JP4590997B2 - Substrate film for display and organic electroluminescence device - Google Patents

Description

  The present invention relates to a transparent film for a display substrate having a gas barrier laminate film having excellent water vapor barrier properties, high flexibility and excellent productivity, and a long-life organic electroluminescence device using the transparent film for display substrates It relates to the manufacturing method.

  Conventional liquid crystal display elements, organic electroluminescence elements (organic EL elements), substrates for flat panel display elements such as plasma displays and electronic paper, or substrates for electro-optical elements such as CCD and CMOS sensors, or substrates for solar cells, Glass has been used because of its high thermal stability, high transparency, and low water vapor permeability. Recently, however, with the widespread use of mobile phones or portable information terminals, there has been a demand for lightweight plastic substrates that are flexible and hard to break, with respect to glass that is easily broken and heavy.

  However, since the plastic substrate has gas permeability, it is difficult to apply to a use that deteriorates due to moisture or oxygen, such as an organic electroluminescence display device, and how to seal them. It was a problem.

  In order to suppress such permeation of water vapor and oxygen, it is known to provide a layer (gas barrier layer) that inhibits various gases from permeating the plastic substrate. As a layer having such a function, silicon oxide Film, silicon nitride film, silicon oxynitride film, silicon carbide film, aluminum oxide film, aluminum oxynitride film, titanium oxide film, zirconium oxide film, magnesium oxide film, boron nitride film, carbon nitride film, diamond-like carbon film, fluorine It is known that inorganic films such as magnesium fluoride and aluminum fluoride films are effective.

  Although these inorganic thin films have a high gas barrier property with a very thin film thickness of several tens to several hundreds of nanometers, a film with a higher gas barrier property can be obtained as the film thickness increases.

  However, the thicker the film thickness or the denser the inorganic thin film that is to improve the gas barrier properties, the higher the internal stress in the inorganic thin film, and the more easily it becomes brittle and susceptible to cracking from external impacts and bending, There was a problem that it was difficult to achieve both desired gas barrier properties and durability.

  To solve these problems, it is an organic thin film that is flexible and can relieve stress, and by overcoating a hard and brittle inorganic thin film, it can suppress the occurrence of cracks and pinholes due to external impact and film bending. The method is used. In Patent Document 1, an overcoat layer made of an acrylic resin obtained by vacuum-depositing a polyfunctional acrylic group-containing compound after vacuum deposition, in Patent Document 2, an overcoat layer made of a cycloolefin polymer deposited film, and in Patent Document 3, an epoxy compound is added. An overcoat layer of epoxy resin cured after dip coating is disclosed. Also, a gas barrier film that achieves both high gas barrier properties and durability by alternately forming and laminating inorganic thin films and organic thin films instead of achieving a gas barrier property with one thick inorganic thin film is also known. (Patent Document 4).

  In recent years, attempts to obtain a plastic film having high gas barrier properties have been actively conducted by alternately laminating inorganic thin films having gas barrier properties and brittleness and organic thin films having stress relaxation ability. It has become to.

However, in general, organic and inorganic materials have poor adhesion, and there is a problem that the inorganic thin film and the organic thin film are easily peeled off. In general, when the organic monomer is cured to become a polymer, volume shrinkage occurs, so that the film curls and it becomes difficult to form the next inorganic thin film on the organic thin film, or the inorganic thin film is caused by shrinkage during curing. There was a problem that the gas barrier properties were reduced due to cracks.
JP 2003-53881 A JP 2002-234103 A JP 2003-48293 A International Publication No. 00/36665 Pamphlet

  Accordingly, an object of the present invention is to provide a substrate film for a display which is excellent in gas barrier properties, adhesion and flex resistance. A second object is to provide an organic EL element with little deterioration with time.

  As a result of intensive studies on the above problems, it is possible to increase the durability of an inorganic thin film having high internal stress by laminating an organic resin layer containing an oxetane resin and an inorganic thin film. It has been found that a substrate film having excellent gas barrier properties and flexibility can be obtained because of its high adhesiveness. Also, by adding a specific ratio of epoxy compound to oxetane resin or using sulfonium salt compound as photoacid generator for curing oxetane resin, the curing rate which is a drawback of oxetane resin can be maintained while maintaining the above characteristics. The present invention has been completed by finding that it can be improved.

（Ｒ_１１〜Ｒ_１６は１価の置換基を表し、Ｌ_１はｍ価の連結基を表し、ｍは２以上の整数を表す。また、ｍが３以上の場合複数のＲ_１４〜Ｒ_１６はそれぞれ異なっていてもよい。）

（Ｒ_２１〜Ｒ_２４は１価の置換基を表し、Ｌ_２はｎ価の連結基を表し、ｎは２以上の整数を表す。また、ｎが３以上の場合複数のＲ_２３、Ｒ_２４はそれぞれ異なっていてもよい。但し、一般式（２）で表される化合物が下記化合物（１）または下記化合物（６）であることはない。）

２．前記活性線照射により酸を発生する化合物が、下記一般式（３）で表されるスルホニウム塩化合物であることを特徴とする前記１に記載のディスプレイ用基板フィルム。

（Ｒ_３１〜Ｒ_３３は１価の置換基を表し、Ｘ⁻は対イオンを表す。）
３．前記無機薄膜が、プラズマＣＶＤ法によって形成されていることを特徴とする前記１または２に記載のディスプレイ用基板フィルム。
４．前記無機薄膜が、大気圧または大気圧近傍の圧力下におけるプラズマＣＶＤ法によって形成されていることを特徴とする前記１〜３のいずれか１項に記載のディスプレイ用基板フィルム。
５．前記無機薄膜が、酸化珪素膜であることを特徴とする前記１〜４のいずれか１項に記載のディスプレイ用基板フィルム。
６．前記透明プラスチックフィルムが、主としてセルロースエステルからなることを特徴とする前記１〜５のいずれか１項に記載のディスプレイ用基板フィルム。
７．前記１〜６のいずれか１項に記載のディスプレイ用基板フィルムに挟持されていることを特徴とする有機エレクトロルミネッセンス素子。
なお、以下（１）〜（１２）については参考とされる手段である。 That is, the above object of the present invention is achieved by the following means 1 to 7.
1. At least a transparent plastic film, an inorganic thin film, a substrate film for display composed of the active ray curable resin layer, the active ray curable resin layer, an oxetane compound represented by the following general formula (1) 5 0 mass% As mentioned above , an active ray is irradiated to the composition containing 10-50 mass% of epoxy group-containing compounds represented by the following general formula (2) and 0.1-10 mass% of a compound that generates an acid by irradiation with active rays. A substrate film for a display, which is a resin layer cured by this.

(R _{11 to} R ₁₆ represent a monovalent substituent, L ₁ represents an m-valent linking group, m represents an integer of 2 or more, and a plurality of R _{14 to} R ₁₆ when m is 3 or more. May be different.)

(R _{21 to} R ₂₄ represent a monovalent substituent, L ₂ represents an n-valent linking group, and n represents an integer of 2 or more. When n is 3 or more, a plurality of R ₂₃ and R _{24 are present.} May be different from each other, provided that the compound represented by the general formula (2) is not the following compound (1) or the following compound (6).

2. 2. The display substrate film as described in 1 above, wherein the compound that generates an acid upon irradiation with actinic radiation is a sulfonium salt compound represented by the following general formula (3).

(R _{31 to} R ₃₃ represent a monovalent substituent, and X ⁻ represents a counter ion.)
3. 3. The display substrate film as described in 1 or 2 above, wherein the inorganic thin film is formed by a plasma CVD method.
4). 4. The display substrate film as described in any one of 1 to 3 above, wherein the inorganic thin film is formed by a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure.
5). 5. The display substrate film according to any one of 1 to 4, wherein the inorganic thin film is a silicon oxide film.
6). 6. The display substrate film according to any one of 1 to 5, wherein the transparent plastic film is mainly composed of a cellulose ester.
7). 7. An organic electroluminescence element characterized by being sandwiched between the display substrate films according to any one of 1 to 6 above.
Note that the following (1) to (12) are means to be referred to.

(1 )
A display substrate film comprising at least a transparent plastic film, an inorganic thin film, and an actinic radiation curable resin layer, wherein the actinic radiation curable resin layer comprises a composition containing 50% by mass or more of a compound having a plurality of oxetane rings. A substrate film for a display, which is a resin layer cured by the method.

(2 )
The substrate film for a display as described in ( 1 ) above, wherein the compound having a plurality of oxetane rings is an oxetane compound represented by the following general formula (1).

(R _{11 to} R ₁₆ represent a monovalent substituent, L ₁ represents an m-valent linking group, m represents an integer of 2 or more, and a plurality of R _{14 to} R ₁₆ when m is 3 or more. May be different.)
(3 )
The active ray curable resin layer comprises 50 to 99.9% by mass of an oxetane compound represented by the general formula (1), 0 to 50% by mass of an epoxy group-containing compound, and a compound that generates an acid upon irradiation with active rays. The substrate film for a display according to the above ( 1 ) or ( 2 ) , which is a resin layer cured by irradiating an active ray on a composition containing 0.1 to 10% by mass.

(4 )
The substrate film for a display as described in ( 3 ) above, wherein the epoxy group-containing compound is an epoxy compound represented by the following general formula (2).

(R _{21 to} R ₂₄ represent a monovalent substituent, L ₂ represents an n-valent linking group, and n represents an integer of 2 or more. When n is 3 or more, a plurality of R ₂₃ and R _{24 are present.} May be different.)
(5 )
The display substrate film as described in ( 3 ) or ( 4 ) above, wherein the compound that generates an acid upon irradiation with actinic radiation is a sulfonium salt compound represented by the following general formula (3).

(R _{31 to} R ₃₃ represent a monovalent substituent, and X ⁻ represents a counter ion.)
(6 )
The substrate film for a display according to any one of ( 1 ) to ( 5 ) , wherein the inorganic thin film is formed by a plasma CVD method.

(7 )
The substrate film for a display according to any one of ( 1 ) to ( 6 ) , wherein the inorganic thin film is formed by a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure.

(8 )
The substrate film for a display according to any one of ( 1 ) to ( 7 ) , wherein the inorganic thin film is a silicon oxide film.

(9 )
The glass substrate temperature of the said transparent plastic film is 180 degreeC or more, The substrate film for a display of any one of said ( 1 ) - ( 8 ) characterized by the above-mentioned .

(10 )
The substrate film for a display according to any one of ( 1 ) to ( 9 ) , wherein the transparent plastic film is mainly composed of a cellulose ester.

(1 1)
The substrate film for display according to any one of ( 1 ) to ( 10 ) above, wherein the water vapor transmission rate is 1.0 g / m ² / d or less.

(1 2)
An organic electroluminescence element, which is sandwiched between the display substrate films according to any one of ( 1 ) to ( 11 ) .

By this invention, the substrate film for a display excellent in water vapor | steam barrier property, adhesiveness, and durability was able to be provided.
Further, by using the display substrate film of the present invention, an organic EL element having a long life and high durability against bending could be obtained.

  Next, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

  An oxetane compound is a compound having a functional group in which three carbon atoms and one oxygen atom form a four-membered ring. When the oxetane ring reacts with a strong acid, the oxetane ring is ring-opening polymerized to form an oxetane resin.

  As described above, since the oxetane resin is polymerized by an acid (cation), the oxetane resin is less susceptible to polymerization inhibition by oxygen than an acrylic resin or the like that is polymerized by radicals. Further, since a hydroxyl group is generated by polymerization, it has high adhesiveness to an inorganic substance and the like, and is a resin suitable for applications in which an organic thin film such as a display substrate film is laminated with an inorganic thin film.

  In general, acrylic resins and the like undergo volume shrinkage during curing, and the ratio of volume shrinkage before and after curing (curing shrinkage ratio) is large (3 to 15% or more), so when formed on a film, curls and inorganic thin films However, it is known that an oxetane resin has a very low cure shrinkage (0% to 2%), and the effect of curing cure shrinkage is less likely to occur. There is.

  In addition, since it is necessary to form and pattern a transparent conductive film on the substrate film for display, solvent resistance is required for strong acid / strong alkaline aqueous solution and organic solvent used when patterning the transparent conductive film. Therefore, the resin forming the organic thin film of the present invention is preferably a crosslinked oxetane resin obtained by polymerizing a composition in which at least 50% by mass is a compound having a plurality of oxetane rings. Solvent resistance can be shown with respect to the said solvent by making 50 mass% or more of a composition into a compound which has a some oxetane ring.

  Any compound having a plurality of oxetane rings can be used for the display substrate film of the present invention without limitation. Among them, a crosslinked oxetane resin obtained by polymerizing a compound represented by the general formula (1). It is preferable that

In the general formula (1), R _{11 to} R ₁₆ represent a monovalent substituent, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; Fluoroalkyl group of 1-6, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl An alkenyl group having 2 to 6 carbon atoms such as a group, an aryl group such as a phenyl group, a furyl group or a thienyl group, a group having an aromatic ring such as a benzyl group, a fluorobenzyl group, a methoxybenzyl group or a phenoxyethyl group, ethylcarbonyl Group, alkylcarbonyl group having 2 to 6 carbon atoms such as propylcarbonyl group and butylcarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl And an alkoxycarbonyl group having 2 to 6 carbon atoms such as a group, or an N-alkylcarbamoyl group having 2 to 6 carbon atoms such as an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group.

  This is because such an oxetane ring at the 2-position is an unsubstituted compound, because the oxetane ring has low steric hindrance and a high polymerization rate, and thus is excellent in productivity when forming an oxetane resin.

L ₁ represents an m-valent linking group, and m is an integer of 2 or more and less than 5. When m = 1, the curability is low and an organic thin film having solvent resistance cannot be obtained. Further, when 5 ≦ m, the degree of cross-linking becomes too high, and the internal stress is so high that the organic thin film becomes brittle and easily cracked. A necessary and sufficient solvent resistance can be obtained when m = 2, but a compound having two oxetane rings (m = 2) is most preferred because the larger m is, the higher the internal stress is and the more fragile the film is.

Preferred L ₁ groups include, for example, ether groups, thioether groups, carbonyl groups, thiocarbonyl groups, amino groups, amide groups, methylene groups, ethylene groups, propylene groups, butylene groups and the like linear or branched alkylene groups, Divalent arylene groups such as phenylene group, biphenylene group, naphthalene group, xylylene group, linear or branched poly (alkyleneoxy) group such as poly (ethyleneoxy) group, poly (propyleneoxy) group, propenylene group, A linear or branched unsaturated hydrocarbon group such as a methylpropenylene group or a butenylene group, a dimethylsiloxane group, a diphenylsiloxane group, a dimethoxysiloxane group, a diethoxysiloxane group, or a linking group in which these are combined. is there.

  Examples of the trivalent or higher linking group include groups formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, and an —O— group, —S— group, —CO— group, Examples include groups formed by combining a plurality of —CS— groups.

When m is 3 or more, the plurality of R _{14 to} R ₁₆ may be different from each other.
Specific examples of the compound having a plurality of oxetane rings include the following compounds.

  Moreover, even if it is a monovalent oxetane compound, if it is the range of 0-30 mass% in the composition, it may be contained. Within the above range, the solvent resistance of the organic thin film after curing is sufficient, and the internal stress of the film can be reduced to improve the brittleness of the film, or various functional groups can be added to the oxetane resin layer. This is because a functional thin film can also be introduced.

Functional groups include anti-oxidation functional groups such as hindered amines and hindered phenols, hydrophilic or lipophilic groups that adjust the surface tension of the coating solution, and water and water repellency such as fluoroalkyl groups. Oily functional groups, functional groups with chromophores that adjust the color of light emitted from the display, antibacterial functional groups such as silver ions, silane coupling groups that can reinforce adhesion with inorganic thin films, etc. Is mentioned.
Specific examples of such monovalent oxetane compounds include the following compounds.

  The production method of each compound having these oxetane rings is not particularly limited, and may be a conventionally known method, for example, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79). (1957)) discloses a method for synthesizing an oxetane ring from a diol.

<Polyfunctional alicyclic epoxy compound>
In the organic resin layer (thin film) forming the display substrate film of the present invention, it is preferable to use an epoxy compound together with the oxetane compound. When the epoxy compound is mixed in an amount of 10 to 50% by mass, it is preferable because the polymerization rate of the oxetane compound is improved and the film strength and solvent resistance are improved. If it exceeds 50% by mass, the volume shrinkage after curing may increase, and the durability as a gas barrier film may decrease, which is not preferable. A more preferable addition amount is 20 to 40% by mass.

  The effect of improving the curing rate of the oxetane resin can be seen with monofunctional or bifunctional or higher epoxy compounds, but the polyfunctional epoxy compound is more effective. From the viewpoint of the solvent resistance of the organic resin layer, it is preferable to use a polyfunctional epoxy compound because the monofunctional epoxy compound has a reduced crosslinking density and solvent resistance.

  As such an epoxy compound, a compound having two or more oxirane rings in the molecule, and those usually used as an epoxy resin can be any monomer, oligomer or polymer. Specific examples include conventionally known aromatic epoxides, alicyclic epoxides, and aliphatic epoxides. Hereinafter, the epoxide means a monomer or an oligomer thereof. These compounds may be used alone or in combination of two or more as required.

  A preferable aromatic epoxide is a di- or polyglycidyl ether produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, such as bisphenol A or an alkylene thereof. Examples thereof include di- or polyglycidyl ethers of oxide adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or alkylene oxide adducts thereof, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Examples of the alicyclic epoxide include those obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. A cyclohexene oxide or a cyclopentene oxide-containing compound is preferable, and specific examples thereof include, for example, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2080, Celoxide 3000, Celoxide 2000, Epoxide GT301, and Epode GT302 manufactured by Daicel Chemical Industries, Ltd. , Epolido GT401, Epolide GT403, EHPE-3150, EHPEL3150CE, Union Carbide UVR-6105, UVR-6110, UVR-6128 Mention may be made of UVR-6100, UVR-6216, UVR-6000 and the like.

  Preferable aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers, polypropylene glycols or diglycidyl ethers of alkylene oxide adducts thereof Jill ether, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  In addition to these compounds, monoglycidyl ethers of higher aliphatic alcohols and phenols, monoglycidyl ethers of cresol, and the like can also be used. Among these epoxides, it is preferable to use alicyclic epoxides having a high curing rate, especially alicyclic epoxides represented by the general formula (2).

In the general formula (2), R _{21 to} R ₂₄ represent a monovalent substituent, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; Fluoroalkyl group of 1-6, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl An alkenyl group having 2 to 6 carbon atoms such as a group, an aryl group such as a phenyl group, a furyl group or a thienyl group, a group having an aromatic ring such as a benzyl group, a fluorobenzyl group, a methoxybenzyl group or a phenoxyethyl group, ethylcarbonyl Group, alkylcarbonyl group having 2 to 6 carbon atoms such as propylcarbonyl group and butylcarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl And an alkoxycarbonyl group having 2 to 6 carbon atoms such as a group, or an N-alkylcarbamoyl group having 2 to 6 carbon atoms such as an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group.

If the carbon atom on the epoxy ring is substituted, the polymerizability of the epoxy group is slightly lowered, and the polymer domain between epoxy compounds having a slightly larger volume shrinkage than the oxetane compound does not become too large. It is preferable that any one of R _{21 to} R ₂₄ has a substituent other than a hydrogen atom, since it tends to have high durability and high durability.

L ₂ represents an n-valent linking group, and 1 ≦ n ≦ 4. When 5 ≦ n, the degree of cross-linking becomes too high, and the internal stress is so high that the organic thin film becomes brittle and easily broken, which is not preferable. In addition, when n = 1, a solvent-resistant organic thin film may not be obtained, and the effect of improving the curing rate of the oxetane resin may not be as good as that of a compound of 2 ≦ n. While n = 2 can provide necessary and sufficient solvent resistance, the larger n is, the higher the internal stress becomes and the more brittle the film is. Therefore, a compound having two epoxycyclohexyl rings (n = 2) is particularly preferable. As the preferred L ₂ group, like the L ₁ group, an ether group, a thioether group, a carbonyl group, a thiocarbonyl group, an amino group, an amide group, a methylene group, an ethylene group, a propylene group, a butylene group and the like are linear or branched. Linear or branched poly (alkyleneoxy) groups such as divalent arylene groups such as linear alkylene groups, phenylene groups, biphenylene groups, naphthalene groups, xylylene groups, poly (ethyleneoxy) groups, poly (propyleneoxy) groups, etc. , Propenylene group, methylpropenylene group, butenylene group or the like linear or branched unsaturated hydrocarbon group, dimethylsiloxane group, diphenylsiloxane group, dimethoxysiloxane group, diethoxysiloxane group, or a combination thereof A linking group or the like.

  Examples of the trivalent or higher linking group include a group formed by removing as many hydrogen atoms as necessary from the divalent linking groups listed above, an —O— group, an —S— group, and a —CO— group. , A group formed by combining a plurality of —CS— groups.

When n is 3 or more, the plurality of R ₂₃ and R ₂₄ may be different from each other.

  Specific examples of preferable alicyclic epoxides are shown below, but the present invention is not limited thereto. One kind of polyfunctional epoxy compound may be used alone, or two or more kinds may be used in appropriate combination.

  Below, the compound example of a preferable epoxy compound is described.

  These alicyclic epoxy compounds may be produced by any method, for example, see Maruzen KK Publishing Co., Ltd., Fourth Edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic compounds, Vol. 5, Adhesive No. 5, Small, Heterocyclic compounds, 1989, Vol. 5, Ad. No. 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-100308, Japanese Patent Application Laid-Open No. 4-36263, Japanese Patent Application Laid-Open No. 4-69360, and the like.

<Cationic polymerization initiator, photoacid generator>
In order to cure the oxetane resin of the present invention, it is necessary to contain a photoacid generator that generates an acid upon irradiation with actinic rays.

As a photoacid generator used for polymerization of a cationic polymerizable polymer, for example, a chemical amplification type photoresist or a compound used for photocation polymerization is used (edited by Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), see pages 187-192). Suitable compounds for the present invention include, for example, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium. _{-CH 3 C 6 H 4 SO 3} - salt, CF ₃ SO ₃ ^- sulfonate, such as salts, sulfonated materials that generate a sulfonic acid, halide which generates hydrogen halide, but iron arene complexes can be cited, Preferable photoacid generators used in the present invention are onium salts such as sulfonium salts, iodonium salts, ammonium salts, phosphonium salts, and the like. Among them, the acid generating ability is high, the polymerization reaction is fast, and the resistance of the cured oxetane resin is high. A sulfonium salt compound capable of increasing solvent resistance and durability is preferred. As a more preferable structure of the sulfonium salt compound, a sulfonium salt represented by the general formula (3) can be given.

In the general formula _{(3), R 31, R} 32, R 33 represents a monovalent substituent. Examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Etc.), a cycloalkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group having 1 to 6 carbon atoms (for example, vinyl group, 1-propenyl, etc.) Group, 2-propenyl group, 2-butenyl group, etc.), alkynyl group having 1 to 6 carbon atoms (for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, etc.), carbon number 1 to 6 alkoxy groups (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), carbon number -6 alkylthio groups (for example, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, tert-butylthio group, etc.), aryl groups having 6 to 14 carbon atoms (for example, phenyl group) , Naphthyl group, anthracenyl group, etc.), aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, naphthoxy group, etc.), arylthio group having 6 to 10 carbon atoms (for example, phenylthio group, naphthylthio group, etc.), acyl Group (for example, acetyl group, propionyl group, trifluoroacetyl group, benzoyl group, etc.), acyloxy group (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl) Group, ethoxycarbonyl group, tert-butyl group Alkoxycarbonyl group, etc.), heteroatom-containing aromatic Hajime Tamaki (such as furyl group having 4 to 8 carbon atoms, a thienyl group, etc.), a nitro group, a cyano group, and the like.

  Preferred examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylthio group, and an acyl group.

  Of these substituents, possible ones may be further substituted.

X ⁻ represents a counter anion. As a counter anion, complex ions such as BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ −, AsF ₆ ⁻ and SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , CF ₃ SO ₃ ^- may be mentioned sulfonate ion such. As the counter anion, borate ion and PF ₆ ^- are preferable because of their high acid generation ability.

  Specific examples of the sulfonium salt represented by the general formula (3) are shown below, but the present invention is not limited thereto.

  As photopolymerization accelerators, anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), phenothiazine derivatives (for example, 10-methylphenothiazine, 10-ethylphenothiazine, 10-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylphenothiazine-5,5-dioxide) and the like are used in combination with a photopolymerization initiator. can do. These photopolymerization accelerators can be used alone or in combination.

<Other additives>
In the organic resin layer of the present invention, various additives can be used in addition to the oxetane compound, epoxy compound, photopolymerization initiator, and photopolymerization accelerator. For example, leveling additives that improve coatability and surface smoothness, matting agents that improve winding properties during film winding, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, Acrylic resins, rubber resins, waxes, water and oil repellents, dyes such as dyes and pigments, antioxidants, antibacterial agents and the like can be added. A silane coupling agent may be added in order to improve the adhesion with the inorganic thin film. These additives are effective when added in a range that does not impair the low cure shrinkage and solvent resistance of the oxetane resin, and the amount used is in the range of 0.1 to 5% by mass, preferably 0. 0.1 to 3% by mass.

<Active energy ray light source>
After forming a layer of a composition containing such various compounds on a support film or an inorganic thin film, it is cured by irradiating active energy rays such as ultraviolet rays to form an organic resin layer (organic thin film) and To do.

  Examples of the method for forming the organic resin layer include coating methods such as dip coating, extrusion coating, knife coating, doctor blade, wire bar, and ink jet printer. Also, means such as vacuum vapor deposition, cryo vapor deposition and the like may be used.

As an ultraviolet light source for curing a composition containing an oxetane ring, a light source having an emission wavelength peak at 250 to 370 nm, more preferably 270 to 340 nm is preferable. A light source having an illuminance of 1 to 3000 mW / cm ² , more preferably 1 to 200 mW / cm ² is preferable.

  Examples of such light sources include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, UV lasers, xenon. Examples include, but are not limited to, flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, and LEDs. Moreover, when forming an inorganic thin film using the plasma CVD method mentioned later, you may harden an organic resin layer using the ultraviolet light radiated | emitted from plasma space. In that case, it is preferable to form an inorganic thin film by the atmospheric pressure plasma CVD method mentioned later so that the organic substance before hardening may not volatilize.

  In addition, it may be cured using an electron beam instead of ultraviolet rays, and when cured with an electron beam, it is usually cured with an electron beam having an energy of 300 eV or less, but is instantaneously cured with an irradiation dose of 1 to 5 Mrad. It is also possible.

<Inorganic thin film>
The substrate film for display includes an inorganic thin film having low water vapor permeability, such as glass, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, aluminum oxide, aluminum oxynitride, titanium oxide, zirconium oxide, boron nitride, carbon nitride, It is necessary to form a thin film of magnesium fluoride, aluminum fluoride, diamond-like carbon or the like.

  As a method for forming a gas barrier film made of an inorganic material as described above on a plastic film, physical vapor deposition methods (PVD method) such as vacuum deposition, sputtering method, ion plating method, heat, light, plasma, etc. There are three types of coating methods such as chemical vapor deposition method (CVD method) using sol-gel and the like, and sol-gel method. However, since it is difficult to obtain a dense thin film having a high gas barrier property by the coating method, the method for forming an inorganic thin film having a high gas barrier property on a plastic film is actually limited to the PVD method and the plasma CVD method. Among these, the plasma CVD method is most preferable because it can obtain a thin film having high adhesion to an organic substance such as a plastic film or an organic resin layer. Further, among the plasma CVD methods, the atmospheric pressure plasma CVD method in which an inorganic thin film is formed by generating plasma under atmospheric pressure is most preferable. In the plasma CVD method under atmospheric pressure, the mean free path of particles is very short, the resulting inorganic thin film has no directionality, and the film thickness is extremely uniform, so that defects are hardly generated in the inorganic thin film. This is because the in-plane distribution of gas barrier properties can also be reduced. Further, as described above, the volatilization of the monomer forming the oxetane resin layer can be made extremely small, and the deterioration of the film quality can be prevented. In addition, there is an advantage that the productivity is very high because a decompression step when forming the inorganic thin film is unnecessary.

  In the plasma CVD method, since light in the infrared to ultraviolet region is emitted from plasma, the above-described oxetane compound can be cured by these lights. Among these, when the discharge gas is nitrogen gas, the oxetane compound can be efficiently cured because it has a strong emission line in the ultraviolet region such as 337 nm.

<Atmospheric pressure plasma CVD method>
Next, an apparatus for forming an inorganic thin film by atmospheric pressure plasma CVD will be described in detail. In addition, in this invention, the atmospheric pressure vicinity represents the pressure of 20 kPa-110 kPa, More preferably, it is 93 kPa-104 kPa.

  FIG. 1 is a side view illustrating a schematic configuration of the thin film forming apparatus 1.

  The thin film forming apparatus 1 generates an electric field between opposed electrodes under atmospheric pressure or a pressure close to atmospheric pressure, so that a mixed gas (a gas obtained by mixing a discharge gas, a raw material gas, a decomposition gas, or the like) between the electrodes. Represents a plasma state, and the substrate is exposed to the mixed gas in the plasma state to form a film on the substrate. In the plasma CVD method, there are a plasma jet method in which the base material does not enter the plasma space, and a direct plasma method in which the base material enters the plasma space. In the atmospheric pressure plasma CVD method of the present invention, both are applied. be able to. In addition, since the direct plasma method can easily obtain a thin film having high adhesion to the substrate, the case where the thin film is formed by the direct plasma method will be described below.

  As shown in FIG. 1, the thin film forming apparatus 1 is rotatably provided with a support member (also serving as a discharge electrode) 10 that conveys a sheet-like base material 2 in close contact with the peripheral surface thereof.

  FIG. 2 is a perspective view showing the support member 10, which is a roll-shaped dielectric member in which a dielectric 12 is coated on the surface of a conductive metallic base material 11. In order to adjust the surface temperature inside the support member 10, for example, a temperature adjusting medium such as water or silicon oil can be circulated. A temperature control device 4 is connected via a pipe 3. P represents a pump for circulating the medium. Further, on the periphery of the support member 10, a base material transport mechanism 13 for transporting the base material 2 in close contact with the peripheral surface of the support member 10, and a plurality of thin films for forming a thin film on the base material 2 A forming unit 20 is provided.

  The substrate transport mechanism 13 peels off the first guide roller 14 and the nip roller 15 that guide the substrate 2 to the peripheral surface of the support member 10 and the substrate 2 that is in close contact with the peripheral surface, and guides it to the next step. A second guide roller 16 and a drive source 51 (see FIG. 6) that rotates the first guide roller 14, the second guide roller 16, and the support member 10 so as to interlock with each other are provided.

  FIG. 3 is a side view showing the direct plasma type thin film forming unit 20. The support member 10 provided in the thin film forming unit 20 is connected to the first power supply 9 via the noise filter 8 and functions as a discharge electrode while conveying the substrate 2. The opposing surfaces 21a and 21b of the support member 10 and the rod electrodes 21A and 21B function as discharge surfaces. That is, if the gas is ejected from the gas supply unit 24 to fill the gap a between the support member 10 and the rod electrodes 21A and 21B and an electric field is applied to the support member 10A and the rod electrodes 21A and 21B, the gap Discharge plasma is generated in a. And since the base material 2 is arrange | positioned in the plasma space h, the base material 2 is exposed to the activated gas and a thin film is formed in the surface.

  As will be described later, when the discharge is performed without using the two-frequency superposition of the high-frequency power source for generating the plasma, the plasma discharge is performed without using either the first power source 9 or the second power source 23. Just do it.

  The distance between the electrodes forming the discharge space is preferably 0.3 mm to 20 mm, and particularly preferably 1 mm ± from the viewpoint of performing uniform discharge, between the support member 10 and the rod electrodes 21A and 21B. 0.5 mm. The distance between the electrodes is determined in consideration of the thickness of the dielectric around the electrodes, the magnitude of the applied voltage, and the type of discharge gas.

  FIG. 4 is a perspective view showing the rod electrodes 21A and 21B. The rod electrodes 21A and 21B are quadrangular columnar electrodes in which a dielectric 212 is coated on the surface of a conductive metallic base material 211. FIG. The corner portions 215 of the rod electrodes 21A and 21B are formed in an arc shape. That is, since the four surfaces of the rod electrodes 21A and 21B are continuous through the corner portion 215, the surfaces other than the discharge surfaces 21a and 21b and the discharge surfaces 21a and 21b are also continuous. The rod electrodes 21A and 21B are hollow inside, and a temperature adjusting device 6 is connected to the hollow portion 213 via a pipe 5 as shown in FIG. By flowing a temperature adjusting medium through the hollow portion 213, the temperature of the electrode surface can be adjusted. A second power source 23 is connected to the rod electrodes 21 </ b> A and 21 </ b> B of each thin film forming unit 20 via a filter 22.

  Further, in the thin film forming unit 20, as shown in FIG. 3, a gas supply unit 24 for ejecting a discharge gas toward the gap b between the pair of rod electrodes 21A and 21B is disposed so as to face the gap b. ing. That is, the gap b functions as a flow path that guides the discharge gas supplied from the gas supply unit 24 to the base material 2 on the support member 10.

  In addition, the thin film forming unit 20 is provided with a cleaning film transport mechanism 30 that transports the cleaning film 27 continuously or intermittently in close contact with the rod electrodes 21A and 21B according to the rod electrodes 21A and 21B. .

  In the plasma CVD method, fine particles generated from the raw material compound in the plasma space are deposited not only on the target substrate but also on the discharge electrode. If such dirt on the electrode is left unattended, the discharge state becomes unstable, and the stable / homogeneous glow discharge shifts to unstable / local arc discharge, and a homogeneous thin film cannot be obtained under the arc discharge. Covering the discharge electrode with a cleaning film, preventing contamination from being deposited on the discharge electrode, and keeping the discharge electrode always clean is very effective in obtaining a homogeneous thin film.

  The cleaning film transport mechanism 30 is provided with a first cleaning film guide roller 31 for guiding the cleaning film 27 in the vicinity of the gas supply unit 24. An unillustrated unwinding roller for the cleaning film 27 or an original roll for the cleaning film 27 is provided on the upstream side of the first cleaning film guide roller 31.

  Further, a winding unit 29 (see FIG. 6) that winds the cleaning film 27 through the second cleaning film guide roller 32 at a position farther than the first cleaning film guide roller 31 with respect to the gas supply unit 24. Is provided. The full widths of the first cleaning film guide roller 31, the second cleaning film guide roller 32, and the cleaning film 27 are set to be longer than the full width of the support member 10, as shown in FIG. Specifically, the entire width of the cleaning film 27 is preferably set so that both ends protrude from the both ends of the support member 10 by 1 to 100 mm. Thereby, the cleaning film 27 becomes larger than the discharge space. That is, the rod electrodes 21A and 21B are not exposed to the discharge plasma by being covered with the cleaning film 27, so that the rod electrodes 21A and 21B can be prevented from being contaminated. Further, since the edge of the cleaning film 27 does not enter the discharge space, arc discharge due to concentration of discharge can be prevented.

  Further, the thin film forming unit 20 has a cleaning film 27 with respect to the discharge surfaces 21a and 21b of the rod electrodes 21A and 21B in order to prevent slippage and wrinkles that occur when the cleaning film 27 contacts the discharge surfaces 21a and 21b. A heating member 28 for heating the cleaning film 27 is provided on the upstream side in the transport direction.

  That is, the cleaning film 27 is drawn from the unwinding roller by the cleaning film transport mechanism 30 and is then guided by the first cleaning film guide roller 31 to contact the periphery of the nozzle body 25 of the gas supply unit 24. Then, after contacting the surface of the heating member 28 and being heated, it contacts the discharge surfaces 21a and 21b via the corners 215 of the rod electrodes 21A and 21B, and then guides to the second cleaning film guide roller 32. Then, it is wound up by the winding unit 29. At this time, since the corner 215 is formed in an arc shape, the cleaning film 27 can be prevented from being caught when moving from the surface other than the discharge surface 21a (surface of the corner 215) to the discharge surfaces 21a and 21b. It can be transported smoothly. In this embodiment, the discharge surfaces 21a and 21b of the rod electrodes 21A and 21B are flat, but the discharge surfaces 21a and 21b are formed in curved surfaces that protrude toward the other discharge surfaces 21a and 21b. Also good. In such a case, the adhesion between the discharge surfaces 21a and 21b of the rod electrodes 21A and 21B and the cleaning film 27 can be further enhanced.

  As described above, since the cleaning film 27 and the gas supply unit 24 are in contact with each other, the space from the gas supply unit 24 to the discharge space B is partitioned by the cleaning film 27, so that the discharge gas is discharged. It can prevent flowing out of the flow path.

  Such a cleaning film 27 needs to withstand high temperatures and heat generated in the plasma space, and therefore needs to have high heat resistance, and therefore, such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. A film made of cellulose ester, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone, polysulfone, polyether imide, polyamide, fluororesin, or the like is preferable.

  In addition, since the cleaning film is conveyed on a rectangular discharge electrode, a film having a high slip property is preferable. However, this slipperiness may be imparted by applying a slipping agent such as silicone oil to the surface in contact with the discharge electrode even if the slipperiness of the cleaning film substrate itself is poor, and the slipperiness is high. The slipperiness may be imparted by thinly laminating a polymer such as Teflon (registered trademark).

  As shown in FIG. 6, the thin film forming apparatus 1 is provided with a control device 50 that controls each drive unit. The control device 50 includes a drive source 51, a storage unit 52, a first power supply 9, a second power supply 23, a gas supply unit 24, a heating member 28, temperature control devices 4 and 6, and a winding unit 29. It is connected. In addition to the above, each drive unit, pump, and the like of the thin film forming apparatus 1 are connected to the control device 50. The control device 50 controls various devices in accordance with a control program and control data written in the storage unit 52.

  The power source of the plasma film forming apparatus used for forming the film of the present invention, such as the power source 23 of FIGS. 1 and 6, is a high frequency voltage and a certain amount of power to increase the film forming speed and control the film quality. A power supply capable of supplying Specifically, a high-frequency power source of 1 kHz to 2500 MHz is preferable, and a voltage of any frequency between 1 kHz and 1 MHz and a voltage of any frequency between 1 MHz to 2500 MHz are applied in a superimposed manner. It is more preferable. This is because the frequency required for excitation of various gases existing in the discharge space may be different, so that the decomposition of the source gas is faster and the film forming speed is faster when a plurality of frequencies are applied. . In order to obtain a thin film having a high gas barrier property, it is preferable to use a frequency of 10 KHz or higher, and more preferably to use a frequency of 100 kHz or higher. If a frequency of 2500 MHz or more is used, the uniformity of discharge in the plasma space may not be obtained, and the uniformity of the obtained thin film thickness, film quality, etc. may not be obtained.

The power density supplied between the electrodes is preferably 1 W / cm ² or more and 50 W / cm ² or less, and preferably 5 W / cm ² or more in order to obtain a high gas barrier thin film. In addition, when a voltage having a frequency of 1 KHz to 1 MHz and a voltage having a frequency of 1 MHz to 2500 MHz are superimposed, the voltage of 1 MHz to 2500 MHz is preferably smaller than the voltage having a frequency of 1 kHz to 1 MHz. The voltage is preferably 20% to 90%. The voltage with a frequency of 1 kHz to 1 MHz may be either the second power source 23 connected to the rod electrodes 21A and 21B or the first power source 9 connected to the support member 10, but it superimposes two frequencies and has a high force. In order to supply power at a rate, it is preferable that a power source of 1 kHz to 1 MHz is used as the first power source 9 connected to the support member 10.

  The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave, but a sine wave is preferable because the film forming speed increases.

  Such a power source is not particularly limited, but is a Shinko electric high frequency power source (3 kHz), a Shinko electric high frequency power source (5 kHz), a Shinko electric high frequency power source (15 kHz), a Shinko electric high frequency power source (50 kHz), HEIDEN High frequency power source manufactured by R & D Laboratories (continuous mode, 100 kHz), high frequency power source manufactured by Pearl Industry (200 kHz), high frequency power source manufactured by Pearl Industry (800 kHz), high frequency power source manufactured by Pearl Industrial (2 MHz), high frequency power source manufactured by JEOL (13.56 MHz) Pearl industrial high frequency power supply (27 MHz), Pearl industrial high frequency power supply (40 MHz), Pearl industrial high frequency power supply (54 MHz), Pearl industrial high frequency power supply (60 MHz), and the like can be used. Alternatively, a power source that oscillates 100 MHz, 200 MHz, 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, 10 GHz, or 28 GHz may be used.

  Further, the temperature control devices 4 and 6 can adjust the temperature of the base material to 0 ° C. to 250 ° C. in order to suppress the adverse effect due to the high temperature during discharge or to adjust the composition and film quality of the thin film to be formed. The rod electrodes 21A and 21B, the support member 10 and the like are cooled or heated as necessary.

  Next, the mixed gas used for forming the gas barrier layer will be described. The mixed gas contains at least a discharge gas and a raw material gas containing an element constituting the thin film. Furthermore, a cracking gas that assists the decomposition reaction of the raw material gas may be added.

  The discharge gas is a gas that can be easily ionized into a plasma state when a high frequency electric field is applied. A thin film is obtained by indirectly exciting and reacting the source gas contained in the mixed gas with the discharge gas in the plasma state.

  Examples of such discharge gas include Group 18 elements of the periodic table, specifically, noble gases such as helium, neon, argon, krypton, xenon, and radon, or nitrogen. In order to obtain the described effects, helium, argon and nitrogen are preferably used. Among these, in order to form a dense thin film having a high gas barrier property, it is most preferable to use nitrogen as a discharge gas. This is because when nitrogen is used, since a discharge is stable even when a decomposition gas other than the discharge gas and a raw material gas are mixed at a high concentration (-10% by volume), a high-density film can be obtained. The nitrogen gas is preferably contained in the mixed gas in an amount of 90.0 to 99.9% by volume.

  The mixed gas contains a discharge gas and a raw material gas, but may contain a cracked gas that assists in the decomposition of the raw material gas. When the reactivity of the raw material gas is low, it is preferable to include a cracked gas.

  These cracked gases include hydrogen gas, methane gas, ammonia gas, reducing gas such as hydrogen sulfide gas, carbon monoxide gas, carbon dioxide gas, nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, An oxidizing gas such as water vapor or sulfur dioxide gas can be used.

  By appropriately selecting and adding a decomposition gas, decomposition of the raw material compound is promoted, and a thin film having a high density and a high gas barrier property can be obtained.

  Next, source gases preferable for obtaining various inorganic thin films will be described.

  The raw material for the inorganic thin film may be in the state of gas, liquid, or solid as long as it is a volatile low-molecular compound having a vapor pressure in the temperature range of 0 ° C. to 250 ° C. under atmospheric pressure. It is an organometallic compound that exhibits a liquid state in a temperature range of ˜250 ° C. This is because the pressure in the plasma deposition chamber is close to atmospheric pressure, and if it cannot be vaporized under atmospheric pressure, it is difficult to send gas into the plasma deposition chamber, and if the raw material compound is liquid, a vaporizer is used. Therefore, the vaporization amount can be managed with an accuracy of ± 1%, and the film forming conditions can be strictly determined.

  Examples of such organometallic compounds include silicon-containing compounds such as silane, disilane, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, and tetra n-butoxysilane. , Tetra-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) Trimethoxysilane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, bis (dimethylamino) dimethyl Lan, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethyl Cyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, Allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-buta In, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) ) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, and the like.

  Examples of the titanium-containing compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), and titanium diisopropoxy. (Bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, butyl titanate dimer, and the like.

  The compounds containing zirconium include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate. , Zirconium acetate, zirconium hexafluoropentanedionate and the like.

  The compounds containing aluminum include aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethylaluminum, triethyl-tri-s-butoxydialuminum. Etc.

  Examples of the boron-containing compound include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, Examples thereof include triethylborane, trimethoxyborane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Compounds containing tin include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, Diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin di Examples of tin halides such as acetoacetonate and tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Examples of organic compounds composed of other metals include magnesium acetate, magnesium trifluoroacetate, magnesium trifluoropentanedionate, magnesium hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, indium acetylacetonate, Indium 2,6-dimethylaminoheptanedionate, ferrocene, zinc acetylacetonate, diethylzinc, and the like can be given.

  When the inorganic thin film to be formed is a film called a diamond-like carbon film (DLC film) or an amorphous carbon film (aC: H film), the raw material compound is not an organometallic compound. For example, organic compounds such as methane, ethane, ethylene, acetylene, propane, propylene, butane, pentane, hexane, cyclohexane, benzene, toluene, xylene, mesitylene, methanol, ethanol and the like may be used.

  Of these organometallic compounds and organic compounds, organosilicon compounds are preferred. This is because the organosilicon compound has high volatility and is relatively inexpensive, and the silicon oxide thin film obtained from the organosilicon compound has high gas barrier properties and transparency.

  The inorganic thin film may be a single layer, or two or more different types of inorganic thin films may be laminated. However, the total thickness of the layers composed of inorganic substances is 500 nm or less in terms of maintaining flexibility and resistance to bending. preferable. More preferably, it is 200 nm or less. On the other hand, if it is thinner than 5 nm, it is difficult to form a uniform film, which is not preferable.

  In the atmospheric pressure plasma CVD method, since plasma generation is performed under atmospheric pressure, it is not necessary to reduce the pressure of the entire apparatus, and the operation, maintenance, and inspection of the apparatus are easy and high productivity can be achieved. . In particular, when an organic layer and an inorganic layer are alternately laminated, a mechanism for maintaining airtightness between the film forming zones is unnecessary, and the organic monomer layer in the vacuum zone is volatilized by the evaporation of the raw material monomer. The possibility of causing monomer loss, chamber contamination, contamination of organic matter in the inorganic thin film (layer), etc. is small, and extremely high productivity can be raised.

<Resin substrate>
The resin base material used as the support for the substrate film for display of the present invention is not particularly limited as long as it is substantially transparent. Specifically, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, and cellophane , Cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic Polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfone Emissions, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, or can be given a transparent plastic film of organic-inorganic hybrid resins and the like of these resins and silica.

  However, since the substrate film for a display may be subjected to various heating processes in forming a transparent conductive film on the surface thereof, the support for the substrate film for a display preferably has a glass transition temperature of 180 ° C. or higher. This is because the crystallization temperature of an ITO (indium-tin oxide) film, which is a typical transparent conductive film, is around 180 ° C., and the conductivity of the ITO film can be improved by crystallization. .

  Examples of the resin base material satisfying such conditions include some polycarbonates, some cycloolefin polymers, polyethersulfone, polyetheretherketone, polyimide, fluororesin, cellulose esters such as diacetylcellulose and triacetylcellulose, Examples thereof include organic-inorganic hybrid resins of these resins and silica.

  An organic-inorganic hybrid resin (or called an organic-inorganic polymer composite or the like) is a material in which an organic polymer and an inorganic compound are combined to give both characteristics. By using a technique (sol-gel method) for synthesizing an inorganic substance to be mixed with an organic polymer from a liquid state such as a metal alkoxide, the generated inorganic fine particles are formed on a nanoscale below the wavelength of visible light (up to about 750 nm). It is possible to disperse the material in the inside, and an optically transparent material having high heat resistance can be obtained.

  In addition, as a method of measuring the glass transition temperature of the resin base material, it can be measured by DSC (differential scanning calorimetry), TMA (thermal stress strain measurement), DMA (dynamic viscoelasticity measurement) and the like.

Further, the display substrate film of the present invention can be used as a transparent film for a display substrate. However, the transparent film for a display substrate preferably has low birefringence, and further preferably has a birefringence dispersion of positive dispersion. Most preferred are cellulose esters such as diacetyl cellulose and triacetyl cellulose, and organic-inorganic hybrid films mainly composed of these cellulose esters. The wavelength dispersion of birefringence is positive dispersion. For example, the polymer is dissolved in a soluble solvent and cast on a glass plate so that the thickness upon drying of the film is 100 μm. The value obtained by dividing the in-plane retardation value R ₀ (480) at a wavelength of 480 nm of the film made of the polymer by the in-plane retardation value R ₀ (590) at a wavelength of 590 nm is smaller than 1.

  In a transparent film having a positive birefringence wavelength dispersion, for example, 4 nm for 400 nm light and 7 nm for 700 nm light can be compensated for polarization according to the wavelength of light. A liquid crystal panel employing a display method utilizing refraction has no color shift, and an organic EL display element is preferable because the contrast is good.

  Moreover, since the resin base material is directly exposed to the plasma atmosphere, it may have an undercoat layer on one side or both sides as a plasma etching layer. Examples of the undercoat layer include an organic resin layer formed by applying a polymer or the like. A thin film obtained by curing an acrylic compound, an epoxy compound, or an oxetane compound of the present invention can also be preferably used.

<Organic EL device>
Next, the organic EL element will be described. Since organic EL elements are sensitive to moisture, sealing is necessary. The display substrate film of the present invention is used as a film for sealing these elements.

  The organic EL element has at least a structure in which an organic light emitting layer is held between an anode and a cathode, and the organic light emitting layer represents a layer containing an organic compound that emits light when a current is passed. Of the elements constituting the organic EL element, the cathode and the light emitting layer are vulnerable to moisture, so the organic EL element needs to be sealed. Therefore, a gas barrier layer is essential for a display substrate film for forming an organic EL element.

  After the organic EL element is formed on the substrate film for display, it is necessary to seal the cathode side. For example, the display of the present invention is applied directly on the cathode or after being sealed with epoxy resin or the like. Sealing may be performed by laminating a substrate film for use. With such a configuration, moisture permeation is suppressed, the moisture resistance of the organic EL display device is further improved, generation and growth of dark spots can be suppressed, and the organic EL has high luminance and long life. An element can be obtained.

  The display substrate film of the present invention can be used not only for organic EL elements but also for devices using organic materials that are weak against moisture and oxygen, such as organic electrochromic elements and organic thin film transistor (TFT) elements.

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

Example 1
A diacetylcellulose-silica hybrid film is formed as a high heat-resistant transparent film, and an undercoat layer (organic resin layer) / gas barrier layer (silicon oxide layer) / overcoat layer (organic resin) is formed on the diacetylcellulose-silica hybrid film. Layer), a film formed with three layers was prepared.

<Film formation of diacetylcellulose-silica hybrid film>
Into the mixing tank, 25 parts by mass of tetramethoxysilane, 15 parts by mass of ethanol, 15 parts by mass of methylene chloride, and 12 parts by mass of 0.5% nitric acid aqueous solution were added and stirred while cooling to 0 ° C. to carry out a sol-gel reaction.

  Furthermore, 45 parts by mass of ethanol, 660 parts by mass of methylene chloride, and 100 parts by mass of diacetylcellulose were added to the mixing tank, and dissolved by stirring while heating at 80 ° C. in a sealed state.

  The obtained dope (solution) was cast using a band casting machine, and when the residual solvent amount reached 30%, it was peeled off from the band, immediately transported to a tenter, and then 30% in the orthogonal direction. The film was stretched 30% in the flow direction and then dried at 120 ° C. for 5 minutes and then at 220 ° C. for 5 minutes to obtain a diacetylcellulose-silica hybrid film. In addition, it adjusted so that the shape of the film obtained might become width 10cm and a film thickness of 100 micrometers.

The glass transition temperature of the obtained diacetylcellulose-silica hybrid film was 225 ° C. when measured with TMA (thermal stress strain measuring device). The average linear expansion coefficient from 30 ° C. to 180 ° C. was 27 ppm / ° C. The moisture permeability was 1000 g / m ² / d.

On the above-mentioned diacetylcellulose-silica hybrid film, a polymer composition having the composition shown in Table 1 was applied so that the film thickness when dried was 1 μm, and then irradiated with ultraviolet rays of 50 mJ / cm ^2. An undercoat layer was formed. In the table, the number of times of irradiation is the number of times of irradiation with ultraviolet rays and the amount of irradiation increased.

Note oxetane compound DOX, XDO represent respectively bis oxetane (manufactured by Toagosei Co. OXT221) and xylylene bis oxetane (manufactured by Toagosei Co. OXT121). Acrylic compound 3EG-A represents Kyoei Chemical's triethylene glycol diacrylate, and RS600 represents Sanyo Chemical's Sun Rad RS600. Also, the epoxy compound PNO is Daicel Chemical's α-pinene oxide, S530 is Amax Max Silaace S530, C2021 is Daicel Chemical's Celoxide 2021, C3000 is Daicel Chemical's Celoxide 3000, VF9080 is Atfina's Vikoflex 9080, and VF7190 is Atofin's Vik x 190 To express.

  The photopolymerization initiator Irgacure 184 is manufactured by Ciba Geigy Japan, and the photoacid generator DPI-PF6 is diphenyliodonium hexafluorophosphate manufactured by Tokyo Chemical Industry. Since epoxy compound EP-17 and photoacid generators TAS-4 and TAS-13 are not commercially available, they were synthesized according to the following synthesis example.

(Synthesis Example 1) Synthesis of EP-17 <Synthesis of 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3-cyclohexenecarboxylate)>
1 g of toluenesulfonic acid monohydrate was added to 340 g (2 mol) of methyl- (4-methyl-3-cyclohexanecarboxylate) and 104 g (1 mol) of 2,2-dimethyl-propane-1,3-diol. It reacted at 80-90 degreeC for 12 hours. The reaction solution was washed with aqueous sodium bicarbonate, and then distilled under reduced pressure to obtain the target compound. The yield was 86%.

<Synthesis of Exemplified Compound EP-17>
348 g (1 mol) of 2,2-Dimethyl-propane-1,3-diol-bis- (4-methyl-3-cyclohexenecarboxylate) was placed in a 2 L three-headed flask, and the internal temperature was kept at 40 ° C. 770 g of an acetone solution having an acetic acid content of 25% by mass (192 g (2.5 mol) of peracetic acid) was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out after 4 hours at the same temperature. The reaction solution was stored at −11 ° C. overnight, and then the remaining amount of peracetic acid was examined to confirm that 98% or more of the theoretical amount had reacted.

  Next, the reaction solution was diluted with 1 L of toluene, heated to 50 ° C. under reduced pressure using a water aspirator, and the low boiling point components were distilled off and removed until the distillate disappeared.

  The remaining reaction composition was distilled under reduced pressure to obtain the target exemplified compound EP-17. The yield was 70%.

  The structure of exemplary compound EP-17 was confirmed by NMR and MASS analysis.

¹ H-NMR (CDCl ₃ ) δ (ppm): 0.96 (s, 6H, CH ₃ —), 1.31 (s, 6H, CH ₃ —), 1.45 to 2.50 (m, 14H) , Cyclohexane ring), 3.00 (m, 2H, epoxy root), 3.87 (s, 4H, —O—CH ₂ —)
Synthesis Example 2 Synthesis of TAS-4 32 g of phosphorus oxide and 150 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of about 80 ° C. for 3 hours. After allowing to cool to room temperature, 54 g of bis (4-methoxyphenyl) sulfoxide and 46.8 g of 1-tert-butyl-4-phenoxybenzene were added and stirred for 3 hours under water cooling. When 42 g of potassium hexafluorophosphate was dissolved in 1 L of ice water in a 2 L conical beaker and the above reaction solution was added little by little while stirring with a mechanical stirrer, a soft white amorphous solid was produced. Stirring was stopped, the supernatant was removed by decantation, 1 L of methylene chloride was added to the residue, and after washing with water, the methylene chloride layer was concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment, the solvent was concentrated under reduced pressure to obtain a light brown oil component. Add about 100 ml of methanol and concentrate under reduced pressure again to completely remove methylene chloride, and then dry under reduced pressure with a rotary pump. TAS-4 was obtained by crushing the amorphous solid foamed into a bowl-like firmness. Yield 60.9 g (49% yield). It identified with the target object in < ¹ > H-NMR and a mass spectrum.

(Synthesis Example 3) Synthesis of TAS-13 32 g of phosphorus oxide and 288 g of methanesulfonic acid were added to a 1 L flask equipped with a calcium chloride tube and a thermometer, and the mixture was heated and stirred at an internal temperature of 80 ° C. to 90 ° C. for 3 hours. After allowing to cool to room temperature, 69.1 g of p-toluyl sulfoxide and 33 g of anisole were added and stirred at room temperature for 3 hours. When 55.2 g of potassium hexafluorophosphate was dissolved in 3 L of pure beaker in a 5 L beaker and the above reaction solution was added little by little while stirring with a mechanical stirrer, a nougat amorphous solid was formed. Stirring was stopped, the supernatant was removed by decantation, 600 ml of methylene chloride was added to the residue, and a 25 g potassium hexafluorophosphate / pure 500 ml solution was added and dispersed for 1 hour. After separation of the aqueous layer, the methylene chloride layer was decolorized by adding activated carbon, and the activated carbon was filtered off and concentrated under reduced pressure to obtain a crude product. After purification by activated alumina column treatment and concentration of the solvent under reduced pressure, 132.6 g of crude crystals were obtained. Add 300 ml of isopropyl alcohol and 10-30 ml of methylene chloride, heat and disperse in a 60-70 ° C. water bath, allow to cool to near room temperature, add 200 ml of isopropyl alcohol, and stir at room temperature for 1 hour. -13 was obtained. Yield 123.7 g (88% yield). It identified with the target object in < ¹ > H-NMR and a mass spectrum.

  After forming the undercoat layer under the above conditions, a silicon oxide layer was formed under the following conditions.

<Formation of silicon oxide layer>
The silicon oxide layer was formed by atmospheric pressure plasma CVD using a thin film forming apparatus 1 shown in FIG. The generation of plasma, a high-frequency power 12W / cm ² (Heiden Research Laboratory high-frequency power source PHF-6KB use) of 100kHz, the 13.56MHz high-frequency power 6W / cm ² (Japan Electronics Co., Ltd., a high-frequency power source JRF-10000 Use) It was generated by applying in a superimposed manner. The shape of the electrode is 40 mm × 40 mm × 120 mm on the rod electrode side, 316 mmφ × 100 mm on the roll electrode side, and the shortest distance between the rod electrode and the roll electrode is 0.5 mm. Both electrode temperatures were set to 150 ° C.

  The flow rate of the gas used for forming the silicon oxide layer is as follows.

<Silicon oxide layer source gas>
Discharge gas: Nitrogen 95.0 L / min Decomposed gas: Oxygen 5.0 L / min Raw material gas: Tetramethoxysilane 200 mg / min As a cleaning film, a silicone release agent is applied to the back surface of a 25 μm-thick polyimide film. The coated film was used such that the silicone release agent coating surface was in contact with the discharge electrode. The cleaning film was transported at a speed of 5 cm / min.

  The diacetylcellulose-silica hybrid film provided with the undercoat layer was transported at a transport speed of 10 m / min, and a film of 30 passes was formed to obtain a silicon oxide layer having a thickness of 100 nm.

  After the formation of the silicon oxide layer, an overcoat layer is formed on the obtained silicon oxide layer under the same film forming conditions as those of the undercoat layer described above. The obtained display substrate films 101 to 120 are as follows. Evaluation was performed.

<Water vapor permeability test>
Using a water vapor transmission rate measuring device PERMATRAN-W3G manufactured by Modern Control, each water vapor transmission rate was measured under the condition of 40 ° C. and 90% RH.

  Moreover, the water vapor transmission rate immediately after film formation and the water vapor transmission rate after carrying out the durability test wound 10 times around a 10 mm diameter rod were also measured.

<Cross-cut test>
A cross-cut test based on JIS K5400 was performed. On the surface of the formed thin film, 11 single-edged razor blades with 90 ° cuts with respect to the surface were placed 11 by 1 mm vertically and horizontally to make 100 1 mm square grids. A commercially available cellophane tape was affixed on this, and one end of the tape was peeled off vertically by hand, and the ratio of the area where the thin film was peeled to the affixed tape area from the score line was evaluated according to the following rank.

  ○: Not peeled off at all.

  Δ: The peeled area ratio was less than 10%.

  X: The peeled area ratio was 10% or more.

  From Table 1, the durability of the display substrate film is hardly improved in the display substrate films 102 and 103 overcoated with an acrylic organic thin film. Although the display substrate films 104 and 105 overcoated with an epoxy organic thin film show some improvement in durability, they are greatly deteriorated compared to before the durability test.

  On the other hand, when an oxetane-based thin film is used, durability of gas barrier properties is improved as compared with an epoxy-based film. This is presumed to be due to the high stress relaxation ability even when external stress is applied because the internal stress in the organic thin film is small.

However, when only the oxetane compound is cured, the curing rate is slower than that of acrylic or epoxy, so the number of passes for UV irradiation has increased, but the photoacid generator should be a sulfonium salt compound. In addition, the sensitivity can be increased, and by mixing an oxetane compound with an epoxy compound, the curing rate can be increased as well as an acrylic resin or an epoxy resin. As can be seen from the results of the display substrate films 110 to 113, the gas barrier property after the durability test is 1.0 g / m ² / d or less if the mixing ratio of the epoxy compound is up to about 50% by mass. It can be seen that the durability of the gas barrier layer is high.

As described above, by protecting the organic gas layer containing the oxetane resin with the inorganic gas barrier layer interposed therebetween, the gas barrier property is 1.0 g / m ² / d or less even after a durability test such as winding a film. A certain durable display substrate film could be obtained.

Example 2
A silicon oxide thin film was further formed on the organic resin layer formed under the above conditions from the polymer composition containing the oxetane resin used in the display substrate film of 118 which had good durability in Example 1. The organic resin layers formed from the composition containing the oxetane resin used in No. 118 were laminated alternately by the number of layers shown in Table 2, and the gas barrier properties immediately after the film formation and the durability test were performed. The gas barrier property was evaluated.

  In addition, with reference to WO 00/36665, a transparent laminated film 205 of a comparative example was produced, and the same evaluation was performed.

<Substrate film 205 of comparative example>
A gas barrier layer was formed on a diacetylcellulose-silica hybrid film with reference to the method described in WO00 / 36665.

Methyl methacrylate monomer was introduced from an introduction nozzle into a vacuum deposition apparatus maintained at 1.333 × 10 ⁻⁴ MPa, cryodeposited on a diacetylcellulose-silica hybrid film cooled to 0 ° C., and then irradiated with ultraviolet rays in a vacuum chamber. And polymerized to form a polymethyl methacrylate (PMMA) film having a thickness of 1 μm.

Next, a silicon oxide thin film having a thickness of 100 nm was formed on this film by reactive vapor deposition (vacuum process).
Raw material compound: Degree of vacuum in silicon monoxide deposition chamber: Oxygen 4.00 × 10 ⁻⁸ MPa
Degree of vacuum in winding chamber: oxygen 2.00 × 10 ⁻⁶ MPa
Electron beam power: 15 kW
By repeating such a process, a total of 11 laminated films were alternately formed of PMMA films and silicon oxide layers to obtain a transparent laminated film 205 of a comparative example.

  About this, the water-vapor-permeation rate and the cross cut test were done similarly to the above.

From Table 2, since the display substrate film of the present invention has good adhesion between the organic thin film and the inorganic thin film, the durability of the gas barrier film is good even when the inorganic layer and the organic layer are laminated, and five layers are laminated. Thus, the water vapor transmission rate could be increased to the measurement limit (0.05 g / m ² / d) or less of the measuring machine.

  On the other hand, the transparent laminated film 205 of the comparative example was an unfavorable display substrate film, although the water vapor permeability immediately after film formation was good due to lamination, but deteriorated greatly after the durability test.

Example 3
<< Creation of organic EL elements >>
Organic EL elements 301 to 305 were formed after forming a transparent conductive film on the substrate films 201 to 205 created in Example 2 by sputtering.

<Film formation of transparent conductive film>
FIG. 7 is a cross-sectional view showing the configuration of the manufactured organic EL display device. First, a mixture of indium oxide and tin oxide (Sn atomic ratio Sn / (In + Sn) as a sputtering target on the gas barrier film (oxetane resin film) of the substrate films 201 to 205 produced in Example 2 as the transparent substrate 61. = 0.08) was used, and an ITO (Indium Tin Oxide) film, which is a transparent conductive film, was formed by a DC magnetron sputtering method. That is, the inside of the vacuum apparatus of the sputtering apparatus is depressurized to 1 × 10 ⁻³ Pa or less, and a mixed gas of 1000: 2.8 in terms of volume ratio of argon gas and oxygen gas is 1 × 10 ⁻¹ Pa Then, an ITO film as a transparent conductive film was formed to a thickness of 250 nm by a DC magnetron method at a target applied voltage of 420 V and a substrate temperature of 60 ° C. After patterning the ITO film to form an anode 62, the transparent support substrate provided with the transparent conductive film is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. It was.

<Formation of organic EL element>
On the obtained transparent conductive film 62, an α-NPD layer (film thickness: 25 nm), CBP and Ir (ppy) ₃ are deposited as an organic EL layer 63 in FIG. 8 by a vacuum deposition method through a square perforated mask. A co-evaporated layer (film thickness 35 nm) with a speed ratio of 100: 6, a BC layer (film thickness 10 nm), an Alq ₃ layer (film thickness 40 nm), and a lithium fluoride layer (film thickness 0.5 nm) were sequentially stacked ( 7 (not shown in detail in FIG. 7), a cathode (cathode) 64 made of aluminum having a thickness of 100 nm was formed through a mask on which another pattern was formed.

<Sealing>
The gas barrier layer 68 in which the same substrate films 201 to 205 as the substrate 65 of FIG. 7 and the silicon oxide film 66 and the organic film 67 are laminated is placed inside the obtained laminate in a dry nitrogen stream. And the periphery was sealed with a photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) to obtain organic EL elements 301 to 305. Although not shown in FIG. 7, each of the transparent electrode and the aluminum cathode can be taken out as a terminal.

  The following evaluation was performed about the light emission part of these organic EL elements.

<Evaluation item 1>
Immediately after sealing, a 10 V DC voltage was applied to these organic EL elements 301 to 305, and the luminance at the time when 1 minute had elapsed from the application was evaluated.

  Thereafter, the organic EL elements 301 to 305 were stored in an environment room of 40 ° C. and 90% RH for 300 hours in a non-light emitting state. Thereafter, a DC voltage of 10 V was applied again, and the luminance was measured when 1 minute had passed since the application. The rate of decrease in brightness before and after entering the environment room was evaluated.

<Evaluation item 2>
Immediately after sealing, a 10 V DC voltage was applied to these organic EL elements 301 to 305, and the luminance at the time when 1 minute had elapsed from the application was evaluated.

  The bending test in which the organic EL elements 301 to 305 were bent at 45 ° and returned to the original was repeated 1000 times. Thereafter, a DC voltage of 10 V was applied again, and the luminance was measured when 1 minute had passed since the application.

For evaluation items 1 and 2, the luminance reduction rate was evaluated according to the following criteria.
Luminance reduction rate is less than 10% ◎
Decrease rate of brightness is less than 30% and 10% or more ○
Decrease rate of brightness is less than 50% 30% or more
Reduced brightness is 50% or more ×

  From these results, the organic EL element 305 of the comparative example was easily deteriorated with respect to bending, and was an undesirable organic EL element. On the other hand, it can be seen that the organic EL elements 301 to 304 of the present invention are preferable organic EL elements having good humidity resistance and durability against bending. Among them, the organic EL element 304 of the present invention was an organic EL element having excellent durability.

  In this embodiment, no material that adsorbs or reacts with moisture (for example, barium oxide) is enclosed in the device, but this does not prevent the materials from being enclosed in the device.

It is a side view showing the schematic structure of the thin film forming apparatus which concerns on this embodiment. It is a perspective view showing the supporting member 10 with which the thin film forming apparatus of FIG. 1 is equipped. It is a side view showing the thin film formation unit 20 with which the thin film formation apparatus of FIG. 1 is equipped. It is a perspective view showing rod electrode 21A, 21B which forms the thin film formation unit of FIG. It is a front view showing the positional relationship of the supporting member 10 and the thin film formation unit 20 in the thin film formation apparatus of FIG. It is a block diagram showing the main control part of the thin film forming apparatus of FIG. It is a side view showing the structure of an organic EL element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thin film formation apparatus 2 Base material 9 1st power supply 10 Support member 20 Thin film formation unit 21A, 21B Bar electrode 23 2nd power supply 27 Cleaning film 30 Cleaning film conveyance mechanism 50 Control apparatus 51 Drive source 52 Memory | storage part

Claims (7)

At least a transparent plastic film, an inorganic thin film, a substrate film for display composed of the active ray curable resin layer, the active ray curable resin layer, an oxetane compound represented by the following general formula (1) 5 0 mass% As mentioned above , an active ray is irradiated to the composition containing 10-50 mass% of epoxy group-containing compounds represented by the following general formula (2) and 0.1-10 mass% of a compound that generates an acid by irradiation with active rays. A substrate film for a display, which is a resin layer cured by this.

(R _{11 to} R ₁₆ represent a monovalent substituent, L ₁ represents an m-valent linking group, m represents an integer of 2 or more, and a plurality of R _{14 to} R ₁₆ when m is 3 or more. May be different.)

(R _{21 to} R ₂₄ represent a monovalent substituent, L ₂ represents an n-valent linking group, and n represents an integer of 2 or more. When n is 3 or more, a plurality of R ₂₃ and R _{24 are present.} May be different from each other, provided that the compound represented by the general formula (2) is not the following compound (1) or the following compound (6).

The substrate film for a display according to claim 1, wherein the compound that generates an acid upon irradiation with actinic radiation is a sulfonium salt compound represented by the following general formula (3).

(R _{31 to} R ₃₃ represent a monovalent substituent, and X ⁻ represents a counter ion.)   The display substrate film according to claim 1, wherein the inorganic thin film is formed by a plasma CVD method.   The display inorganic film according to any one of claims 1 to 3, wherein the inorganic thin film is formed by a plasma CVD method under atmospheric pressure or a pressure in the vicinity of atmospheric pressure.   The display inorganic film according to claim 1, wherein the inorganic thin film is a silicon oxide film.   6. The display substrate film according to any one of claims 1 to 5, wherein the transparent plastic film is mainly composed of a cellulose ester.   An organic electroluminescence element, which is sandwiched between the display substrate films according to claim 1.

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