vacuum apparatus (VM-504 manufactured by Acton, VTM300 manufactured by HORIBA Jobin Yvon).

As shown in Table 1 above, the examples to which the reforming method of the present invention was applied showed excellent gas barrier properties (low water vapor transmission rate) and wet heat resistance as compared with the comparative examples, and the treatment time. Was a short time. In contrast to Comparative Example 1 in which the introduced gas type is only Ar, Example 3 using a carbon-containing gas in addition to Ar is more excellent in that the peak wavelength of vacuum ultraviolet light is longer and the processing time is shortened. It exhibited gas barrier properties and heat and humidity resistance. In addition, compared to Example 1 in which the introduced gas was only CO, Example 3 in which Ar was added to CO further shortened the processing time. This is presumably because the emission of vacuum ultraviolet light was further enhanced by using the rare gas as the main gas. In addition, Example 7 in which NO, which is a nitrogen-containing gas, was further added to Ar and CO showed further superior gas barrier properties compared to Example 3 in which only Ar and CO were used. This is probably because the use of NO that emits ultraviolet light by plasma modified the polysilazane film to the inside in a short time and improved the gas barrier properties. Moreover, compared with Example 8 only with vacuum ultraviolet irradiation, Example 9 which irradiated the plasma in addition to the vacuum ultraviolet irradiation further shortened processing time.

Further, when attention is paid to the surface energy, the values are the same in Examples 1 to 12 and Comparative Examples 1 to 4. From this, it can be seen that according to the method of the present invention, in order to perform the surface modification equivalent to that according to the prior art, a very shortened processing time is required. Therefore, the modification method of the present invention is effective as a film surface treatment method because the treatment time is short and the productivity is high.

Note that this application is based on Japanese Patent Application No. 2012-231497 filed on October 19, 2012, the disclosure of which is incorporated by reference in its entirety.

1 Peripheral magnetic field (S pole)
2 Central magnetic field (N)
3 Magnetic field short- circuit member 4, 4 ′ reforming roll 5 Plasma forming power source 6, 25 Gas supply pipe 7 Electrode 8 Roll space 9 Vacuum exhaust port 11, 11 ′ Magnetic field generating members 21a, 21b Microwave power sources 22a, 22b Waveguide 23a 23b Tapered waveguide 24 Short waveguide 26 Gas processing chamber 31 Microwave plasma generator 32 Base material 33 Guide roller 34 Unwinding portion 35 Winding portion S Base material

Claims (11)

1. At least one of a laminate comprising a base material and an oxide film, nitride film, oxynitride film, and carbonation film containing at least one of Si, Al, and Ti formed on the base material. A reforming method for reforming a part,
   A modification step of modifying at least a part of the laminate by exposing the at least one layer of film to vacuum ultraviolet light;
   A reforming method, wherein the vacuum ultraviolet light is generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ .
2. The reforming method according to claim 1, wherein the at least one film is further exposed to the plasma simultaneously with the vacuum ultraviolet light.
3. The reforming method according to claim 1 or 2, wherein a peak wavelength of the vacuum ultraviolet light at a wavelength of 100 nm or more and less than 200 nm exceeds 150 nm.
4. The reforming method according to any one of claims 1 to 3, wherein the at least one film contains polysilazane.
5. The reforming method according to any one of claims 1 to 4, wherein the gas further contains a rare gas or H ₂ .
6. The reforming method according to claim 5, wherein the rare gas is at least one of Ar, Ne, Xe and Kr.
7. The reforming method according to any one of claims 1 to 6, wherein the gas further includes a gas that generates ultraviolet light having a wavelength of 200 nm to 300 nm by plasma.
8. The reforming method according to claim 7, wherein the gas generating ultraviolet light having a wavelength of 200 nm to 300 nm is a nitrogen-containing gas.
9. The reforming method according to claim 8, wherein the nitrogen-containing gas is at least one of NO, N ₂ O, NO _2, and NH ₃ .
10. The reforming method according to any one of claims 1 to 9, wherein the laminate is a gas barrier film.
11. A laminate modified by the modification method according to any one of claims 1 to 10.

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