JP2016172399A - Method for producing gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a gas barrier film having excellent adhesion even after stored for the long term under a high-temperature and high-humidity environment.SOLUTION: A method for producing a gas barrier film comprises the steps of forming a group 5 metal-containing layer on a cycloolefin polymer base material by gas phase film formation method; and drying a polysilazane-containing coating film formed on the group 5 metal-containing layer to form a gas barrier layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a gas barrier film.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.

  In addition to packaging applications, gas barrier films are required to be developed into flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, and liquid crystal display elements, and many studies have been made. However, these flexible electronic devices are required to have an extremely high gas barrier property at the glass substrate level. In particular, there is a demand for an organic EL device in which the generation of dark spots is suppressed even when stored for a long time in a high temperature and high humidity environment such as 85 ° C. and 85% RH.

  Here, in Patent Document 1, a clear hard coat layer is formed and cured on the surface of a cycloolefin polymer base material that has been hydrophilized by vacuum ultraviolet irradiation treatment, and a gas barrier layer is formed on the clear hard coat layer. A process for producing a gas barrier film characterized by the above is described. Patent Document 2 includes a silicon-containing film formed on a base material, and the silicon-containing film is modified by irradiating the polysilazane film with energy rays in an atmosphere substantially free of oxygen or water vapor. A laminated body having a high nitrogen concentration region is disclosed.

Japanese Patent Laying-Open No. 2015-024536 International Publication No. 2011/007543

  In Patent Document 1, a gas barrier film that has excellent flatness, excellent adhesion even after being stored for a long time in a high-humidity environment, and can maintain high gas barrier properties can be obtained. There existed the subject that the base material became weak, and there were many man-hours and work efficiency was not high. Moreover, when it preserve | saved in high temperature environments, such as 80 degreeC, there existed a subject that adhesiveness was not enough.

  In addition, the laminate described in Patent Document 2 has a problem that it does not have a high gas barrier property that suppresses the occurrence of dark spots of organic EL elements in a high temperature and high humidity environment such as 85 ° C. and 85% RH. It was.

  Then, this invention aims at providing the method of manufacturing efficiently the gas barrier film excellent in adhesiveness, even after preserve | saving for a long period of time in high temperature, high humidity environment like 85 degreeC85% RH. To do.

  The present inventor has intensively studied to solve the above problems. As a result, a step of forming a Group 5 metal-containing layer on the cycloolefin polymer substrate by a vapor deposition method; and a polysilazane-containing coating film formed on the Group 5 metal-containing layer is dried to form a gas barrier layer. It has been found that the above-mentioned problems can be solved by a method for producing a gas barrier film including a step of forming, and the present invention has been completed.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film excellent in durability in a high temperature, high humidity environment can be manufactured efficiently.

FIG. 1 is a schematic cross-sectional view showing a gas barrier film produced by a production method according to an embodiment of the present invention.

  In the production method according to the present invention, a step of forming a Group 5 metal-containing layer on a cycloolefin polymer substrate by a vapor deposition method; and a polysilazane-containing coating film formed on the Group 5 metal-containing layer is dried. And forming a gas barrier layer. By adopting the production method, a gas barrier film excellent in durability in a high-temperature and high-humidity environment can be produced efficiently. Hereinafter, although the mechanism estimated in this invention is described, the technical scope of this invention is not restrict | limited at all.

  Cycloolefin polymer substrate (film substrate based on cycloolefin polymer or cycloolefin copolymer; hereinafter, “cycloolefin polymer” is also referred to as “COP” and “cycloolefin copolymer” is also referred to as “COC”) is flexible When used as a base material for a gas barrier film for electronic devices, the retardation is low, and the moisture permeability is as low as 0.1 times that of PET and as low as 0.001 times that of a triacetyl cellulose film. There is an advantage. However, conventionally, a gas barrier film using a cycloolefin polymer base material has a gas barrier layer such as silica easily peeled off in a high-temperature and high-humidity environment, and has insufficient adhesion. For this reason, the quality of such a gas barrier film is easily deteriorated by pressure or the like, and it is difficult to maintain the quality. In addition, the gas barrier film using the cycloolefin polymer base material has a problem that dark spots are likely to occur when it is used for an organic EL device or the like, possibly due to low adhesion.

The inventor speculated that the decrease in adhesion in a high-temperature and high-humidity environment may be due to weak bonding between Si and O in the gas barrier layer. That is, when a gas barrier layer such as silica is formed on a cycloolefin polymer substrate, carbon (C) of the cycloolefin polymer substrate and oxygen (O) or silicon (Si) of the gas barrier layer are C—O—. It is considered that a bond of Si is formed. The present inventor has also considered the bonding of C—O—Si so that the siloxane bond is easily hydrolyzed in the presence of water (Si—O—Si + H ₂ O → Si—OH + HO—Si). It was speculated that the C—O bond could be easily broken in a high temperature and high humidity environment. In addition, it was speculated that the cycloolefin polymer base material being hydrophobic may contribute to a decrease in adhesion to a hydrophilic gas barrier film such as silica. Based on the above estimation, the present inventor has conducted extensive studies and found that the present inventor has provided a Group 5 metal-containing layer between the cycloolefin polymer substrate and the gas barrier layer, thereby increasing the temperature and the temperature as high as 85 ° C. and 85% RH. It has been found that a gas barrier layer having excellent adhesion can be obtained even in a wet environment. This is presumably because the Group 5 metal-containing layer is more easily oxidized than the gas barrier layer, and the oxidation of the gas barrier layer is suppressed by oxidizing the Group 5 metal-containing layer first.

  In addition, unlike the case of forming a gas barrier layer on a hydrophobic surface such as a cycloolefin polymer substrate, it is also possible to form a gas barrier layer on a non-hydrophobic surface having many binding species such as a Group 5 metal-containing layer. It is presumed to be related to the improvement of adhesion.

  Further, by employing a vapor phase film forming method, the Group 5 metal-containing layer can be efficiently formed on the cycloolefin polymer substrate. Therefore, in the production method according to the present invention, the gas barrier property with excellent adhesion can be obtained without performing the hydrophilization treatment of the cycloolefin polymer substrate and the curing of the clear hard coat layer as in the production method described in Patent Document 1. Since the film can be produced, the production efficiency can be improved.

In a preferred embodiment of the present invention, the energy applied to the surface of the polysilazane-containing coating film is less than 0.1 mJ / cm ² . For example, as described in Patent Document 2, the gas barrier property of the gas barrier layer can be improved by performing a modification treatment such as energy ray irradiation on the polysilazane-containing coating film. However, the present inventor does not substantially modify in the step of drying the polysilazane-containing coating film formed on the Group 5 metal-containing layer to form a gas barrier layer, that is, the polysilazane-containing coating film. It has also been found that the adhesiveness can be further improved by setting the energy applied to the surface of the film to less than 0.1 mJ / cm ² . Although the details are unknown, it is assumed that this is the following mechanism. That is, when a substrate that is difficult to absorb moisture, such as a cycloolefin polymer substrate, is applied to the polysilazane-containing coating film by applying energy, the polysilazane coating film shrinks and distortion is likely to occur. it is conceivable that. Therefore, it is considered that the energy applied to the surface of the polysilazane-containing coating film is less than 0.1 mJ / cm ² , so that the above-described shrinkage of the polysilazane coating film and generation of strain can be prevented. . Furthermore, there is an advantage that the production efficiency can be further improved by substantially not performing the modification treatment in the step of forming the gas barrier layer.

  Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In the present specification, unless otherwise specified, measurement of operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

  FIG. 1 is a schematic cross-sectional view showing a gas barrier film produced by a production method according to an embodiment of the present invention. In the gas barrier film 10 of FIG. 1, a base material 11, a Group 5 metal-containing layer 12, and a gas barrier layer 13 are arranged in this order. The gas barrier film 10 is composed of three layers of a base material 11, a Group 5 metal-containing layer 12 and a gas barrier layer 13, but the gas barrier film produced by the production method according to the present invention consists of only the three layers. For example, in the gas barrier film 10, the Group 5 metal-containing layer 12 is formed adjacent to the base material 11, but the base material 11 and the Group 5 metal-containing layer 12 are not limited to the configuration. There may be included layers having various functions described later. Further, another functional layer such as a hard coat layer may be formed on the surface layer of the gas barrier layer.

<Step of forming a Group 5 metal-containing layer>
The production method according to the present invention is also referred to as a step of forming a Group 5 metal-containing layer on a cycloolefin polymer substrate by a vapor deposition method (hereinafter simply referred to as “step of forming a Group 5 metal-containing layer”). )including.

(Cycloolefin polymer substrate)
In the production method according to the present invention, a cycloolefin polymer base material containing a cycloolefin polymer or a cycloolefin copolymer as a main component is used. The cycloolefin polymer substrate is not only flexible, but also has the advantage of low retardation and moisture permeability.

  In the present invention, “main component” means that the proportion of COP and COC in the resin component constituting the substrate is 60% by mass or more. The ratio of COP and COC contained in the cycloolefin polymer substrate is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more (the upper limit is 100% by mass). .

  The cycloolefin polymer substrate used in the present invention has low moisture permeability as compared with a polyethylene terephthalate film that has been widely used heretofore, and has excellent light transmittance (transparency). For this reason, when it uses for an organic EL element, luminous efficiency can improve. Furthermore, since the cycloolefin polymer base material has low retardation, there is an advantage that the color viewing angle dependency is small when used for an organic EL device.

  As a polymerization method of cycloolefin, a method of addition polymerization of cycloolefin with α-olefin or the like (Method A) and a method by ring-opening polymerization of cycloolefin (Method B) are known. Method A provides a cycloolefin copolymer (COC) and Method B provides a cycloolefin polymer (COP). The polymerization reaction is usually performed in the presence of a catalyst.

As the main component of the film substrate used in the present invention, a resin obtained by polymerizing or copolymerizing cycloolefin is used. As the cycloolefin, for example, norbornene, dicyclopentadiene, tetracyclododecene, ethyl tetracyclododecene, ethylidene tetracyclododecene, tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7 ] polycyclic unsaturated hydrocarbons such as trideca-2,4,6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- Unsaturated hydrocarbons having a monocyclic structure such as (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene And derivatives thereof. These cycloolefins may have a polar group as a substituent. Examples of the polar group include a hydroxy group, a carboxy group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. , A carboxy group or a carboxylic anhydride group is preferred.

  As the main component of the film substrate used in the present invention, a cycloolefin copolymer obtained by addition copolymerization of a monomer other than cycloolefin is also preferably used. Examples of addition copolymerizable monomers include chain olefins such as ethylene, propylene, 1-butene and 1-pentene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

  The main component of the film substrate used in the present invention is preferably one obtained by polymerizing or copolymerizing cycloolefin and then hydrogenating it to convert unsaturated bonds in the molecule into saturated bonds. The hydrogenation reaction may be performed by blowing hydrogen in the presence of a known hydrogenation catalyst.

  A commercial item can also be used as a cycloolefin polymer and a cycloolefin copolymer. Examples of such commercially available products include ZEONOR (registered trademark), ZEONEX (registered trademark) (Nippon Zeon Co., Ltd.), Arton (registered trademark) (JSR Co., Ltd.), Essina (registered trademark) (Sekisui Chemical Co., Ltd.). And Apel (registered trademark) (Mitsui Chemicals).

  As a method for producing a cycloolefin polymer base material, a normal inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, a hot press method, or the like can be used. The conventionally known solution casting film forming method or melt casting film forming method can be selected.

  The surface of the cycloolefin polymer base material may be subjected to various known treatments for improving adhesion, such as ultraviolet irradiation treatment, corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, as necessary. The above processes may be combined.

  The thickness of the cycloolefin polymer substrate is, for example, 10 to 500 μm, and preferably 25 to 150 μm.

(Group 5 metal-containing layer)
In the production method according to the present invention, a Group 5 metal-containing layer (hereinafter, also referred to as “layer (A)”) is formed on the cycloolefin polymer substrate by a vapor deposition method.

  The Group 5 metal contained in the layer (A) may be in a metal state, for example, a state of a compound such as an oxide, nitride, carbide, oxynitride, or oxycarbide of the Group 5 metal. It may be. Among these, from the viewpoint that oxidation of the gas barrier layer can be more effectively suppressed, the Group 5 metal compound is preferably a Group 5 metal oxide. Group 5 metals may be used alone or in combination of two or more.

The layer (A) is a metal in which n1 ≦ ((3/5) × n2), where M is a Group 5 metal and MO _n2 is a Group 5 metal oxide obtained stoichiometrically. The oxide MO _n1 is preferably included. By including such a metal oxide, the gas barrier performance of the gas barrier film is improved, and high gas barrier performance is maintained even under high temperature and high humidity conditions. By including the metal oxide MO _{n1 in} which n1 ≦ ((3/5) × n2), there is a region having an oxidation degree lower than the stoichiometric oxidation degree, that is, a region having a room for further oxidation. Therefore, it is considered that higher gas barrier performance is exhibited.

The inclusion of the metal oxide MO _n1 satisfying n1 ≦ ((3/5) × n2) means that when the composition profile in the thickness direction is measured by a composition analysis method such as XPS, n1 ≦ ((3/5) Xn2) means that a measurement point is obtained, and in the case of Nb, it means that a measurement point where n ≦ 1.5 is obtained. Even when the layer (A) contains a plurality of types of metals, the stoichiometric n2 can be calculated and used from the ratio of each metal and the total thereof.

  The n1 / n2 ratio can be adjusted by using a metal or a group 5 metal oxide that is stoichiometrically deficient in oxygen as a target when the layer (A) is formed by sputtering. This can be done by appropriately adjusting the amount of oxygen to be introduced.

n1 can be determined by the atomic ratio of O to M using XPS analysis in the thickness direction. If the minimum value of n1 is n1 ≦ (3/5 × n2), it can be said that the layer (A) includes the metal oxide MO _n1 where n1 ≦ (3/5 × n2).

<< XPS analysis conditions >>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Measurement area: Si2p, C1s, N1s, O1s, etc., set by a regular method according to the metal to be measured.
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so that the thickness is about 2.5 nm in terms of SiO _2.・ Quantification: The background is obtained by the Shirley method, and the relative sensitivity coefficient method is calculated from the obtained peak area. And quantified. Data processing uses MultiPak manufactured by ULVAC-PHI.

Group 5 metals include V, Nb, Ta, and Db. The Group 5 metal has a lower oxidation-reduction potential than silicon, and can effectively suppress oxidation of the gas barrier layer formed by drying the polysilazane-containing coating film. Among these, niobium and tantalum are particularly preferable as the Group 5 metal from the viewpoint of optical properties, because a compound having good transparency can be obtained. That is, in one embodiment of the present invention, the Group 5 metal is one or more selected from the group consisting of Nb and Ta. Niobium and tantalum may be oxides such as Nb ₂ O ₃ , Nb ₂ O ₅ , Ta ₂ O ₃ and Ta ₂ O ₅ .

  The standard redox potentials of major metals and n2 are shown in the table below.

  The content of the Group 5 metal in the layer (A) is not particularly limited as long as the effects of the present invention are exhibited. For example, the content of the Group 5 metal (in the case of a Group 5 metal compound, as the compound) is preferably 90% by mass or more, and 98% by mass or more based on the total mass of the layer (A). More preferably, the content is 100% by mass (that is, the layer (A) is made of a Group 5 metal or a Group 5 metal compound).

  The formation method of the layer (A) is a vapor phase film formation method from the viewpoint of easy adjustment of the composition ratio between the metal element and oxygen. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical vapor deposition), and ALD (Atomic Layer Deposition). Chemical vapor deposition methods such as Among them, it is preferable to form by sputtering since film formation is possible without damaging the lower layer and high productivity is obtained. That is, in one embodiment of the present invention, the Group 5 metal-containing layer is formed by sputtering.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. 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, a metal oxide film can be formed at a high film formation speed, which is preferable. For example, when performing DC sputtering or DMS sputtering, a Group 5 metal can be used as a target, and oxygen can be introduced into the process gas to form a Group 5 metal oxide thin film. . In the case of forming a film by RF (high frequency) sputtering, for example, a group 5 metal oxide target can be used. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide and carbon monoxide into the process gas, a Group 5 metal compound thin film such as Group 5 metal oxide, nitride, nitride oxide, carbonate, etc. is made. Can do.

  Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, film material, film thickness, and the like. A sputtering method using a Group 5 metal or a Group 5 metal oxide as a target is preferable because it has a higher film formation rate and higher productivity.

  More specifically, for example, an Nb target or a Ta target can be used as the target. In the present invention, the Nb target has an oxygen deficiency type (having a composition ratio on the oxygen deficiency side with respect to the stoichiometric ratio) from the viewpoint that conductivity is improved and film formation by DC sputtering can be performed and a high film formation speed can be obtained. ) It is preferable to use an Nb target.

  The layer (A) may be a single layer or a laminated structure of two or more layers. When the layer (A) has a laminated structure of two or more layers, the Group 5 metals contained in each layer (A) may be the same or different.

  Since the layer (A) is considered to have a function of suppressing the oxidation of the gas barrier layer and maintaining the gas barrier property, the gas barrier property is not necessarily required. Therefore, even if the layer (A) is a relatively thin layer, the effect can be exhibited. Specifically, the thickness of the layer (A) (the total thickness in the case of a laminated structure of two or more layers) is preferably 1 to 200 nm from the viewpoint of in-plane uniformity of the barrier property. More preferably, it is -150 nm, and it is further more preferable that it is 20-150 nm.

<Step of forming a gas barrier layer>
In the production method according to the present invention, a polysilazane-containing coating solution is applied onto the Group 5 metal-containing layer to form a coating film, and the coating film is dried to form a gas barrier layer.

(Polysilazane)
Polysilazane is a polymer having a silicon-nitrogen bond, and has a bond such as Si—N, Si—H, or N—H, SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _{y and the} like. Known as a ceramic precursor inorganic polymer.

  Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different.

In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ^″ and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, an organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like, and perhydropolysilazane may be selected, 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. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available 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 a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  Another example of the polysilazane that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827) or glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Fine particle added polysila Emissions, such as (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

  The content of polysilazane in the gas barrier layer can be 100% by mass when the total solid mass of the gas barrier layer is 100% by mass. When the gas barrier layer contains a solid content other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. Is more preferably 70% by mass or more and 95% by mass or less.

  The solvent for preparing the polysilazane-containing coating solution is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups that easily react with polysilazane (for example, hydroxyl groups or amine groups). An organic solvent inert to polysilazane is preferred, and an aprotic organic solvent is more preferred. Specifically, the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the polysilazane-containing coating solution is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, and still more preferably. It is 10-40 mass%.

  The following additives can be used in the polysilazane-containing coating solution as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

  As a method of applying the polysilazane-containing coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the preferred thickness and purpose. As an example, the thickness of the coating liquid (coating film) after drying (when forming a coating film a plurality of times, the thickness per one time) is preferably 40 nm or more and 1000 nm or less, more preferably 100 nm or more. 400 nm or less.

  After coating the coating solution, the coating film is dried. By drying the coating film, the organic solvent contained in the coating film can be reduced or removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. The drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  The coating film obtained by applying the polysilazane-containing coating solution may optionally include a step of removing moisture. The step of removing moisture may be performed during application of energy. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. 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. The preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the maintaining time depends on the film thickness of the gas barrier layer. It is preferable to set appropriately. Under the condition that the film thickness of the gas barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher.

(Energy application)
When a gas barrier layer is formed by drying a polysilazane-containing coating film, for example, as described in Patent Document 2 above, plasma treatment, ultraviolet irradiation treatment, or the like is modified on the polysilazane-containing coating film before or after drying. Quality processing is generally performed. By such a modification treatment, polysilazane is converted into silicon oxide or silicon oxynitride, and gas barrier properties can be improved. Also in the present invention, a modification treatment may be performed to improve gas barrier properties. However, in the production method according to the present invention, when the modification treatment of polysilazane is performed, the adhesion of the gas barrier layer to the cycloolefin polymer substrate may be lowered. Accordingly, in the production method according to the present invention, the polysilazane is formed by substantially forming the gas barrier layer without performing the modification treatment, that is, after the polysilazane-containing coating film is formed and dried to obtain a gas barrier film. The energy applied to the contained coating film is preferably less than 0.1 mJ / cm ² . That is, in one embodiment of the present invention, the energy applied to the polysilazane-containing coating film is less than 0.1 mJ / cm ² .

If the energy applied to the polysilazane-containing coating film is less than 0.1 mJ / cm ² , the oxidation conversion reaction of polysilazane does not proceed in the production process, and the adhesion can be improved. The energy applied to the polysilazane-containing coating film is more preferably 0.05 mJ / cm ² or less (lower limit is 0 mJ / cm ² ).

  In addition, the above-mentioned “substantially no modification treatment” means that plasma treatment, ultraviolet irradiation treatment, and 450 ° C. or higher, which will be described later, are applied in the steps from applying the polysilazane-containing coating solution to obtaining a gas barrier film. This means that heat treatment is not performed. For example, the application of energy that does not affect the modification of polysilazane such that the polysilazane coating film is exposed to visible light exceeding 400 nm is not prevented. The fact that the modification treatment is not substantially carried out is that the atomic ratio of the gas barrier layer in the obtained gas barrier film is measured, and the elemental ratio (at%) of nitrogen to silicon within 10 nm from the gas barrier layer surface layer is 0. It can be confirmed by being in the range of .9 to 1.0.

  When the polysilazane-containing coating film is modified, the conversion reaction of polysilazane to silicon oxide, silicon oxynitride, or the like can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or higher, so that it is difficult to adapt to a flexible substrate such as plastic. . For this reason, the heat treatment is preferably performed in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable. Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

(Plasma treatment)
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

The energy applied in the plasma treatment is, for example, 1 to 5000 mJ / cm ² in terms of the strength of the substrate surface.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation can be mentioned. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The conversion to ceramics is promoted, and the resulting gas barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to 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 375 nm. Use ultraviolet light.

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

For example, when a plastic film is used 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. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. As a base material temperature at the time of ultraviolet irradiation, those skilled in the art can set suitably by the kind of base material. 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. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. Moreover, when irradiating the generated ultraviolet rays to the gas barrier layer, it is preferable to apply the ultraviolet rays from the generation source to the gas barrier layer after reflecting the ultraviolet rays from the generation source with a reflecting plate from the viewpoint of improving efficiency and uniform irradiation.

  The ultraviolet 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 laminate having a gas 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. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. In addition, when the laminated body having the gas barrier layer on the surface is a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and gas barrier layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the modification treatment method may be a 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 with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above.

  The radiation source in the present invention is not limited as long as it generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (for example, Xe excimer lamp), and has an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. 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.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction during ultraviolet irradiation, but vacuum ultraviolet rays are absorbed by oxygen. For this reason, since the efficiency in the ultraviolet irradiation step is likely to decrease, it is preferable to perform the irradiation with vacuum ultraviolet rays in a state where the oxygen concentration and the water vapor concentration are as low as possible. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that can occur in the coating film and damage to the substrate can be reduced.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably 100 mJ / cm ^{2 to} 50 J / cm ² , more preferably 200 mJ / cm ^{2 to 20} J / cm ² , and 500 mJ / cm 2. More preferably, it is ^{2 to} 10 J / cm ² . If it is 100 mJ / cm ² or more, modification is sufficient, and if it is 50 J / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be suppressed.

Further, the vacuum ultraviolet ray to be used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . 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. Examples of plasma generation methods include capacitively coupled plasma.

  Note that the composition distribution and thickness in the thickness direction of the gas barrier layer can be determined by measuring by the following method using XPS (photoelectron spectroscopy) analysis.

Since the etching rate of the gas barrier layer varies depending on the composition, in the present invention, the thickness in the XPS analysis is obtained once based on the etching rate in terms of SiO ₂ , and based on the cross-sectional TEM image of the same sample, In the composition distribution in the thickness direction, the interface between each region of the formed region is specified to determine the thickness per region, and this is compared with the composition distribution in the thickness direction obtained from XPS analysis. Each region is identified, and the thickness of each region obtained from the XPS analysis corresponding to each region is equal to the thickness of each region obtained from the XPS analysis so that the thickness of each region obtained from the cross-sectional TEM image matches. The thickness direction is corrected by applying a uniform coefficient.

  The XPS analysis in the present invention was performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

  The measurement method according to the gist of the present invention is mainly resolution in the thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 1 to 15 nm. It is preferable that the thickness is 1 to 10 nm.

<< XPS analysis conditions >>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so that the thickness is about 2.8 nm in terms of SiO _2.・ Quantification: The background is obtained by the Shirley method, and the relative sensitivity coefficient method is calculated from the obtained peak area. And quantified. Data processing uses MultiPak manufactured by ULVAC-PHI.

  In this way, primary data of the profile of the composition distribution in the film thickness direction of the gas barrier layer is obtained.

  Moreover, the cross section of each sample is image | photographed with TEM, and each film thickness of a laminated structure is calculated | required. The composition distribution profile in the film thickness direction obtained above is corrected using the actual film thickness data obtained from the TEM image to obtain the composition distribution in the film thickness direction of the region. Based on this, the thickness of the region (c) is obtained.

  As a method for obtaining the thickness per region from the TEM image, a gas barrier film may be prepared by observing a cross-section TEM according to a conventional method after producing a thin piece by the following FIB processing apparatus. In this way, the thickness of each region can be calculated. An example that can be used for FIB processing and TEM observation is shown below.

《FIB processing》
・ Apparatus: SII SMI2050
・ Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
<< TEM observation >>
Apparatus: JEM2000FX (acceleration voltage: 200 kV) manufactured by JEOL Ltd.

  The gas barrier layer formed in the present invention may be a single layer or a laminated structure of two or more layers. When the gas barrier layer has a laminated structure of two or more layers, the gas barrier layers may have the same composition or different compositions.

  The thickness of the gas barrier layer (in the case of a laminated structure of two or more layers, the total thickness) is preferably 10 to 1000 nm, and more preferably 50 to 600 nm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the gas barrier layer can be measured by TEM observation.

<Layers with various functions>
The manufacturing method according to the present invention can include a step of providing layers having various functions.

(Anchor coat layer)
An anchor coat layer may be formed on the surface of the resin substrate on the side where the gas barrier layer is formed for the purpose of improving adhesion.

  As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

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 5.0 g / m ² (dry state).

  The anchor coat layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
The gas barrier film produced by the production method according to the present invention may have a smooth layer between the base material and the Group 5 metal-containing layer. The smooth layer used in the present invention flattens the rough surface of the resin base material on which protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. Provided for. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  As the photosensitive material 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. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. 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.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

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

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a barrier layer is apply | coated with an application | coating form, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability is impaired. In addition, it is easy to smooth the unevenness after coating.

(CHC layer)
In the gas barrier film produced by the production method according to the present invention, a clear hard coat layer (CHC layer) may be provided on the substrate surface. By providing the clear hard coat layer, the durability and smoothness of the gas barrier film can be improved.

  The curable resins used for forming the CHC layer include thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinyl benzyl resins, and ultraviolet curable resins. Examples include urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins.

  Also, the clear hard coat layer has fine particles of inorganic compounds such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide to adjust the scratch resistance, slipperiness and refractive index; or polymethacrylic acid Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder Further, an ultraviolet curable resin composition such as polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added. Moreover, in order to improve the heat resistance of a clear hard-coat layer, the antioxidant which does not suppress photocuring reaction can be selected and used. Further, the clear hard coat layer may contain a silicone-based surfactant or a polyoxyether compound or a fluorine-siloxane graft polymer.

  Examples of the organic solvent contained in the clear hard coat layer forming coating solution include hydrocarbons (eg, toluene, xylene, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), ketones. (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (for example, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, other organic solvents, or a mixture thereof. Available.

  The curable resin content contained in the clear hard coat layer forming coating solution is, for example, 5 to 80% by weight.

  The clear hard coat layer can be applied by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method using a clear hard coat layer forming coating solution. The layer thickness of the hard coat layer coating solution is, for example, 0.1 to 30 μm. Before applying the clear hard coat layer to the base material, it is preferable to subject the base material to surface treatment such as vacuum ultraviolet ray irradiation in advance.

A clear hard coat layer is formed by irradiating an active energy ray such as ultraviolet rays to the coating film formed by applying the clear hard coat layer forming coating solution to cure the effect resin. As a light source used for curing, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions are in the range of, for example, 50 to 2000 mJ / cm ² .

<Electronic device>
The gas barrier film produced by the production method of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, in one embodiment of the present invention, an electronic device including the gas barrier film manufactured by the above manufacturing method is provided.

  Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

[Comparative Example 1]
The gas barrier film 1 was obtained by the following method.

(Surface treatment of film substrate and formation of CHC layer)
ZEONOR (registered trademark) ZF14 (Nippon Zeon Co., Ltd., film thickness: 100 μm) was used as a cycloolefin polymer substrate.

The cycloolefin polymer substrate was surface treated by the following method to form a clear hard coat layer (CHC layer). That is, the gap between the discharge-like electrode of the corona discharge treatment apparatus (AGI-080, Kasuga Denki Co., Ltd.) and the cycloolefin polymer substrate is set to 1 mm, and the surface corona treatment is performed for 10 seconds under the condition that the treatment output is 600 mW / cm ^2. Went. Next, an ultraviolet curable resin-containing coating solution (purple UV-1700B, manufactured by Nippon Gosei Kagaku Co., Ltd.) containing polyurethane acrylate and acrylic acid as the main components on a cycloolefin polymer substrate subjected to corona treatment, using a wet coater. Then, it was applied so as to have a dry film thickness of 4 μm. Then, using a high-pressure mercury lamp in the atmosphere on the coating film dried at 80 ° C. for 3 minutes, the UV curable resin is cured under the condition of 1.0 J / cm ² , and a clear hard coat layer (CHC layer) is formed. Formed.

(Formation of gas barrier layer)
A polysilazane-containing coating solution as shown below was applied on the clear hard coat layer (CHC layer) to form a coating film, and then dried.

  A 10% by mass dibutyl ether solution of perhydropolysilazane (PHPS; Aquamica NN120-10, non-catalytic type, AZ Electronic Materials Co., Ltd.) was prepared as a polysilazane-containing coating solution. The prepared polysilazane-containing coating solution is coated on the clear hard coat layer with a wireless bar so that the average layer thickness after drying is 300 nm, and treated for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. And dried. Furthermore, it was kept in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) for 10 minutes to perform a dehumidification treatment to form a polysilazane-containing dry coating film.

Subsequently, the polysilazane-containing dry coating film was subjected to an excimer light irradiation treatment under the following conditions to perform a modification treatment to form a gas barrier layer;
Ultraviolet irradiation device: excimer light irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp 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 apparatus: 1.0% (v / v)
Excimer lamp irradiation time: 5 seconds.

[Comparative Example 2]
The gas barrier film 2 was obtained by the following method.

(Formation of zirconium-containing layer)
ZEONOR (registered trademark) ZF14 (Nippon Zeon Co., Ltd., film thickness: 100 μm) was used as a cycloolefin polymer substrate.

  Using the above magnetron sputtering apparatus, the following film formation conditions No. A zirconium-containing layer was formed on the cycloolefin polymer substrate under the condition of M1.

Deposition conditions No. M1: ZrOx, x = 2 conditions A Zr target was used as a target, and a film was formed by DC sputtering using Ar and O ₂ as process gases. The condition of the composition was determined by adjusting the oxygen partial pressure by film formation using a glass substrate in advance, and the condition that the composition near the depth of 10 nm from the surface layer was ZrO ₂ was found. By applying this condition, a film was formed with a thickness of 15 nm.

(Formation of gas barrier layer)
According to the method of Comparative Example 1, a polysilazane-containing dry coating film was formed on the zirconium-containing layer, and a gas barrier layer was formed by performing a modification treatment.

[Example 1]
Instead of the zirconium-containing layer, the following film formation conditions No. A gas barrier film 3 was obtained in the same manner as in Comparative Example 2, except that a Group 5 metal-containing layer was formed on the cycloolefin polymer substrate under the condition of M2.

Deposition conditions No. M2: NbOx, x = 1.5 Condition An oxygen-deficient Nb target (conductive Nb ₂ O ₅ target (manufactured by Mitsubishi Materials)) is used as a target, and process sputtering is performed by DC sputtering using Ar and O _2. Filmed. The condition of the composition was determined by adjusting the oxygen partial pressure by film formation using a glass substrate in advance, and the condition that the composition in the vicinity of a depth of 10 nm from the surface layer was NbO _1.5 was found. By applying this condition, a film was formed with a thickness of 15 nm.

[Example 2]
A gas barrier film 4 was obtained in the same manner as in Example 1 except that the modification treatment of the polysilazane-containing dry coating film was not performed.

[Example 3]
A gas barrier film 5 was obtained in the same manner as in Example 1 except that an F film (manufactured by Gunze Co., Ltd., film thickness: 100 μm, mainly composed of cycloolefin copolymer) was used as the cycloolefin polymer substrate.

[Example 4]
The formation conditions of the Group 5 metal-containing layer are set as film formation conditions No. A gas barrier film 6 was obtained in the same manner as in Example 2 except for changing to M3.

Deposition conditions No. M3: TaOx, x = 2.5 conditions A Ta target was used as a target, and a film was formed by DC sputtering using Ar and O ₂ as process gases. The conditions of the composition were determined by adjusting the oxygen partial pressure by film formation using a glass substrate in advance, and the condition was found that the composition near the depth of 10 nm from the surface layer was TaO _2.5 . By applying this condition, a film was formed with a thickness of 15 nm.

[Example 5]
A gas barrier film 7 was obtained in the same manner as in Example 3 except that the modification treatment of the polysilazane-containing dry coating film was not performed.

≪Method for manufacturing organic EL element≫
Using the gas barrier films 1 to 7 described above, bottom emission type organic electroluminescence elements (organic EL elements) were produced by the method as described below so that the area of the light emitting region was 5 cm × 5 cm.

(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.

Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(Organic functional layer-second electrode)
Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.

  Next, compound A-3 (blue light-emitting dopant), compound A-1 (green light-emitting dopant), compound A-2 (red light-emitting dopant) and compound H-1 (host compound), compound A-3 is film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35% by mass to 5% by mass, and the compound A-1 and the compound A-2 each had a concentration of 0.2% by mass without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate depending on the location from 64.6% to 94.6% by mass. A light emitting layer was formed.

  Thereafter, Compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.

  The compound 118, compound HT-1, compound A-1 to compound 3, compound H-1, and compound ET-1 are the compounds shown below.

(Solid sealing)
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a decompression condition of 0.1 MPa at 90 ° C. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration is 0.00. It was performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

  In this way, four electronic devices each having a light emitting region size of 5 cm × 5 cm were prepared for each gas barrier film.

(Dark spot (DS) evaluation)
The organic EL element obtained as described above was energized in an environment of 85 ° C. and 85% RH. The number of occurrences of dark spots having a circle-equivalent diameter of 300 μm or more was determined by averaging four devices.

Specifically, the organic EL elements 1 to 7 were made to emit light by applying a current of 1 mA / cm ² . Next, as for the light emission state immediately after application and after continuous light emission at 200 ° C. and 500 hours as the light emission time in an environment of 85 ° C. and 85% RH, a 100 × optical microscope (MS-804 manufactured by Moritex Corporation, A part of the organic EL element was magnified and photographed with a lens MP-ZE25-200). Next, the photographed image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.

5: No generation of dark spots was observed even in the sample after 500 hours of light emission 4: No occurrence of dark spots was observed in the sample after emission of 200 hours, but it was slightly observed in the sample after emission of 500 hours Generation of dark spots is observed (generation area 0.1% or more, less than 3.0%)
3: Slight dark spots are observed in the sample after 200 hours of light emission (generation area 0.1% or more and less than 3.0%)
2: Generation of clear dark spots is observed in the sample after 200 hours of light emission (generation area of 3.0% or more and less than 6.0%)
1: Generation of many dark spots is observed in the sample after 200 hours of light emission (generation area of 6.0% or more)

10 Gas barrier film,
11 cycloolefin polymer substrate,
12 Group 5 metal-containing layer,
13 Gas barrier layer.

Claims (5)

Forming a Group 5 metal-containing layer on the cycloolefin polymer substrate by a vapor deposition method; and drying a polysilazane-containing coating formed on the Group 5 metal-containing layer to form a gas barrier layer ;
A method for producing a gas barrier film, comprising: The manufacturing method of the gas-barrier film of Claim 1 whose energy applied to the said polysilazane containing coating film is less than 0.1 mJ / cm < ² >.   The method for producing a gas barrier film according to claim 1 or 2, wherein the Group 5 metal is at least one selected from the group consisting of Nb and Ta.   The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the Group 5 metal-containing layer is formed by a sputtering method.   The electronic device containing the gas barrier film manufactured by the manufacturing method of any one of Claims 1-4.